Home

Nova 1.10 Getting Started

1. Figure 2 35 The log i signal added to the data grid The newly created log i signal can now be used as any other signal to plot the data either in 2D or 3D Switch to the 2D plot by clicking the button in the toolbar Set the plot settings for the X axis to WE 1 Potential applied and for the Y axis to log i as shown in Figure 2 36 The log i has been added to the list of signals available using the right click menu Quick start cyclic voltammetry CY staircase 3 E ivsE fn dG X Potential applied oe logi gt 9 3 5 Ae Z Time Potential applied Time 4 WE 1 Current Scan _ 48 Index g 5 WE 1 Potental logi 55 log i 6 6 5 1 0 5 0 0 5 1 Potential applied Y Figure 2 36 Changing the plot settings to create the Tafel plot 121 Page NOVA Getting started 2 2 5 Saving to the database In Nova it is possible to save the changes in the database at any time This allows you to keep all the modifications on a given data set as well as the results of data analysis tools or additions to the data To update a database entry click the located in the analysis toolbar see Figure 2 37 File View Profile Run Tools Help 0164 et aa Ena SE 33 co 2 Jo ce oe Save all open data in database Figure 2 37 Saving the modifications in the data base Saving the changes to the database in this case adds the log i signal
2. ccccccccssseecceeseeseeeeeseeneeesseeeeesees 194 4 4 14 Temperature overload ccccccccseseecceseeecceeeeeseauseeseeseeesseneeesees 194 Agel INOUS S a E E AAA AE E EA 194 4 5 Autolab PGSTAT101 and M101 informatiOn cccceceeeccceeeeeeeeeeeeees 195 4 5 1 Front panel and cell cable connection PGSTAT101 cceeeee 195 4 5 2 Front panel and cell cable connection M101 cccecccseeeeeeeeeees 196 FF OV SE E E E penton 198 4 5 4 Connections for analog signals ccccceccceeeeeeeeeeeeeeeeeeeeeeeeseaeeeees 198 4 5 5 High stability High speed and Ultra high speed cceeeeeeee ees 200 4 5 6 RE input impedance and stability cccccsseesssseeeseeseeeseeeeeeeees 202 4 5 7 Galvanostat potentiostat and iR compensation bandwidth 202 4 5 8 Galvanostatic operation and current range linearity c 203 4 5 9 Maximum reference electrode Voltage cceeecccceeeestseeeeeeeeeeaeeeees 204 UI WO AGU 2 E a a Sarees sete og E E A E E N 204 aer EEE OC e E EE E E EE E 205 4 5 12 Environmental conditions ccccccccsseeecceeeeeseeseeeceeseeeseeseeesees 205 ano IN ONS E E E T E A E E 205 4 6 Autolab PGSTAT204 InformatiOn ccccccccceececeeeeeeeeeeeeeeeeeeeesaaeeseeeanes 206 4 6 1 Front panel and cell cable connections cceccceeecceeeeeeeaeeeeeneeees 206 AO PONT UID e E 208 4 6
3. EE Diagnostics Flease select an instrument AUTS83071 USB 0547 Cancel Figure 1 31 A selection menu is displayed if more than one instrument is detected The test can only be performed on a single instrument at a time Select the instrument that needs to be tested and click the _ button to proceed When the diagnostics application is started with a Multi Autolab connected the application will search for the available M101 modules installed in the Multi Autolab and will list the available modules as shown in Figure 1 32 36 Page NOVA Getting started E Diagnostics Please select an instrument MACS000 1 MACS000 2 MACS000 3 MACS000 4 MACS000 5 MACS000 6 Cancel Figure 1 32 A selection menu identifying the M101 modules by position is displayed when a Multi Autolab is detected by the diagnostics application The test can only be performed on one channel at a time Select the M101 module that needs to be tested and click the OK button to proceed Instruments with serial number beginning with AUT9 or with p2AUT7 connected through an external USB interface are identified by the serial number of the interface USB7XXXX see Figure 1 31 Instruments with an internal USB interface or instruments with serial number beginning with AUT7 connected through an external USB interface are identified by their own serial number When the appli
4. Hardware setup u3AUT70530 0 EZ File Tools Main Module Additional Module s _ PGSTAT302N L_JFRA32M PGSTAT302F V FRA2 _ PGSTAT302 JADCIOM _ PGSTAT30 JADC 50 L PGSTAT30 AUT9 JADC 50r4 PGSTAT128N SCAN Z50 _ PGSTAT12 _ SCANGEN DLAN L PGSTATIO0N a BA PGSTAT100 Amen ai PGSTAT100 AUT Seo iii _ PGSTAT101 _ Fl20 Filter _ M101 be eE iv UAutolab Ill v iel a iia _ pAutolab II _ Bo0 eer PGSTAT204 Booster OA _ PGSTAT20 JEQCM PGSTAT10 aa 000 px _ ECN _ External V External cable pAutolab _ IME303 JIME663 MUX Power Supply Frequency 50 Hz v Import FRA Calibration N BY OK Auto Cancel C Program Data Metrohm Autolab 11 0 HardwareSetup p3AUT 0530 xmI Figure 1 26 Import the FRA2 calibration file The serial number of the instrument can be found on label s attached to the cell cables or on the back panel of the instrument NOVA Getting started You will be prompted to define the type of instrument for which the fra2cal ini file is intended see Figure 1 27 C1 C calibration factors Please select the module tor which the calibration file is applicable C PGSTAT302N PGSTATI2 O PGSTAT302F PGSTAT30 O PGSTATI28N O PGSTAT20 pAutolab Ill O PGSTATIO O PGSTATIOON O PGSTAT100 O PGSTAT302 Figure 1 27 Selecting the instrument type for the fra2cal ini file Click the OK button to confirm the selection o
5. cccceccceeeseeeeeeeeeeeeeeeesaeeeeeeeeaeeees 108 22 4 USING WIS Gala GIO s sosctassemsnacvtsnaccanuderntacssodsbandsvsaaneiooicantedosaianaoaieas 114 D2 SAVING to the datapase aaicreaccteacetereemreestatnenneerncatuce a 122 3 The Autolab procedures group s enussnrnosrrnrsnrrrrnrrronnrirrnrerrnrersnrersnrerrnnn 123 3 1 Cyclic voltammetry POteNtiOSstatiC ce ceeceeceeeeeeeeeeeeeeaeeeeeeseeeeeeeeeaes 126 3 2 Cyclic voltammetry GalVanOstatiC ccccccceeeeeeeeeseeeeeeeeeaeeeeeeeaeeeeeeeeaes 128 3 3 Cyclic voltammetry Current integration cece eeeeeeneeeeeeeeeeeeeeeeaes 130 3 4 Cyclic voltammetry linear SCAN ccccccecceccsseeseeceeesseeeceesseeesseesseeessees 131 3 5 Cyclic voltammetry linear scan Nigh SPeed eceeeceeeeeeeeeeeeeeeeeeeeeeees 131 3 6 Linear sweep voltammetry potentiOstatic ccccceeeeeeeseeeeeeeeeeeeeeeeeaes 132 3 7 Linear sweep voltammetry galvanostatic ccccceeeceeeeeeeeeeeeeeeeeeeeeeaes 134 3 8 Linear polariza liO Msasa a E E EO a S E E AE 136 3 9 Hydrodynamic linear SW CC isola st carssrcro oc yeniaceeaeisewe aes deisuseleemonaseeateusedosmeoer 138 3 10 Differential pulse voltammetry cc sccecccseessseeeesceeesseeenesseeesseees 141 3 11 Square wave voltammetry aepusieceeceddecayatoassesetocesanatoasegransceserdipaveeiciscese 141 3 12 Sampled DC polarography cccccsccccsesseeceesee
6. HSTAB High speed and Ultra high speed The bandwidth can be defined using the Autolab control command see Figure 4 34 ava Autolab control Oo J PGSTAT101 lt Basic Uka cel or Integrator oo Mode Potentiostatic v Summary Current range 1 mA e Bandwidth High stability ka iR compensation High stability Q High speed N Ultra high speed wJ Advanced Cancel Figure 4 34 The Autolab control window can be used to set the bandwidth of the PGSTAT101 The purpose of these different modes of operation is to provide a maximum bandwidth maintaining stability in the PSTAT or GSTAT control loop The normal mode of operation is High stability This gives the Control Amplifier a bandwidth of 12 5 kHz The HSTAB indicator in the Autolab display is lit when the High stability mode is active see Figure 4 35 Power up default setting 200 NOVA Getting started Autolab display Ed a Autolab manual control AUT40008 Figure 4 35 A HSTAB indicator is provided on the Autolab display This setting is the most appropriate for measurements at low frequencies or low scan rates The noise in the and E signals will be minimized Measurements at high frequency or at high scan rates require a faster mode of operation When operating in High speed mode the control amplifier will have its bandwidth extended with one decade up to 125 kHz Some cells can show ringing or oscillation using
7. In a four electrode setup each of the cell cable connectors is used independently In a three electrode set up the working electrode and sense lead are both connected to the working electrode In a two electrode set up the counter and reference electrode lead are both connected to the same electrode see Figure 4 39 RE CE WE S RE CE WE S RE S CE WE Figure 4 39 Overview of the possible cell connections with the Autolab PGSTAT204 from top to bottom two electrode three electrode and four electrode setup 207 NOVA Getting started 4 6 2 Power up The settings of the PGSTAT204 on power up are pre defined The following settings are used e Cell off e Mode Potentiostatic e Bandwidth High stability e iR Compensation off e Current range 1 pA 4 6 3 Connections for analog signals With the optional I O cable four additional connections are provided to the PGSTAT204 analog circuits see Figure 4 40 All the signals are with respect to Autolab ground and indirectly to protective earth Avoid creating ground loops as this will often degrade the performance of the PGSTAT Figure 4 40 The optional I O cable for the PGSTAT204 The following signals are available Eour This output corresponds to the differential potential of RE versus S The output voltage will vary between 10 V The output impedance is 1 kQ so a correction should be made if a load lt 2 MQ is connected The maximu
8. JECN 4 External External cable pAutolab IME303 IMEB6E3 MUS Power Supply Frequency 50 Hz FRAZ offset DAC range BW ka C Program Data Metrohm Autolab 11 0 HarcdwareSetup AUT84530 xml 1 61E 11 C TE 5 43E 1 3 C2 OK Auto Cancel Figure 1 115 Change the value of C2 to the value reported in the Message box 8 Click OK to save the changes and wait for the Autolab to be reinitialized using the updated Hardware setup 97 Page NOVA Getting started 98 Page NOVA Getting started Nova Getting started The aim of the NOVA Getting started is to give new users a feel of the main features of the software as well as to introduce them to its mechanics It is also intended to test the installation of the software The example illustrated in this section will be presented without a specific clarification for each instruction or command This chapter is meant to be used as a walkthrough for first time users All of the aspects of the software are discussed in more detail in the User Manual The document can be accessed in Nova by pressing the F1 key or through the Help menu 2 A typical Nova measurement A typical Nova measurement starts with a procedure This procedure must be selected modified if necessary and executed Nova will run through the instructions of the procedure and carry them out sequentially While this happens the coll
9. Message Command AUT40008 O The specified value 8 mA is too high for the selected currentrange 1mA Set curent The specified value 8 mA is too high for the selected current range 1 mA The current range must be 10 mA or higher OK Cancel Figure 4 36 The procedure validation step always checks the applied current values for the allowed linearity 203 Page NOVA Getting started In potentiostatic mode this check is not performed It is possible to measure a current value in a fixed current range even if the current value exceeds the linearity limit of the active current range This triggers a current overload warning When this happens during a measurement a message will be shown in the user log suggesting a modification of the current range see Figure 4 37 User log message Time Date Command i Autolab USB connected AUT40008 10 20 35 AM 1 15 2013 amp Overload occurred in 1 pA current range use a higher current range 10 2318 AM 1 15 2013 CV staircase Figure 4 37 When a current overload is detected a suggestion is shown in the user log 4 5 9 Maximum reference electrode voltage The differential electrometer input contains an input protection circuitry that becomes active after crossing the 10 V limit This is implemented to avoid electrometer damage The red status LED indicator on the front panel not light up for this type of voltage overload The measured voltage will be cutoff at an absolu
10. Specific information on Multi Autolab can be found in the Multi Autolab tutorial available from the Help menu The cell cable is labelled as follows e Working or indicator electrode WE red e Sense electrode S red e Reference electrode RE blue e Auxiliary or counter electrode CE black An additional ground connection for shielding purposes e g a Faraday cage is also provided with the cell cable In a four electrode setup each of the cell cable connectors is used independently In a three electrode set up the working electrode and sense lead are both connected to the working electrode In a two electrode set up the counter and reference electrode lead are both connected to the same electrode see Figure 4 30 4 5 3 Power up The settings of the PGSTAT101 on power up are pre defined The following settings are used e Cell off e Mode Potentiostatic e Bandwidth High stability e iR Compensation off e Current range 1 pA 4 5 4 Connections for analog signals With the optional I O cable four additional connections are provided to the PGSTAT101 analog circuits see Figure 4 33 All the signals are with respect to Autolab ground and indirectly to protective earth Avoid creating ground loops as this will often degrade the performance of the PGSTAT 198 NOVA Getting started Figure 4 33 The optional I O cable for the PGSTAT101 top and M101 bottom The following signals are availabl
11. Chrono potentiometry fast Hardware Tags None Profile Tags Basic Application Tags Interfacial electrochemistry The Chrono potentiometry fast procedure uses the Chrono methods command instead of the Record signals command The Chrono methods command can be used for fast electrochemical measurements The interval time can be lower than 1 ms Because this command works with higher sampling rates compared to the Record signals command the data cannot be plotted real time The procedure has the following parameters e Preconditioning current 0 A e Duration 5 s e Potential step 1 0A e Potential step 2 3 A e Potential step 3 3 A e Potential step 4 0 A The response of the cell is measured with an interval time of 100 us At the end of the measurement switch to the analysis view to see the measured data points Figure 3 22 shows an overview of the Chrono potentiometry fast procedure Commands Parameters Links Remarks Chrono potentiometry fast al End status Autolab m Signal sampler Time WE 1 Potential m Options No Options rn Instrument AUT40008 Instrument description Autolab control mm Set current 0 000E 00 Set cell On izes Wait time s 5 E Chrono methods galvanostatic 1 04 a Number of repeats 1 Total duration s 04 Estimated number of points 400 Signal sampler Time WE 1 Potential al Corrected time lt _ array gt 5 Level lt aray Time lt _amay gt s WE 1 Potential lt _amay gt V Inde
12. PER MWS a If a temperature overload takes place repeatedly for no obvious reason Metrohm Autolab recommends having the instrument checked by their service department 4 4 15 Noise When measuring low level currents some precautions should be taken in order to minimize noise The personal computer must be placed as far away as possible from the electrochemical cell and the cell cables The cell cables should not cross other electrical cables Other equipment with power supplies can also cause noise For instance the interface for mercury electrodes IME should also be placed with some care If possible place the computer between the PGSTAT302F and other equipments Avoid using unshielded extension cables to the electrodes The use of a Faraday cage is also advised gt 4 This must never occur 194 NOVA Getting started A Warning Instrument performance can be substantially degraded when the PGSTAT302F is operated in floating mode The instrument specifications provided by Metrohm Autolab can only be achieved when the PGSTAT302F is used in non floating mode If the cell system has a ground connector it can be connected to the analog ground connector at the front of the PGSTAT302F If a Faraday cage is used it should be connected to this ground connector Some experiments concerning optimization of the signal to noise ratio can readily indicate whether or not a configuration is satisfactory More information on noise is p
13. VVECT Current A deel 2E 20 At BO zii 100 120 Time 5 Figure 3 26 The measured data obtained with the standard dummy cell a with the Chrono charge discharge procedure 3 21 I Interrupt Hardware Tags None Profile Tags Intermediate Application Tags None This procedure can be used to perform a current interrupt measurement in order to determine the value of the uncompensated resistance This procedure cannot be used in combination with the PGSTAT10 and the UAutolab type II Ill More information about the use of this procedure is provided in the iR compensation tutorial available from the Help menu in NOVA 3 22 i Interrupt high speed Hardware Tags ADC10M or ADC750 module Profile Tags Intermediate Application Tags None This procedure is similar to the i Interrupt procedure This procedure uses the optional fast sampling ADC module ADC750 or ADC10M 154 NOVA Getting started This procedure can be used to perform a current interrupt measurement in order to determine the value of the uncompensated resistance This procedure cannot be used in combination with the PGSTAT10 and the uAutolab type II Ill This procedure requires the fast sampling ADC module More information about the use of this procedure is provided in the iR compensation tutorial available from the Help menu in NOVA 3 23 Positive feedback Hardware Tags None Profile Tags Intermediate Application Tags None The
14. 0 C to 40 C ambient temperature without derating 80 relative humidity 10 C to 60 C ambient temperature NOVA Getting started Dimensions W x H x D uAutolab type III uAutolab type III FRA2 27 x 27 x9 cm PGSTAT101 9x21x15 cm PGSTAT204 15 x 26 x 20 cm PGSTAT302N PGSTAT302F PGSTAT128N 52 x 42 x 17 cm PGSTAT100N Booster20 52 x 49 x 20 cm BSTR10A 36 x 47 x 15 cm IME303 IME663 20 x 24 x 8 cm Multi Autolab 52 x 42 x 17 cm Weight kg uAutolab type III 3 6 UAutolab type III FRA2 4 2 PGSTAT101 2 1 PGSTAT204 4 1 PGSTAT302N PGSTAT302F 18 PGSTAT128N 16 PGSTAT100N 21 Booster20A 25 BSTR10A 9 IME303 IME663 2 Multi Autolab 12 8 Safety designed to EN61010 1 EMC compliance EN61326 1 EN61326 1 Note full EMC compliance with all cell types can only be achieved with cell placed in a faraday cage Warm up time 30 minutes Remote interface USB Pollution degree 2 Installation category II 5 3 Warranty The warranty on Autolab products is limited to defects that are traceable to material construction or manufacturing error which occur within 36 months from the day of delivery 12 months for instruments delivered before January 1 2012 In this case the defects will be rectified by Metrohm Autolab free of charge Transport costs are to be paid by the customer 3 year instrument warranty Glass breakage in the case of electrodes cells or other parts is not covered by the warranty Consumables e
15. Hardware Tags IME663 or IME303 interface Profile Tags Basic Application Tags Electroanalysis This procedure intended to be used in combination with a Mercury Drop Electrode MDE stand Metrohm 663 VA Princeton Applied Research 303 303A or other compatible MDE provides an example of a differential pulse voltammetry measurement in NOVA This procedure requires the optional IME663 or IME303 module to be selected in the Hardware setup More information about the use of these Autolab accessories is provided in the Voltammetric analysis tutorial available from the Help menu in NOVA 3 11 Square wave voltammetry Hardware Tags IME663 or IME303 interface Profile Tags Basic Application Tags Electroanalysis This procedure intended to be used in combination with a MDE stand Metrohm 663 VA Princeton Applied Research 303 303A or other compatible MDE provides an example of a square wave voltammetry measurement in NOVA This procedure requires the optional IME663 or IME303 module to be selected in the Hardware setup More information about the use of these Autolab accessories is provided in the Voltammetric analysis tutorial available from the Help menu in NOVA 3 12 Sampled DC polarography Hardware Tags IMIE663 or IME303 interface Profile Tags Basic Application Tags Electroanalysis This procedure intended to be used in combination with a MDE stand Metrohm 663 VA Princeton Applied Research 303 303A or other compatible MDE
16. Showing the data in 3D The 3D plot displays time current and potential on the same plot use the WE 1 Current as the Signal for the Z axis This plot can be turned and rotated by NOVA Getting started clicking the graph and moving the mouse around while holding the left button see Figure 2 24 Figure 2 24 Spinning the 3D graph around While holding the left mouse button the mouse pointer changes to the pointer highlighted in Figure 2 24 Feel free to try to change the plot either in the 2D or the 3D view We recommend that you take the time to get familiar with the Nova basics before exploring the rest of the manual for more information 113 Page NOVA Getting started 2 2 4 Using the data grid A very important feature of Nova is the Data grid and its functionality During a measurement several signals are sampled and are stored in the database when the measurement is completed These signals are then available in the analysis view for plotting purposes as shown in the previous section For the standard Cyclic voltammetry potentiostatic measurement these signals are e Potential applied e WE 1 Current e WE 1 Potential e Scan e Time e Index The data grid provides an overview of all the signals To access the data grid click the corresponding button in the toolbar see Figure 2 25 File View Profile Run Tools Help Be an PTS coe LE ow EI Show data grid Figure 2
17. b TastSiCANGEN H Wy procedures Figure 1 42 The Module test procedures The first two procedures PGSTAT C1 calibration and PGSTAT C2 calibration are special procedures used to determine the C1 and C2 factors required for the operation of the FRA32M or the FRA2 module in combination with the Autolab These procedures are intended to be used under the experimental conditions described in the module installation documentation Please refer to Section 1 6 18 for more information The other 23 procedures can be used at any time to test the different hardware modules installed in the instrument This section provides a short description of the test procedures included in the Hardware test database Make sure that the hardware setup is defined correctly see Section 1 3 45 NOVA Getting started 1 6 1 Test of the Autolab PGSTAT 1 6 1 1 Test of the Autolab PGSTAT128N 302N 302F normal mode 100N 204 and pAutolab III This simple test is designed to verify the basic functionality of the potentiostat It can be used to test all the Autolab PGSTAT instruments except the Autolab PGSTAT101 the Autolab M101 potentiostat galvanostat module and the PGSTAT302F in normal mode Load the TestCV procedure from the Standards database connect dummy cell a and press the start button see Figure 1 43 AUTOLAB CE RE WE S e Cc WE S d Tp OkQ DUMMY CELL2 MIF Figure 1 43 The
18. instrument is characterized by a specific linearity limit and this specification determines the maximum current that can be applied in galvanostatic mode The linearity limitation also applies on measurements performed in potentiostatic mode in a fixed current range Table 4 9 provides an overview of the current range linearity for the PGSTAT204 Current range Linearity 100 mA 4 10 mA 7 1 mA 7 10 1 mA 7 100 1 pA 7 100 10 nA 7 Table 4 9 Linearity limit for the PGSTAT204 For example in the 1 mA current range the maximum current that can be applied galvanostatically using the PGSTAT204 is 7 mA The maximum current that can be measured in the 1 mA current range is 10 mA although currents exceeding 7 mA will be measured outside of the linearity limit of this current range In galvanostatic operation the applied current values are checked during the procedure validation step When the applied current exceeds the linearity limit for the specified current range an error message will be shown in the procedure validation screen see Figure 4 43 212 NOVA Getting started Validation results The following problems were encountered during validation Message Command AUTS50001 O The specified value 8 mA is too high for the selected currentrange 1 mA Set curent The specified value 8 mA Is too high for the selected current range 1 mA The current range must be 10 mA or higher OK Cancel Figu
19. is not supported in NOVA 216 Page NOVA Getting started RE CE WE RE CE WE Figure 4 47 Overview of the possible cell connections with the pAutolab two electrode top and three electrode setup bottom 4 7 2 Power up The settings of the uAutolab on power up are pre defined The following settings are used Cell off Mode Potentiostatic Bandwidth High stability e Current range 1 pA 4 7 3 Connections for analog signals On the rear panel there are four BNC connectors All signals are with respect to uAutolab ground and indirectly to protective earth Avoid creating ground loops as this will often degrade the performance of the instrument From top to bottom the following signals are available iour This signal corresponds to the output of the current to voltage converter circuit of the pAutolab A 1 V signal corresponds to 1 x the selected current range The output level varies between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load impedance is 200 Q Eour This output corresponds to the differential potential of RE versus S The output voltage will vary between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load impedance is 200 Q The Eout value corresponds to WE 1 Potential 217 NOVA Getting started Vour This output cor
20. the residual current from the reference data red curve and the absolute limits green lines 1 6 1 2 Test of the Autolab PGSTAT101 and M101 This simple test is designed to verify the basic functionality of the Autolab PGSTAT101 and the Autolab M101 potentiostat galvanostat module Load the TestCV PGSTAT101 procedure from the Standards database This test uses the internal dummy cell of the instrument Connect the CE and the RE electrode leads and the WE and S from the cell cable as shown in Figure 1 48 and press the start button 1 gt For testing the PGSTAT302F in floating mode please refer to section 1 6 1 3 For testing all the other Autolab instruments please refer to section 1 6 1 1 49 Page NOVA Getting started Figure 1 48 The connections required for the PGSTAT101 test A warning message indicating that the internal dummy cell is used will be shown during validation see Figure 1 49 This warning is provided as a reminder and the OK button can be clicked to proceed with the measurement Validation results 2 The following problems were encountered during validation Message Command AUT40008 amp The internal dummy cell is on Autolab control amp The internal dummy cell is on Set potential amp The internal dummy cell is on set cell Time remaining 15 seconds Cancel Figure 1 49 A warning message is shown during validation A message will be displayed when the measurement s
21. 11 Specifications 227 Spreadsheet 114 Square wave voltammetry 124 Staircase cyclic voltammetry 101 126 Staircase cyclic voltammetry galvanostatic 128 Standard factory procedures 101 Stop button 106 Summation point 157 158 169 184 Summation point mapping 159 Supported Windows versions 11 Surface Plasmon Resonance 30 Tafel plot 117 124 136 Temperature range 223 Three electrode configuration 166 181 196 198 207 217 Time constant 159 Timing 161 Trigger 160 Trigonometric functions 117 Troubleshooting 35 TTL 160 Two electrode configuration 166 181 196 198 207 217 Ultra fast measurements 151 Ultra high speed 170 200 209 Uncompensated resistance 154 155 173 188 202 211 Unshielded cables 224 Unsupported hardware 29 USB interface 160 User manual 99 VA stand 124 Voltage follower 157 158 159 169 184 199 200 208 209 218 Voltmeter 173 187 202 211 Warranty 227 WE 166 173 181 187 196 198 202 207 211 216 Working electrode 166 173 181 187 196 198 202 207 211 216 03 2013 Kanaalweg 29 G 3526 KM Utrecht The Netherlands L Metrohm
22. 174 189 203 212 221 Load data 110 Load procedure 102 LSV 124 132 134 M101 module 197 Magnetic stirrer 224 Maintenance 225 Mathematical operation 115 Maximum power 178 192 204 214 223 Maximum voltage 222 Measured values 114 Measurement frame 108 Measurement synchronization 160 Measurement timing 161 Measurement view 99 105 Mercury drop electrode 124 Minimum requirements 11 Module test ADC10M 55 Module test ADC750 55 Module test BA 57 Module test BIPOT 60 61 Module test Booster10A 62 Module test Booster20A 62 Module test ECD 64 Module test ECN 65 Module test EQCM 86 Module test Fl20 Filter 67 Module test Fl20 Integrator 68 Module test Fl20 Integrator PGSTAT101 70 Module test FRA2 73 Module test FRA32M 73 Module test MUX 78 Module test PGSTAT 46 Module test PGSTAT101 49 Module test PGSTAT302F 52 Module test pX 80 Module test pX1000 80 Module test SCAN ADC 83 Module test SCAN250 82 Module test SCANGEN 82 Module testCV PGSTAT101 procedure 49 Module testCV procedure 46 Monitor cable 169 184 199 208 Mott Schottky 124 156 Multi Autolab 197 Multi potentiostat 197 My procedures 104 No data display real time 145 Noise 159 172 187 201 210 224 Noise reduction 159 Nova installation 11 Nova Quick Start 99 OCP determination 136 Oscillation 177 191 Overload 192 204 214 Parameters 126 132 134 Pau
23. Contact your Autolab distributor for more information about this modification The shielding of the RE and S cable on the PGSTAT and of the RE cable on the uAutolab is driven or guarded Use isolated cable feedthroughs for these cables in order to extend the driven shield inside the glove box The shield of these cables must not be connected to the ground of the glove box 4 9 Cleaning and inspection It is recommended to clean the Autolab cabinet and the accessories on a regular basis This can be done with a damp cloth optionally using a mild detergent Never use an excessive amount of water it may never enter into the instrument As a precaution disconnect Autolab from the mains when cleaning it Also perform an inspection of the instrument and all of the connecting cables If you find any cables with damaged insulation or other irregularities stop using the instrument until it has been repaired Damaged equipment or damaged cables may be hazardous 225 NOVA Getting started 226 Page NOVA Getting started Warranty and conformity This chapter provides information about warranty safety specifications and conformity 5 Warranty and conformity 5 1 Safety practices Please read the safety practices carefully before starting to use the AUTOLAB instrument This section describes the AUTOLAB instrument The section deals with appearance and use of the instrument and contains necessary information regarding o
24. Summary Current range 1 pA a Bandwidth High stability v IR compensation Ultra high speed wJ Advanced Figure 4 41 The Autolab control window can be used to set the bandwidth of the PGSTAT204 The purpose of these different modes of operation is to provide a maximum bandwidth maintaining stability in the PSTAT or GSTAT control loop The normal mode of operation is High stability This gives the Control Amplifier a bandwidth of 12 5 kHz The HSTAB indicator in the Autolab display is lit when the High Stability mode Is active see Figure 4 42 62 Power up default setting 209 NOVA Getting started Autolab display Ed a Autolab manual control AUT50001 Figure 4 42 A HSTAB indicator is provided on the Autolab display This setting is the most appropriate for measurements at low frequencies or low scan rates The noise in the and E signals will be minimized Measurements at high frequency or at high scan rates require a faster mode of operation When operating in High speed mode the control amplifier will have its bandwidth extended with one decade up to 125 kHz Some cells can show ringing or oscillation using this setting particularly highly capacitive cells in PSTAT mode Increasing the bandwidth also increases the noise levels for the i and E signals It is possible to switch from High stability to High speed by clicking the HSTAB label in the Autolab display In High speed mode this label
25. Temperature overload ccccccccsesceccesseeccesseeseesseeseeeeesseneeesees 178 a S N 9 ce eet ee A E EA eee 179 4 4 Autolab PGSTAT302F information cccccecceeccceeeeeeeeeeeseeeeeeeesaeeeeeeaaes 180 4 4 1 Front panel and cell cable CONNECTION esnnnesnnnssnnneennnennnnnnnnnnns 181 Aa PONV SL U0 aisa a a O O 182 4 4 3 Connections for analog signals ccecccceeeeeeeeeeeeeeeeeeeeeeeeeesaaeeeees 183 4 4 3 1 Connections for analog signals front panel ce eceeeeeeeeeees 183 4 4 3 2 Connections for analog signals monitor cable c cceeeees 184 4 4 4 High stability and High speed 1 2 0 0 cece ceeeeeeeeeeeeeeeeeeeeeeeeeeeeseaeeeeees 185 4 4 5 RE input impedance and stability cc cceccceeteeeeeeeeeeeeaeeeeeeans 187 4 4 6 Galvanostatic FRA measurements ccceeccceeeeeeeeeeeeeeeeeeeeeeaaeeeeeans 188 4 4 7 Galvanostat potentiostat and iR compensation bandwidth 188 4 4 8 Galvanostatic operation and current range linearity 0c6 189 4 4 9 Oscillation detection cccccccseceeeceeeensseseecsseeerssnseeesceeseesseseerens 190 4 4 10 Maximum reference electrode VOItaGe ceecccceeeesteeeeeeeeeeeaeeeees 192 gA ld FAES aeerattsietocamseceaeesaneue uation sete E sce enonedaeon 192 4 4 12 Grounded cells and grounded working electrodes 00 193 4 4 13 Environmental conditions
26. The measured data should be displayed in the data analysis frame like in Figure 2 19 110 Page NOVA Getting started a Quick start cyclic voltammetry CY staircase 0 00 ivs E X 0 0008 0 000E 0 0004 0 0002 0 0002 WELT Current 4 _ 0 0004 0 0006 0 0008 010 1 0 5 0 is Potential applied Vv Figure 2 19 Displaying the measured data in the analysis view The final part of this quick start guide will illustrate some of the features of the analysis view More information can be found in Chapter 4 of the User Manual During this experiment the Autolab instrument recorded values for time current and potential These experimental values are known in Nova as Signals These Signals can be used in any combination to control the way the data is plotted Click the symbol next to the blue i vs E line in the data explorer frame to reveal the signals currently used for this plot see Figure 2 20 Quick start cyclic voltammetry CY staircase ml ivs E a fy Potential applied dg VWE 1 Current Figure 2 20 Expanding the Signal set line in the data explorer frame Figure 2 20 shows that for the current plot the Potential applied signal is used for the X axis and the WE 1 Current signal is used for the Y axis The WE 1 Current signal used for the Z axis is not relevant for a 2D plot It might be useful to show the applied potential on the Y axis as a function of time
27. right calibration factor unchanged Click OK to save the measured value in the hardware setup file of the instrument 10 The determination of the integrator calibration factor does not replace the full test of the module Please refer to Sections 1 6 9 1 6 11 or to the Module test document available from the Help menu for more information on the complete test of the Fl20 Integrator 42 Page NOVA Getting started 1 5 1 Autolab Firmware Update For some instruments a firmware update may be required If this is the case of the connected instrument a message will be displayed during the Diagnostics test see Figure 1 40 During Diagnostics an update message will be displayed if the outdated firmware is detected Clicking the Yes button when prompted will silently update the firmware see Figure 1 40 Firmware Update Firmware upcdate s available for the Autolab instrument Would you like to upgrade to the latest version recommended yes Do not switch off the instrument Figure 1 40 An upgrade message is displayed when the outdated firmware is detected The firmware update is permanent The Firmware Update window will close automatically at the end of the update and the diagnostics test will continue Important Do not switch off the instrument or disconnect the instrument during the firmware update since this will damage the instrument 43 NOVA Getting started 1 6 Mo
28. vs E Corrosion rate fit Set cell lt S Timing guide Linear polarization Time WE 1 Potential WE 1 Current 1 Options AUT40008 0 000 0 000 0 100 On 5 5 0 100 0 100 0 0070000 0 100 0 100 0 00100 00 0010000 200 1 000000 Time WE 1 Potential WE 1 Current 1 Options lt _array gt V lt _amay gt 5 lt _amay gt A lt _amay gt V lt _amay gt Figure 4 3 The Autolab Linear polarization procedure with the timing guide highlighted The procedure contains a series of measurement commands which are interrupted at two commands e OCP determination command e Corrosion rate fit These interruptions are indicated in the timing guide shown in Figure 4 3 by the matching breaks located right next to the two commands The OCP determination command is a host command because it requires the derivative of the measured OCP to be calculated during the measurement The Corrosion rate fit command is like all analysis commands a host command 162 Page NOVA Getting started The timing guide indicates that when this procedure is performed a small interruption can be expected when the OCP determination command and when the Corrosion rate fit command are executed If needed the Corrosion rate fit command can be moved to the end of the procedure to prevent the interruption between the LSV staircase command and the Set ce command 4 2 Consequence of th
29. vs E Scanning bipot mode Reference data Figure 1 61 The data obtained with the TestBA procedure The first two groups contain the measured data points for the WE 2 Current in Bipot mode and in Scanning Bipot mode The other two groups contain data points for the WE 2 Current from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 62 2E 6 _ 1 5E 6 1E 6 WE 2 Current 4 JE 1 0 5 J 0 5 Potential applied W Figure 1 62 The expected result of the TestBA procedure red curve WE 2 Current Bipot mode brown curve WE 2 Current Scanning Bipot mode The test is successful if the measured data can be compared to the reference data 59 NOVA Getting started 1 6 4 Test of BIPOT The TestBIPOT procedure can be used to test the correct functionality of the BIPOT module Load the TestBIPOT procedure connect WE 1 to dummy cell a and WE 2 to dummy cell b as shown in Figure 1 60 and press the start button A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the WE 2 is controlled with respect to the potential of the reference electrode with a potential offset of 1 V At the end of the measurement switch to
30. 0 00003 216 10 When the absolute value of the current is lower than 0 05 current range the resolution equals C R 20 C R 0 000003 216 100 The effect of the limited resolution can be seen for instance when low currents are measured at a high current range In such cases a lower current range has to be applied if possible When automatic current ranging is used the most suitable current range Is selected automatically Care must be taken when using this option in the following situations e High frequency square wave voltammetry is applied e High scan rates in cyclic and linear sweep voltammetry are applied Switching of the current range takes about 0 5 ms to 2 ms Therefore an erroneous point can be measured when the current range is switched Most of the time this error can be corrected by smoothing the plot afterwards 4 3 Autolab PGSTAT information This section provides specific information for the Autolab PGSTAT series of instruments The following instruments fall under this category PGSTAT12 128N 30 302 302N 100 and 100N 4 3 1 Front panel and cell cable connection There are four connectors on the front panel of the PGSTAT The cable that connects to the WE and CE should be plugged into the WE CE socket while the cable with the differential amplifier leading to the RE S and optionally WE2 electrodes connects to the RE S socket A ground cable embedded in the WE CE cable connection
31. 1 000E 03 1 000E 03 0 000E start current A 0 000E 00 Upper vertex current A 1 000E 03 Lower vertex current A 1 000E 03 stop current A 0 000E 00 Number of stop crossings 2 step current A 2 440E 06 Scan rate Afs 1 000E 04 Estimated number of points 1650 Interval time s 0 024400 Signal sampler Time WE 1 Current WE 1 Potential Options No Options m Current applied lt _amay gt A Time lt _amay gt s Scan lt aray WE 1 Potential lt _ array gt V WE 1 Current lt _amay gt A Index lt aray E vsi a Sa Figure 3 5 The Cyclic voltammetry galvanostatic procedure Current applied Time Scan WE 1 Potential WE 1 Current Index The signals sampled during this procedure are Links The automatic current ranging option is not available in galvanostatic mode Please refer to Chapter 4 of this manual for more information on the Galvanostatic control restrictions This procedure uses the Autolab control command to set the instrument to galvanostatic mode and in the 1 mA current range before the measurement starts 129 Page NOVA Getting started Figure 3 6 shows a measurement on the dummy cell c with the Autolab Cyclic voltammetry galvanostatic procedure WWE 1 Potential W 0 001 0 000 J 0 0005 0 001 Current applied A Figure 3 6 The measured data obtained with the standard dummy cell c with the Cyclic voltammetry galvanostatic procedure 3 3
32. 100 1000 Frequency Hz Figure 1 107 Typical Bode plot obtained during the C1 calibration 7 The data is automatically fitted and the results of the fitting are reported in a Message box at the end of the measurement see Figure 1 108 93 NOVA Getting started C1 calibration factor C1 1 61E 11F Figure 1 108 The experimentally determined value of C1 is reported in a Message box at the end of the measurement 8 Open the Hardware setup of Nova Tools Hardware setup Select the instrument type in the Main Module frame in the hardware setup window and adjust the value of C1 to the value reported in the Message box see Figure 1 109 Hardware setup AUT84530 0 File Tools Kain Module Additional Modulels PGSTAT302N FRAIZM ee 1 61E 11 ADC750 Cz 0 00E 00 JADC 5Or4 SCAN250 SCANGEN amp L_ BA BIPFOT ARRAY JEcD Fl20 Filter Fl20 Integrator Booster204 Booster tA JEQCM Jpx1000 px JECN 4 External External cable pAutolab IME303 IMEB6E3 MUS Power Supply Frequency Cl 50 Hz Y Import FRAG Calibration FRA offsetDAC range S w OK Auto Cancel C Program Data Metrohm Autolab 11 0 HarcdwareSetup AUT84530 xml Figure 1 109 Change the value of C1 to the value reported in the Message box 9 Click OK to save the changes and wait for the Autolab to be r
33. 13 000 n 10 000 n A 2 0000 n 0 0000 5 0000 n Residual current 10 000 n 15 000 n 20 000 n 1 0 5 J 0 5 1 Fotential applied V4 Figure 1 56 An overlay of the residual current obtained from the measured data blue curve the residual current from the reference data red curve and the absolute limits green lines 1 6 2 Test of the ADC750 or the ADC10M Two procedures TestADC750 and TestADC10M can be used to test the correct functionality of the fast sampling ADC module ADC750 or ADC10M respectively Load the TestADC750 or the TestADC10M procedure depending on the module to test from the Standards database connect dummy cell c and press the start button A message will be displayed when the measurement starts see Figure 1 57 TestADC10M This procedure ts designed to test the basic functionality of the ADC1OM Analyze the data in the Analysis view Connect dummy c and press OK to continue OK Figure 1 57 A message is displayed at the beginning of the measurement 55 NOVA Getting started No data points can be shown real time during measurements with the fast sampling ADC module The test uses the chrono amperometry high speed method and performs a total of four potential steps At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 58 TestADC
34. 166 181 216 Current follower 157 158 159 169 184 199 200 209 218 Current interrupt 124 Current interrupt method 154 Current range 163 Current range switching 164 Customize plots 111 Cutoff 177 192 204 214 222 Cyclic voltammetry current integration 124 Cyclic voltammetry galvanostatic 124 128 Cyclic voltammetry linear scan high Speed 124 Cyclic voltammetry potentiostatic 124 126 D A converter 163 DAC164 158 163 Data analysis 108 Data display 110 Data explorer 110 Data grid 114 122 Data transfer 161 Database 109 Database storage 104 Default procedures 100 Diagnostics 35 Differential amplifier 173 181 187 202 211 Differential pulse voltammetry 124 Digital base 163 Digital control 160 Digital Input Output 160 Digital signal generator 158 Digital to analog converter 163 DIO 160 DME 141 Driver Manager 19 Dropping Mercury Electrode 141 DSG 158 Dummy cell 101 Earth 178 181 205 214 Ecorr 136 Editing procedures 102 EIS 124 155 Electrochemical impedance spectroscopy 124 155 Electrochemical methods 8 Electrochemical signals 114 Electrochemical spreadsheet 115 Eou 169 184 199 208 Export data to ASCII 115 Export data to Excel 115 External input 158 169 184 External signals 30 Faraday cage 179 181 195 205 215 219 224 225 Fast sampling 124 Fast sampling ADC 159 Feedback 173 188 Feedback
35. 1G sac cnsassaneetaieaqmienceateraewseenemasodeansnae 43 1 6 Module test in NOVA 0 0 ccc eccececcecacceceececeececeeeeeecaeeeeaeceeaeaeeeeaeeeeaeeeeneeenes 44 1 6 1 Test of the Autolab PGSTAT ccccceccecceceececceceeceececeeeessecaeeeeeeeaneess 46 1 6 1 1 Test of the Autolab PGSTAT128N 302N 302F normal mode TOON 204 and pAutolab Ih cccccccccceecceeeeeeeseeeeeee cesses eeeaeeeesaeeeesneeees 46 1 6 1 2 Test of the Autolab PGSTAT101 and M101 oaaae 49 1 6 1 3 Test of the Autolab PGSTAT302F in floating mode 0 52 1 6 2 Test of the ADC750 or the ADC10M 00 0 cece cee eececceccececcecceceeeeeeeeaneees 55 1 6 3 TG Of BA erraren n NAO EENE DEAE EEE 57 1 6 4 Test Of BIPOT cece cecceccececceccecueceecececeececueceececueceececueseececueneeaeeaes 60 1 6 5 Test of ARRAY scdistesascuicaeecadetenecapicecsnthaicqenstiecesnabolesecadcnestatobenccatoeas 61 1 6 6 Test of the Booster10A and the Booster20A ec ceeeecceeceeeeeeeeeees 62 1 6 7 Test of ECD oo cccecccccecceccececceececueceececueceececueceececueneececueaeesecueneeaeeaes 64 1 6 8 Test of ECN oo ccc ccccccecceccececceccececceececeeeuesecaeeeeecaeeeeseeeeeesecaeeeeseeaeeass 65 1 6 9 Test of ol 4 0 as em ene eee ee 67 T6510 Testor F1Z OI VCE ALON sene 68 1 6 11 Test of FI20 Integrator PGSTAT 101 ou ccceeeceeeeeeeeteeeeeeeeeeaae eens 70 1 6 12 Test Of FRA 2 0 0 cccccccceccecceceeceececueceecec
36. 9 41772E 6 5 86896 i E WEC Pot 0 012207 0 0125549 1 16486E 5 5 69137 1 6 0 0146484 0 0150482 1 38672E 5 5 71579 1 7 0 0170898 0 0174652 1 6098E 5 5 7402 1 8 0 0195313 0 0198853 1 83289E 5 5 76462 1 lg 0 0219727 0 0223602 2 05414E 5 5 78903 10 Figure 2 29 Opening the Calculate signal tool The Calculate signal window will be displayed see Figure 2 30 Calculate signal 0 Parameters Functions Full CV staircase Figure 2 30 The Calculate signal window 116 Page NOVA Getting started The calculate signal window works as an electrochemical calculator It has several fields which are used to create a new signal Name this is the name of the new signal a name is mandatory Single value this checkbox can be used to force the calculate signal to return a single value Unit the unit of the new signal Expression this is the mathematical expression used to calculate the new signal Parameters a list of identified parameters used in the expression Functions a list of common mathematical functions that can be used to calculate the new signal Trigonometric functions a list of common trigonometric functions Signals this is a list of the available signals in the data set As an example we are going to calculate the logarithm of the current in order to create a Tafel plot In the calculate signal window type log i as a name to identify the new signal Then scroll down t
37. At the same time the iR compensation bandwidth limits indicate up to which frequency current measurements can be made in potentiostatic mode either with or without iR compensation 220 NOVA Getting started 4 7 7 Galvanostatic operation and current range linearity For galvanostatic experiments automatic current ranging is not possible The measurements are performed in a fixed current range Each current range on the instrument is characterized by a specific linearity limit and this specification determines the maximum current that can be applied in galvanostatic mode The linearity limitation also applies on measurements performed in potentiostatic mode in a fixed current range Table 4 11 provides an overview of the current range linearity for the pAutolab II and Ill Current range Linearity 10 mA 5 1mA 4 10 1 mA 4 100 1 pA 4 100 10 nA 4 Table 4 11 Linearity limit for the pAutolab II and III For example in the 1 mA current range the maximum current that can be applied galvanostatically using the pAutolab Il or Ill is 4 mA The maximum current that can be measured in the 1 mA current range is 10 mA although currents exceeding 4 mA will be measured outside of the linearity limit of this current range In galvanostatic operation the applied current values are checked during the procedure validation step When the applied current exceeds the linearity limit for the specified current range an error me
38. CD delivered with a new instrument the FRA2 calibration file is copied onto the computer automatically if applicable This also applies when upgrading an existing NOVA version installed on the computer If the FRA2 calibration data is missing a warning message will be displayed in the user log after starting NOVA see Figure 1 25 User log message Time APRA calibration data for P34UT 70530 not found lla WD Autolab USB connected U34UT 70530 Figure 1 25 A warning is displayed in the user log when the FRA calibration file is missing 31 Page NOVA Getting started In this case the FRA2 calibration file must be imported manually This file fra2cal ini can be found in two different locations e f the GPES FRA software is already installed on the computer the fra2cal ini file can be found in the C autolab folder e Alternatively the fra2cal ini file can be found on the GPES FRA 4 9 installation CD matching the serial number of the instrument in the D install disk1 folder A Warning If the fra2cal ini file cannot be located contact your local distributor serial number of the instrument required To import the FRA2 calibration file select the Hardware setup from the Tools menu In the Hardware setup window click the button and locate the file fra2cal ini see Figure 1 26 Browse to the folder containing the calibration file and click the Open button to load the file
39. Cyclic voltammetry current integration Hardware Tags FI20 or on board integrator Profile Tags Basic Application Tags Education Energy Interfacial electrochemistry This procedure requires the optional FI20 module or the on board integrator for the yAutolabll Ill and the PGSTAT101 The procedure can be used to perform a cyclic voltammogram using the current integration method This measurement technique uses a staircase potential profile but rather than sampling the current at the end of each step to minimize capacitive currents the total current is accumulated in the analog integrator At the end of each step the accumulated charge is reconverted in current This integrated current includes both the Faradaic and the capacitive currents passed during the potential step If the interval time is large typically gt 20 ms the current response measured during a current integration cyclic voltammetry experiment can be compared in first approximation to the current measured with a true linear scan potential profile More information about the use of the analog integrator is provided in the Filter and Integrator tutorial available from the Help menu in NOVA 130 NOVA Getting started 3 4 Cyclic voltammetry linear scan Hardware Tags SCAN250 or SCANGEN module Profile Tags Basic Application Tags Education Energy Interfacial electrochemistry This procedure requires the optional SCAN250 or SCANGEN module Both modules are linear s
40. FRA potential scan Hardware Tags FRA32M or FRA2 module Profile Tags Intermediate Application Tags Semiconductors The FRA potential scan procedure requires the optional FRA32M or FRA2 impedance analyzer module This procedure can be used to perform a potentiostatic frequency scan at different DC potentials to determine the electrochemical impedance of the cell for each DC potential value More information about the use of the FRA32M or FRA2 module is provided in the Impedance tutorial available from the Help menu in NOVA 156 NOVA Getting started The Autolab Potentiostat Galvanostat Nova can be used to control Autolab potentiostats galvanostats with USB interface While the technical specifications of each of the instruments might be different the operating principle remains the same This chapter provides an overview of the Autolab as well as information concerning the digital nature of the instrument Information regarding noise issues is also provided 4 Autolab Hardware information 4 1 Overview of the Autolab instrument The Autolab instrument combined with the software is a computer controlled electrochemical measurement system It consists of a data acquisition system and a potentiostat galvanostat see Figure 4 1 USB interface Bi time PC DAC164 FRA2 Embedded real SCAN250 En es p a on off re ce decoder Other modules e lt a ep PSTAT GSTAT s We ADC10M FI20 il
41. It can be used at any time to select the driver to use to control the Autolab Driver Manager Select the driver used to control your Autolab instrument Nova only recommended setup Select this driver when you only use Nova 1 7 or higher on your PC Advantages Faster USB data exchange Connect a maximum of 16 Autolab instruments Supports 64 bit Windows Ready for future applications GPES compatible Select this driver when you want to use Nova 1 7 or higher together with Nova 1 6 or lower and or GPES on this PC Restrictions Slower USB data exchange Connect a maximum of 8 Autolab instruments Doesn t support 64 bit Windows No further developments are done with this driver Nova only instruments 1 GPES compatible instruments 0 Total number of instruments 1 Figure 1 11 The Autolab Driver Manager can be used to switch drivers Clicking the GPES compatible button will trigger the installation of the GPES compatible driver for the connected instrument S Warning The GPES compatible driver is not available on a 64 Bit version of Windows A warning will be displayed indicating that the driver cannot be verified see Figure 1 12 20 Page NOVA Getting started x Windows Security Windows can t verify the publisher of this driver software gt Don t install this driver software You should check your manufacturer s website for updated driver softw
42. O ADC164 FRA2 lt lt Figure 4 1 Overview of the Autolab potentiostat galvanostat The Autolab has the following key digital components e USB interface e Embedded real time PC e Decoder and DIO controller 3 Except the PSTAT10 and the pAutolab type l 157 Page NOVA Getting started The digital components are interfaced through the Autolab modules to the analog potentiostat galvanostat circuit The latter consists of the following components The summation point The control amplifier CA The voltage follower VF The current follower CF The summation point 2 is an adder circuit that feeds the input of the control amplifier It is connected to the output of the several key modules of the Autolab DAC164 FRA DSG SCAN2507 Ein Figure 4 2 shows a schematic overview of the different connections to the summation point of the Autolab potentiostat galvanostat The labels shown in Figure 4 2 correspond to the dividing factors used for each signal on the summation point For example the signal generated by the FRA module FRA DSG has a maximum amplitude of 3 5 V RMS which is divided by 10 at the input of the summation point resulting in an effective maximum amplitude of 0 35 V RMS DAC1 64 1 Offset DAC Fa 1 10 ae NOP FRA DSG 3 5 V RMS DAC164 2 r Scanning DAC p mu y 10V DAC1 64 4 AC voltammetry DAC 110 SCAN250 Se 5 Wi 10V Figure 4 2 Mapping of t
43. One additional DAC164 channel is available on the PGSTAT N series DAC164 4 This channel is hardwired to the summation point and it is divided by 10 This input is used for measurements involving a small amplitude modulation like AC voltammetry and AC voltammetry second harmonic Presently these methods and the use of this channel is not yet implemented in NOVA The connection to the summation point can be removed if necessary The DlO part offers the possibility of controlling electrode systems motorburettes or other equipment that can be controlled by TTL signals This module can also be used to send or receive trigger signals to or from TTL devices If an automatic mercury electrode such as PAR303 or Metrohm 663 VA Stand is used gas purging and drop time can be activated The interface for mercury electrodes called IME303 or IME663 provides all necessary signals and connections for these electrodes as well as for a drop knocker of a dropping mercury electrode only for IME303 The embedded PC can be in two different locations depending on the type of interface e Inside of the Autolab USB Interface box e Inside of the Autolab USB instrument 4 Contact your Autolab distributor for more information 160 NOVA Getting started 4 1 1 Event timing in the Autolab The embedded PC is equipped with a 1 MHz timer that is used by the software to control the timing of events during measurements The shortest interval time on th
44. Positive feedback procedure provides the means to determine the value of the uncompensated resistance using the positive feedback method This procedure cannot be used in combination with the PGSTAT10 and the uAutolab type II Ill More information about the use of this procedure is provided in the iR compensation tutorial available from the Help menu in NOVA 3 24 FRA impedance potentiostatic Hardware Tags FRA32M or FRA2 module Profile Tags Basic Application Tags Corrosion Energy Interfacial electrochemistry Semiconductors The FRA impedance potentiostatic procedure requires the optional FRA32M or FRA2 impedance analyzer module This procedure can be used to perform a potentiostatic frequency scan to determine the electrochemical impedance of the cell More information about the use of the FRA32M or FRA2 module is provided in the Impedance tutorial available from the Help menu in NOVA 155 NOVA Getting started 3 25 FRA impedance galvanostatic Hardware Tags FRA32M or FRA2 module Profile Tags Basic Application Tags Energy Semiconductors The FRA impedance galvanostatic procedure requires the optional FRA32M or FRA2 impedance analyzer module This procedure can be used to perform a galvanostatic frequency scan to determine the electrochemical impedance of the cell More information about the use of the FRA32M or FRA2 module is provided in the Impedance tutorial available from the Help menu in NOVA 3 26
45. Potential step 1 0A e Potential step 2 0 5 mA e Potential step 3 0 5 mA Figure 3 17 shows an overview of the Chrono potentiometry At gt 1 ms procedure Commands Chrono potentiometry At gt 1 ms oe ae ea se Remarks End status Autolab Signal sampler Options Instrument Instrument description Autolab control Set current Set cell Wait time s Record signals gt 1 ms galvanostatic Set current Record signals gt 1 ms galvanostatic Set current Record signals 1 ms galvanostatic Set cell lt gt Parameters Chrono potentiometry At gt 1 ms Time WE 1 Current WE 1 Potential No Options AUT40008 0 000E 00 On 5 5 0 01 5 000E 04 5 0 01 5 000E 4 5 0 01 Off Figure 3 17 The Chrono potentiometry At gt 1 ms procedure The signals sampled during this procedure are e Corrected time e WE 1 Potential e WE 1 Current e Time e Index 144 Page NOVA Getting started Figure 3 18 shows a measurement on the dummy cell c with the Autolab Chrono potentiometry At gt 1 ms procedure 0 6 0 4 02 1 Potential v WI 0 2 0 4 E 0 6 6 5 10 12 14 16 18 20 Time sS Figure 3 18 The measured data obtained with the standard dummy cell c with the Chrono potentiometry At gt 1 ms procedure 3 15 Chrono amperometry fast Hardware Tags None Profile Tags Basic Application Tags Interfacial electrochemistry The Chrono am
46. The following hardware is not supported in NOVA pAutolab type and PSTAT10 instruments with ADC124 DAC124 or DAC168 and FRA modules 1 generation FRA Contact you Autolab distributor for more information Please make sure that your copy of Windows has been updated to the latest version 11 NOVA Getting started If the NET framework 4 0 installation is required the following window will be displayed see Figure 1 1 This package is provided by Microsoft and you can read the license agreement by clicking the View EULA for printing button 16 Nova Setup For the following components Microsoft NET Framework 4 x66 and xb4 Flease read the following license agreement Press the page down key to see the rest of the agreement MICROSOFT SOFTWARE SUPPLEMENTAL LICENSE TERMS MICROSOFT NET FRAMEWORK 4 FOR MICROSOFT WINDOWS OPERATING SYSTEM lew EULA for printing Do you accept the terms of the pending License Agreement lfyou choose Don t Accept install will clase To install you must accept this agreement Figure 1 1 The NET framework installation wizard The installation of the NET framework can take some time A progress bar is displayed during the installation see Figure 1 2 A Mova Setup Installing Microsoft MET Framework 4 x86 and xb Cancel Figure 1 2 Installing the NET framework 4 0 12 NOVA Getting started When the NET framework is installed the installation of
47. WE CE cable connection can be used to plug to the earth bulkhead for shielding purposes Finally a monitor cable can be connected to a dedicated connector see Figure 4 16 On Off button Digital display Cell On Off switch en UUQOOVUGOUL ADC164 DAC164 Monitor cable input RE S socket WE CE Ground socket Figure 4 16 Overview of the Autolab PGSTAT302F The cell cables are labelled as follows e Working or indicator electrode WE red e Sense electrode S red e Reference electrode RE blue e Auxiliary or counter electrode CE black In a four electrode setup each of the cell cable connectors is used independently In a three electrode set up the working electrode and sense lead are both connected to the working electrode In a two electrode set up the counter and reference electrode lead are both connected to the same electrode see Figure 4 17 181 NOVA Getting started RE CE WE S RE CE WE S RE S CE WE Figure 4 17 Overview of the possible cell connections with the Autolab PGSTAT302F from top to bottom two electrode three electrode and four electrode setup 4 4 2 Power up The settings of the PGSTAT on power up are pre defined The following settings are used e Cell off e Mode Potentiostatic e Bandwidth High stability e iR Compensation off e Current range 10 mA A Warning In floating mode the iov warning may be lit when the cell is off This warning can be
48. a more stable control loop compared to High speed or Ultra high speed and a significantly lower bandwidth To make use of the full potentiostat bandwidth Ultra high speed mode the impedance between CE and RE has to be lower than 35 kQ This value is derived by testing In galvanostat mode this large impedance between CE and RE will usually not lead to stability problems because of the current feedback regulation 4 5 7 Galvanostat potentiostat and iR compensation bandwidth For galvanostatic measurements on low current ranges the bandwidth limiting factor becomes the current to voltage circuit rather than the control amplifier For stability reasons it is not recommended to use the High speed mode for current ranges lt 10 pA The Ultra high speed mode is also not recommended for current ranges lt 1 MA As the current measurement circuit plays an important role in the iR compensation technique its use is also subject to bandwidth limitations A general indication of the maximum available bandwidth for GSTAT and for iR compensation can be found in Table 4 6 Mode GSTAT IR C PSTAT 10mA 1mA gt 1 MHz gt 1 MHz 100 pA 1 MHz 1 MHz 10 pA 10 kHz 75 kHz 1 pA 10 kHz 20 kHz 100 nA 400 Hz 4 kHz 10 nA 400 Hz 400 Hz Table 4 6 Bandwidth overview for the PGSTAT101 At the same time the iR compensation bandwidth limits indicate up to which frequency current measurements can be made in potentiostatic mode either with or wi
49. and CE are intrinsically safe They may drive the PGSTAT output stage into current limit but will not overload the amplifier On the other hand cells that have an absolute voltage higher than 10 V between WE and CE may only deliver a maximum current Imax given by _ Puax MAX Vmax 4 3 12 Grounded cells The measurement circuitry of the Autolab is internally connected to protective earth P E This can be an obstacle when measurement is desired of a cell that is itself in contact with P E In such a case undefined currents will flow through the loop that is formed when the electrode connections from the PGSTAT are linked to the cell and measurements will not be possible Please note that not only a short circuit or a resistance can make a connection to earth but also a capacitance is capable of providing a conductive path for AC signals The earth connection between the cell and P E should always be broken If there is no possibility of doing this please contact Metrohm Autolab for a custom solution if available 4 3 13 Environmental conditions The PGSTAT may be used at temperatures of O to 40 degrees Celsius The instrument is calibrated at 25 degrees Celsius and will show minimum errors at that temperature The ventilation holes on the bottom plate and on the rear panel may never be obstructed nor should the instrument be placed in direct sunlight or near other sources of heat 4 3 14 Temperature overload As
50. and the reference data because of the tolerance of the resistance included in the special booster test cell 5 63 NOVA Getting started WEFT Current 4 a WEE T Current tA a 1 0 5 0 0 5 1 0 5 0 0 5 Potential applied Vv Potential applied EW Figure 1 68 The expected result of the TestBooster10A procedure left and the TestBooster20A procedure right The test is successful if the measured data can be compared to the reference data 1 6 7 Test of ECD The TestECD procedure can be used to test the correct functionality of the ECD module Load the TestECD procedure connect WE 1 to dummy cell a and press the start button A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the working electrode is scanning between 1 V and 1 V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 69 a TestECD B esECD Measured data B ivs E Measured data d S TestECD Reference dataj a i vs E Reference data Figure 1 69 The data obtained with the TestECD procedure The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained dur
51. at frequencies gt 2 5 kHz will be detected Upon oscillation the OSC indicator on the PGSTAT front panel will be activated The Vou warning will also be shown in the Autolab display An oscillation protection feature can be enabled or disabled in the software using the Autolab contro command see Figure 4 14 hava Autolab control PGSTAT302N lt Basic DIO Advanced Lal External input Off Oscillation protection On Am Reference potential 0 V Offset potential 0 V DAC164 lt 1 0 V Figure 4 14 The Autolab control window can be used to switch the oscillation protection on or off NOVA Getting started If the oscillation protection is enabled the occurrence of oscillation will also immediately turn off the manual cell switch of the Autolab When this happens both the OSC indicator and the manual cell switch start blinking The Autolab display will show the message Cell manually off see Figure 4 15 Autolab display x a Autolab manual control AUT85189 HsTAB i CELL oN Dee ee status cell manually off current range Figure 4 15 The cell manually off is displayed when the oscillation protection circuit is triggered The cell may be switched on again by pressing the manual cell switch button If oscillation resumes the cell switch will be turned off as soon as the button Is released Holding the button pressed in provides an opportunity to observe the system during oscillation Som
52. cell _ off Summary Mode Potentiostatic i Current range 1 mA Bandwidth High stability i High stability ps IR compensation wJ Advanced Figure 4 21 The Autolab control window can be used to set the bandwidth of the PGSTAT The purpose of these different modes of operation is to provide a maximum bandwidth maintaining stability in the PSTAT or GSTAT control loop The normal mode of operation is High stability gt This gives the Control Amplifier a bandwidth of 12 5 kHz The HSTAB indicator on the front panel of the PGSTAT and in the Autolab display is lit when the High stability mode is active see Figure 4 22 Autolab display x a Autolab manual control AUT85189 Figure 4 22 A HSTAB indicator is provided on the Autolab display 2 Power up default setting 186 Page NOVA Getting started This setting is the most appropriate for measurements at low frequencies or low scan rates The noise in the i and E signals will be minimized Measurements at high frequency or at high scan rates require a faster mode of operation When operating in High speed mode the control amplifier will have its bandwidth extended with one decade up to 125 kHz Some cells can show ringing or oscillation using this setting particularly highly capacitive cells in PSTAT mode Increasing the bandwidth also increases the noise levels for the i and E signals The High speed mode is automatically selected during impedance me
53. chapter describes the steps required for the installation of NOVA and the Autolab instrument 1 1 Requirements Nova requires Windows XP Windows Vista Windows 7 or Windows 8 as operating systems in order to run properly Minimum RAM requirement is 1 GB and the recommended amount Is 2 GB Only the instruments with a USB interface internal or USB interface box are supported 1 2 Software installation A Warning Leave the Autolab switched off during the installation of the software Insert the Nova CD ROM in the optical drive of your computer Open the Windows explorer and browse the contents of the disk Locate the Setup exe program and double click to install Nova on your hard drive Installation of the NET 4 0 framework is required in order to install Nova If the NET framework is already installed on your computer the install wizard will directly install Nova skip to Section 1 2 2 Otherwise you will be prompted to accept the installation of the NET 4 0 framework see NET framework installation 1 2 1 NET 4 0 framework installation The Microsoft NET Framework is a component of the Microsoft Windows operating system It provides a large body of pre coded solutions to common program requirements and manages the execution of programs written specifically for the framework The NET Framework is a key Microsoft offering and is intended to be used by most new applications created for the Windows platform 1
54. ee Of i Chrono amperometry At gt 1 ms ze cS _ Chrono potentiometry At gt 1 ms Chrono amperometry fast j Chrono potentiometry fast Procedure editor frame Chrono amperometry high speed j Chrono potentiometry high speed ms Chrono charge discharge interrupt _ Hnterrupt high speed Positive feedback _ FRA impedance potentiostatic FRA impedance galvanostatic i FRA potential scan aa ae Procedure amp Command browser User log message Time Date Command 4 Autolab USB connected AUT40008 9 56 19 AM 1 15 2013 gt Start User log Start Stop button Ready Intermediate _ Figure 2 1 Overview of the Setup view of Nova More information regarding the Setup view of Nova can be found in Chapter 2 of the User Manual The procedure browser frame displays a number of available procedures in the Autolab group Figure 2 2 shows a more detailed view of the Setup view 100 Page NOVA Getting started File View Profile Run Tools Help DAGA SS ma th I SE eo ee EA Eh Me cu gt Commands Procedures Commands Parameters Links New procedure Autolab Sa chee 2i miomani z arrests cp cat es aie ug tients ace ceca Se gga pea encasement cone dees cae vane hae Cyclic voltammetry potentiostatic Bpan i End status Autolab Cyclic voltammetry galvanostatic j l l Signal sampler Time WE 1 Current on Cyclic voltammetry current
55. ignored 182 NOVA Getting started 4 4 3 Connections for analog signals The Autolab PGSTAT302F provides connections for analog signals through two different types of connectors e BNC connectors directly located on the front panel of the instrument e BNC connectors located on the monitor cable 4 4 3 1 Connections for analog signals front panel The ADC164 module and the DAC164 module are fitted with two analog inputs and two analog outputs respectively see Figure 4 18 Oi AUTOLAB IO 00900006006 ADC164 DAC164 Figure 4 18 Overview of the connections for analog signals provided on the front panel of the Autolab PGSTAT ADC164 and DAC164 ADC164 The ADC164 inputs labelled 41 and gt 2 on the front panel can be used to record any analog signal with a 10 V value range The input impedance of the two analog inputs is 50 Q DAC164 The DAC164 outputs labelled lt 1 and lt 2 on the front panel can be used to generate any analog signal with a 10 V value range The output impedance of these two inputs is 50 Q Corrections should be made with loads lt 100 kQ Because of dissipation the minimum load impedance should be 200 Q The DAC164 lt 1 and lt 2 outputs are identified as DAC channels 3 and 4 respectively in the Set DAC command These inputs are floating when the PGSTAT302F is operated in floating mode Connected equipment may not be connected to ground and the shield of the BNC cabl
56. is equipped with three different bandwidth settings High stability HSTAB High speed and Ultra high speed The bandwidth can be defined using the Autolab control command see Figure 4 9 170 NOVA Getting started f i D Revs Autolab control 0 J PGSTAT302N lt Basic ae cell loff Summary Mode Potentiostatic es Current range 1 mA i Bandwidth High stability a iR compensation High stability Q Ultra high speed wJ Advanced Figure 4 9 The Autolab control window can be used to set the bandwidth of the PGSTAT The purpose of these different modes of operation is to provide a maximum bandwidth maintaining stability in the PSTAT or GSTAT control loop The normal mode of operation is High stability This gives the Control Amplifier a bandwidth of 12 5 kHz The HSTAB indicator on the front panel of the PGSTAT and in the Autolab display is lit when the High stability mode is active see Figure 4 10 Autolab display x a Autolab manual control AUT85189 Figure 4 10 A HSTAB indicator is provided on the Autolab display Power up default setting NOVA Getting started This setting is the most appropriate for measurements at low frequencies or low scan rates The noise in the i and E signals will be minimized Measurements at high frequency or at high scan rates require a faster mode of operation When operating in High speed mode the control amplifier will have its bandwidt
57. mode is selected for frequencies below 10 kHz see Figure 4 49 Power up default setting 218 NOVA Getting started High stability High speed 10 kHz Figure 4 49 Bandwidth limits in the pAutolab The HSTAB indicator on the front panel of the uAutolab and in the Autolab display is lit when the High stability mode Is active see Figure 4 50 Autolab display ia A Autolab manual control u3AUT70530 Figure 4 50 A HSTAB indicator is provided on the Autolab display This setting is the most appropriate for measurements at low frequencies or low scan rates The noise in the and E signals will be minimized Measurements at high frequency or at high scan rates require a faster mode of operation When operating in High speed mode the control amplifier will have its bandwidth extended to 500 kHz Some cells can show ringing or oscillation using this setting particularly highly capacitive cells in PSTAT mode Increasing the bandwidth also increases the noise levels for the and E signals The High speed mode is automatically selected during impedance measurement at frequencies gt 10 kHz i Note It is possible to switch from High stability to High speed by clicking the HSTAB label in the Autolab display In High speed mode this label will be unlit both on the front panel of the pAutolab and on the Autolab display Clicking the HSTAT label again switches the bandwidth back to High stability 2
58. number of points 200 Interval time s 1 000000 Signal sampler Time WE 1 Potential WE 1 Current Options 1 Options m Potential applied lt _ array gt V Time lt _amay gt Ss WE 1 Current lt _amay gt A WE 1 Potential lt _ array gt V Index lt aray Log i vs E m Corrosion rate fit Set cell Off z gt Figure 3 11 The standard Linear polarization procedure During the OCP determination the following signals are sampled e Time e WE 1 Potential The signals sampled during the linear sweep voltammetry measurement are e Potential applied e Time e WE 1 Current e WE 1 Potential e Index At the end of the measurement a corrosion rate calculation is performed Figure 3 12 shows a measurement on the dummy cell c with the Autolab Linear polarization procedure 137 Page NOVA Getting started 1E Veo WE TD Current 4 1E 9 Je 10 0 1 U05 0 0 0 0 1 Potential applied W Figure 3 12 The measured data obtained with the standard dummy cell a with the Linear polarization procedure 3 9 Hydrodynamic linear sweep Hardware Tags Autolab RDE connected to DAC164 or Vou of Autolab Profile Tags Basic Application Tags Corrosion Education Electroanalysis Energy Interfacial electrochemistry The Hydrodynamic linear sweep voltammetry procedure performs a linear sweep voltammetry using the Autolab RDE with six different rotation rates The rotation rate of
59. on the X axis This can be easily done within the analysis view by right clicking the active setting for the X axis the WE 1 Potential applied in the data explorer frame and replacing it by the time The same can be done to change the signal plotted on the Y axis from the measured WE 1 Current to the WE 1 Potential see Figure 2 21 111 NOVA Getting started E Quick start cyclic voltammetry El CY staircase El CY staircase E Quick start cyclic voltammetry Ae iws E Ae iws E aaan Ag Potential aqnliad bei Ag Time Lede Y WE 1 Cl Potential applied ey WET Current T TEA Ti A ak Ti otential applied 7 g Z Time wea fy Z Time 7 see al cen a ime as Vaghl Current Potential applied sil WE 1 Current Sel Time Scan Index Index WE 1 Potental WE 1 Potental Figure 2 21 Changing the plot settings After changing these settings the plot should be similar to Figure 2 22 Potential applied W a 10 15 20 fis 30 cle At AS Time sS Figure 2 22 Plotting the applied potential as a function of time The familiar saw tooth profile of a cyclic voltammogram can be easily recognized Nova also provides a 3D plot engine To switch to a 3D plot click the corresponding button amp of the data analysis view toolbar see Figure 2 23 File View Profile Run Tools Help a S a eT eo ee Ee a co EE en Show 3D plot Figure 2 23
60. outcome or interpretations of data measured with AUTOLAB 231 Page NET 4 0 framework 11 uAutolab 216 2D plot 110 3D plot 112 663 VA Stand 160 A D converter 163 Active cells 178 192 204 214 223 ADC10M 124 151 159 ADC164 159 163 ADC750 124 151 159 Add plot 111 Amplifier 163 Amplitude FRA2 158 Analog input 200 209 218 Analog output 200 209 218 Analog scan 124 131 158 Analog signals 168 184 198 208 Analog to digital converter 163 Analysis view 100 108 Autogain 159 163 Autolab control 147 170 185 Autolab display 108 201 210 219 Autolab hardware 157 Autolab procedures 123 Autolab RDE 138 Automatic current ranging 127 129 133 135 164 Bandwidth 170 172 187 200 201 209 210 218 Basic principle of the Autolab PGSTAT 157 C1 and C2 calibration 89 91 95 Calculate signal 114 115 CE 166 181 216 Cell cables 181 Chrono amperometry 124 142 Chrono amperometry fast 124 145 149 Chrono amperometry ultra fast 124 Chrono charge discharge 124 152 Chrono coulometry fast 124 Chrono potentiometry 124 144 Chrono potentiometry fast 124 Chrono potentiometry ultra fast 124 Cleaning of the instrument 225 Commands 103 Compatible hardware 29 Index Compliance voltage 157 Conformity 227 Control amplifier 157 158 171 186 201 210 Corrected time 143 145 147 Corrosion potential 124 136 Counter electrode
61. set includes two groups of data points see Figure 1 72 TestECN I TestECN Measured cata ECN potential vs E Measured data S S TestECN Reference data ae ECN potential vs E Reference data Figure 1 72 The data obtained with the TestECN procedure The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 73 66 NOVA Getting started 0 8 0 6 0 4 0 2 0 2 ECN 1 Potential v _ 1 0 5 J Cis Potential applied W Figure 1 73 The expected result of the TestECN procedure The test is successful if the measured data can be compared to the reference data 1 6 9 Test of FI20 Filter The TestFl20 Filter procedure can be used to test the correct functionality of the filter circuit of the FI20 Filter module Load the TestFl20 Filter procedure connect dummy cell a and press the start button A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the working electrode is scanning between 1 V and 1 V During this measurement the filter is switched on and a filter time constant of 0 1 s Is used At the end of the measure
62. the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 63 TestBIPOT a TestBIPOT Measured data lt iE vs E Bipot mode Measured data el E TestBlPOT Reference dataj WE vs E Bipot mode Reference data Figure 1 63 The data obtained with the TestBIPOT procedure The first group contains the measured data points The other group contains data points for the WE 2 Current from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 64 60 NOVA Getting started 1 08E 6 1 06E 6 1 O4E 6 A 1 02E 6 1E 6 d oE WE 2 Curren OS BE 9 4E 1 0 5 J 0 5 Potential applied W Figure 1 64 The expected result of the TestBIPOT procedure The test is successful if the measured data can be compared to the reference data 1 6 5 Test of ARRAY The TestARRAY procedure can be used to test the correct functionality of the ARRAY module Load the TestARRAY procedure connect WE 1 to dummy cell a and WE 2 to dummy cell 6 as shown in Figure 1 60 and press the start button A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the WE 2 is contro
63. the user Nova uses a generic approach in which in principle any method or any task can be constructed using the available commands Figure 2 shows the Nova strategy schematically Library of individual objects Impedance DC potential F Ampli Automatic current ranging DC potential Figure 2 Schematic overview of the object based design of Nova The Nova approach allows the user to program an electrochemical method in the same anguage used by the instrument This new object based design philosophy has led to the current version of Nova As any task can be solved generically the software is slightly less intuitive than a method based application Depending on the complexity of the experiments the learning curve can be more or less long For this reason we advise you to carefully study this Getting started manual as well as the User manual Because of the large number of possibilities provided by this application it is not possible to include the information required to solve each individual use case Dana rqaUduUet NOVA Getting started A number of typical situations are explained using stand alone tutorials refer to the Help menu Tutorials These tutorials provide practical examples In case of missing information do not hesitate to contact Metrohm Autolab at the dedicated nova metrohm autolab com email address 10 NOVA Getting started Setting up Nova 1 Nova installation This
64. this current range In galvanostatic operation the applied current values are checked during the procedure validation step When the applied current exceeds the linearity limit for the specified current range an error message will be shown in the procedure validation screen see Figure 4 24 Validation results Sia The following problems were encountered during validation Message Command AUT85189 The specified value 5 mA is too high for the selected currentrange 1 mA Set curent The specified value 5 mA is too high for the selected current range 1 mA The current range must be 10 mA or higher OK Cancel Figure 4 24 The procedure validation step always checks the applied current values for the allowed linearity 189 Page NOVA Getting started In potentiostatic mode this check is not performed It is possible to measure a current value in a fixed current range even if the current value exceeds the linearity limit of the active current range This triggers a current overload warning When this happens during a measurement a message will be shown in the user log suggesting a modification of the current range see Figure 4 25 User log message Time Date Command 4 Autolab USB connected AUT85189 405 04 PM 1 15 2013 amp Overload occurred in 1 pA current range use ahighercurrentrange 4 10 43PM 1 15 2013 CV staircase Figure 4 25 When a current overload is detected a su
65. to the data set as well as the plot settings Tafel plot We advise to go through the User Manual chapter by chapter since it provides in depth information on procedures setup measurements and data analysis Alternatively you could skip to chapter 4 of the User Manual which explores the Data analysis features of Nova in detail to further practice on the dummy cell data obtained in the course of this quick start 122 NOVA Getting started Autolab procedures Nova comes with a series of factory standard procedures located in the Autolab group that are available to every user and are intended both as examples and as simple measurement procedures This chapter provides an overview of the available factory standard procedures 3 The Autolab procedures group The Autolab procedures group located in the procedure browser frame contains a series of factory standard procedures These procedures are intended to perform simple measurements and can be used for routine experiments or as templates for more elaborate procedures The current version of Nova provides 26 Factory standard procedures see Figure 3 1 Procedures Cyclic voltammetry potentiostatic z Cyclic voltammetry qalvanostatic z Lyclic voltammetry current integration bee Cyclic voltammetry linear scan e Cyclic voltammetry linear scan high speed fe Linear sweep voltammetry potentiastatic Linear sweep voltammetry galvanastatic Linear polarization Hydrod
66. uses the Automatic current ranging option and displays the measured data as WE 1 Current vs Potential applied in the measurement view Figure 3 8 shows a measurement on the dummy cell a with the Autolab Linear sweep voltammetry potentiostatic procedure 1E 6 9E 7 8E 7 zie E 6E 7 5 5E 7 UO 4E 7 m 3E 7 2E 7 1E 7 J 0 2 0 4 0 6 J E Fotential applied W Figure 3 8 The measured data obtained with the standard dummy cell a with the Linear sweep voltammetry potentiostatic procedure 133 NOVA Getting started 3 7 Linear sweep voltammetry galvanostatic Hardware Tags None Profile Tags Basic Application Tags Energy This procedure is a typical example of a staircase linear sweep voltammetry experiment in galvanostatic conditions The procedure has the following parameters e Preconditioning current 0 A e Duration 5 s e CV Staircase o Start current O A o Stop current 1 mA o Step current 2 44 pA o Scan rate 100 A s Figure 3 9 shows an overview of the Linear sweep voltammetry galvanostatic procedure Commands Parameters Links Linear sweep voltammetry galvanostatic Remarks Linear sweep voltammetry galvanostatic m End status Autolab I Signal sampler Time WE 1 Current WE 1 Potential ma Options No Options m Instrument AUT40008 Instrument description Autolab control a 4 Set current 0 000E 00 Set cell On m H Wait time s 5 B LSV staircase galvanostatic 0 000E 00 1 000E 03 1 00
67. voltammetry Remarks Cyclic voltammetry potentiostatic m End status Autolab Pre Signal sampler Time WE 1 Potential WE 1 Current Options 1 Options Instrument AUT40008 Instrument description H Autolab control a Set potential 0 000 H Set cell On zz Wait time s 5 Optimize current range 5 H CV staircase 0 000 1 000 1 000 0 000 2 0 1000000 5 Set cell Off lt gt Figure 2 6 Editing the procedure name After the title has been edited validate with the Enter key and save the procedure using the File menu Save procedure as New see Figure 2 7 File View Profile Run Jools Help _ New Procedure Ctl N Wi Save Procedure Ctrl s Save Procedure as New New Mult Autolab Configuration Open Mult Autolab Configuration Save Mult Autolab Configuration Page Setup Print Preview Print Procedure Ctrl P Import Procedure i oh be Export Procedure Exit Alt F4 Figure 2 7 Save the procedure The procedure will be added to the My procedures database see Figure 2 8 104 Page NOVA Getting started Commands Procedures Autolat z Cycle voltammetry potentiostatic lt Lyclic voltammetry qalvanostatic 2 Cyclic voltammetry current integration bee Cyclic voltammetry linear scan Cyclic voltammetry linear scan high speed Linear sweep voltammetry potentiostatic z Linear sweep voltammetry galvanostatic Linear polarization Hydrodynamic linear swe
68. z Set potential 0 000 Set cell On m Wait time s 5 Record signals 1 ms 5 0 01 Set potential 0 500 Record signals 1 ms 5 0 01 Set potential 0 500 Record signals 1 ms 5 0 01 Set cell Off zz a Figure 3 15 The Chrono amperometry At gt 1 ms procedure 142 Page NOVA Getting started The signals sampled during this procedure are e Corrected time e WE 1 Potential e WE 1 Current e Time e Index Figure 3 16 shows a measurement on the dummy cell a with the Autolab Chrono amperometry At gt 1 ms procedure 6E 7 AE 7 Ze ia WET Current 4 _ AE 7 SOES 6 5 10 2 14 16 16 20 2 Time 5 Figure 3 16 The measured data obtained with the standard dummy cell a with the Chrono amperometry At gt 1 ms procedure 143 NOVA Getting started 3 14 Chrono potentiometry At gt 1 ms Hardware Tags Profile Tags Application Tags The Chrono potentiometry At gt 1 ms procedure has three consecutive current steps After each current step the potential response is recorded during five seconds with an interval time of 10 ms The Record signals gt 1 ms command is used to measure the electrochemical signals This command samples the signals None Basic Corrosion Energy Interfacial electrochemistry with a smallest possible interval time of 1 30 ms The procedure has the following parameters e Preconditioning current 0 A e Duration 5s e
69. 02N _ FRA32M _ PGSTAT302F V FRA2 _ PGSTAT302 ADCI OM __ PGSTAT30 ADC 50 _ PGSTAT30 AUT9 JADC 50r4 lv PGSTAT128N SCAN250 _ PGSTAT12 SCANGEN _ PGSTATIOON _ C PGSTAT100 LJBA PGSTAT100 AUT9 er ARRAY _ PGSTAT101 M101 FI20 Filter wAutolab III F120 Integrator UAutolab Il Booster20A PGSTAT204 Booster10A _ PGSTAT20 JEQCM PGSTAT10 px1000 _ px JECN v External External cable WAutolab JIME303 JIME663 MUX Power Supply Frequency 50 Hz v Import FRA2 Calibration FRAZ offset DAC range 5V Vv OK Auto Cancel C Program Data Metrohm Autolab 11 0 H arcwareSetu 30 xml Figure 1 29 Adjusting the FRA offset DAC range 34 Page NOVA Getting started i Warning For the FRA2 module make sure that the FRA2 offset DAC range property is set properly in the hardware setup For FRA2 modules the correct value is 5 V For FRA2 V10 modules the correct value is 10 V Failure to set this value properly may result in faulty data at frequencies of 25 Hz and lower refer to front panel labels of the FRA2 module on the instrument 1 5 Diagnostics Nova includes a diagnostics tool that can be used to test the Autolab instrument This tool is provided as a standalone application and can be accessed from the start menu in the Autolab group Start menu All programs Autolab Tools The diagnostics tool can be used to troubleshoot an in
70. 0E 4 start current A 0 000E 00 stop current A 1 000E 03 step current A 2 440E 06 Scan rate Afs 1 000E 04 Estimated number of points 422 Interval time s 0 024400 Signal sampler Time WE 1 Current WE 1 Potential c Options No Options m Current applied lt _armay gt A Time lt _amay gt Ss WE 1 Potential lt _ array gt V WE 1 Current lt _amay gt A Index lt aray E vs H Set cell Off al aoe Figure 3 9 The Linear sweep voltammetry galvanostatic procedure 134 Page NOVA Getting started The signals sampled during this procedure are e Current applied e Time e WE 1 Potential e WE 1 Current e Index The automatic current ranging option is not available in galvanostatic mode Please refer to Chapter 4 of this manual for more information on the Galvanostatic control restrictions This procedure uses the Autolab control command to set the instrument to galvanostatic mode and in the 1 mA current range before the measurement starts Figure 3 10 shows a measurement on the dummy cell c with the Autolab Linear sweep voltammetry galvanostatic procedure a oo oO J E1 Potential v _ TT ha O 0 00010 00020 00030 00040 00030 00060 00070 00080 0009 0 001 Current applied A Figure 3 10 The measured data obtained with the standard dummy cell c with the Linear sweep voltammetry galvanostatic procedure 135 NOVA Getting started 3 8 Linear polarizat
71. 1 Current No Options AUT40008 0 000 On 5 1 04 1 04 400 Time WE 1 Current lt _amay gt s lt aray lt _amay gt s lt _amay gt A lt _array gt Off NOVA Getting started Chrono methods editor H Step lt Basic 25i Text Step Step Potential 0 V Step Duration 0 01 5 Sample Yes Interval time 0 0001 5 Estimated number of points 100 wJ Advanced t aay Figure 3 20 Overview of the levels used in the Chrono amperometry fast procedure The signals sampled during this procedure are e Corrected time e Level e Time e WE 1 Current e Index The automatic current ranging option is not available during the chrono methods measurement This procedure uses the Auto ab control command to set the instrument high speed and in the 1 mA current range before the measurement starts Figure 3 21 shows a measurement on the dummy cell c with the Autolab Chrono amperometry fast procedure 147 Page NOVA Getting started 0 001 0 0005 0 0005 WE TD Current 4 0 001 O 0015 0 O lt 005 0 01 O 015 O02 0 025 0 04 0 045 0 04 Corrected time s Figure 3 21 The measured data obtained with the standard dummy cell c with the Chrono amperometry fast procedure Note More information on time resolved measurements can be found in the Chrono methods tutorial available from the Help menu in NOVA 148 A E Jc NOVA Getting started 3 16
72. 12 Validation results 0 The following problems were encountered during validation Message Command AUT85189 O The specified value 5 mA is too high for the selected current range 1mA Set curent i The specified value 5 mA is too high for the selected current range 1 mA The current range must be 10 mA or higher Cancel Figure 4 12 The procedure validation step always checks the applied current values for the allowed linearity 175 Page NOVA Getting started In potentiostatic mode this check is not performed It is possible to measure a current value in a fixed current range even if the current value exceeds the linearity limit of the active current range This triggers a current overload warning When this happens during a measurement a message will be shown in the user log suggesting a modification of the current range see Figure 4 13 User log message Time Date Command 4 Autolab USB connected AUT85189 40504 PM 1 15 2013 amp Overload occurred in 1 pA current range use ahighercurrentrange 4 1043PM 1 15 2013 CV staircase Figure 4 13 When a current overload is detected a suggestion is shown in the user log 4 3 9 Oscillation detection The PGSTAT has a detector for large amplitude oscillation The detector will spot any signal swing that causes the control amplifier to produce both a positive and a negative Voltage overload within 200 us Thus large oscillations
73. 15 20 Index Index Figure 1 100 The data recorded during the TestEQCM procedure Switch the measurement view to 7wo plots vertically tiled mode by pressing the l button in the toolbar At the end of the measurement a message is displayed providing qualitative validation criteria for the measured data see Figure 1 101 TestEQCM The driving force should be stable within 0 025 W The Af should be stable around 0 Hz 5 Hz O xN ii Figure 1 101 A message is displayed at the end of the measurement Switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 102 88 Page NOVA Getting started TesE CM B TestEQCM Measured data ame Af vs t Measured data Toys tiMeasured data Orving force vs t Measured data TesEQCM Reference dataj f vs t Reterence data vs t Reterence dataj Oriving torce ws t Reference data l sine Figure 1 102 The data obtained with the TestEQCM procedure The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The EQCM measurements depend on the temperature and the crystal used during the experiment Comparison with the provided reference data points should be performed qualitatively 1 6 18 Determination of the C1 and C2 factors of the A
74. 164 and DAC164 167 NOVA Getting started ADC164 The ADC164 inputs labelled 41 and gt 2 on the front panel can be used to record any analog signal with a 10 V value range The input impedance of the two analog inputs is 50 Q DAC164 The DAC164 outputs labelled lt 1 and lt 2 on the front panel can be used to generate any analog signal with a 10 V value range The output impedance of these two inputs is 50 Q Corrections should be made with loads lt 100 kQ Because of dissipation the minimum load impedance should be 200 Q The DAC164 lt 1 and 2 outputs are identified as DAC channels 3 and 4 respectively in the Set DAC command 4 3 3 2 Connections for analog signals monitor cable With the supplied monitor cable there are a number of BNC connectors to the PGSTAT analog circuits see Figure 4 7 All the signals are with respect to Autolab ground and indirectly to protective earth Avoid creating ground loops as this will often degrade the performance of the PGSTAT 168 NOVA Getting started Series 7 Series 8 Figure 4 7 The monitor cable for the Series 8 and the Series 7 PGSTAT The following signals are available Eour This output corresponds to the differential potential of RE versus S The output voltage will vary between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load impedance is 200 Q iour T
75. 164 provides the possibility of measuring analog signals The input sensitivity is software controlled with ranges of 10 V gain 1 1 V gain 10 and 0 1 V gain 100 The resolution of the measurement is 1 in 65536 16 bits ADC164 Analog signals can be measured with a rate of up to 60 kHz The ADC164 is used to measure the output of the Voltage Follower VF and Current Follower CF of the potentiostat galvanostat module The DAC164 generates analog output signals The output is software controlled within a range of 10 V The resolution of the DAC164 is 1 in 65535 300 pV In the Autolab PGSTAT two channels of the DAC are used to control the analog input signal of the potentiostat galvanostat The pAutolab only uses one DAC channel to control the analog input see Figure 4 2 The values of the DACs are added up in the potentiostat and divided by 2 DAC channel 1 Is used as a variable DAC and DAC channel 2 provides a fixed offset This results in an output of 10 V with a resolution of 150 pV In practice this means that the potential range available with the Autolab PGSTAT during an electrochemical experiment is 5 V with respect to the offset potential generated by the offset DAC DAC164 1 The available potential range is therefore 10 V to 10 V with the Autolab PGSTAT and 5 V to 5 V with the uAutolab 3 These inputs are connected to the FRA32M or the FRA2 module 4 Or earlier version ADC750 159 NOVA Getting started
76. 19 NOVA Getting started i Warning The higher the bandwidth the more important it is to pay attention to adequate shielding of the cell and the electrode connectors The use of a Faraday cage is recommended in this case 4 7 5 RE input impedance and stability The electrometer RE input contains a small capacitive load If the capacitive part of the impedance between CE and RE is comparatively large phase shifts will occur which can lead to instability problems when working in potentiostatic mode If the impedance between the CE and the RE cannot be changed and oscillations are observed it is recommended to select the High stability mode to increase the system stability In general the use of High stability leads to a more stable control loop compared to High speed and a significantly lower bandwidth 4 7 6 Galvanostat and bandwidth For galvanostatic measurements on low current ranges the bandwidth limiting factor becomes the current to voltage circuit rather than the control amplifier For stability reasons it is not recommended to use the High speed mode for current ranges lt 10 pA A general indication of the maximum available bandwidth for GSTAT and PSTAT operation can be found in Table 4 10 Mode GSTAT IR C PSTAT 10mA 1mA gt 1MHz gt 1 MHz 100 uA 500 kHz 500 kHz 10 pA 50 kHz 50 kHz 1 pA 5 kHz 5 kHz 100 nA 400 Hz 400 Hz 10 nA 20 Hz 20 Hz Table 4 10 Bandwidth overview for the pAutolab II and III
77. 20 module or the on board integrator for the pAutolabll Ill the PGSTAT101 and Multi Autolab with M101 The procedure can be used to perform chrono coulometric measurements The integrator module provides a direct measurement of the charge More information about the use of the analog integrator is provided in the Filter and Integrator tutorial available from the Help menu in NOVA 3 18 Chrono amperometry high speed Hardware Tags ADC10M or ADC750 module Profile Tags Basic Application Tags None The Chrono amperometry high speed procedure uses the Chrono methods high speed command This command requires the optional ADC10M or ADC750 module Depending on the module the shortest interval time is 100 ns ADC10M or 1 33 us ADC750 More information about the use of these modules is provided in the Chrono methods high speed tutorial available from the Help menu in NOVA 151 NOVA Getting started 3 19 Chrono potentiometry high speed Hardware Tags ADC10M or ADC750 Profile Tags Basic Application Tags None The Chrono potentiometry high speed procedure uses the Chrono methods high speed command This command requires the optional ADC1OM or ADC750 module Depending on the module the shortest interval time is 100 ns ADC10M or 1 33 us ADC750 More information about the use of these modules is provided in the Chrono methods high speed tutorial available from the Help menu in NOVA 3 20 Chrono charge discharge Hardwa
78. 25 Selecting the data grid The data grid displays all the values of each signal that was recorded during the measurement Scrolling down the list allows you to inspect all the data points see Figure 2 26 Potential applied C WE C1 Potential w WELTI Current A Time s Scan Inder p 0 000378418 5 09247E 7 5 5693 1 1 00024414 0 00282898 1E 6 aa te ae ge 2 0 00465251 0 005258618 4 96044E 6 5 618515 J O 00 s2422 0 00771178 7 1859 7E 6 o 64255 4 0 008 765835 0 010156 4 4177 72E 6 o 566696 5 0 012207 0 0125544 1 16486E 5 a belay O0 0146404 O 0150402 1 a5gb 2E 5 oe lage Fj 0 01705495 O 01 4652 1 6098E 5 3 7402 a 0 0195313 O0 0188853 1 659209E 5 o 6462 0 02198727 00223602 2 05414E 5 5 70903 10 114 Page Figure 2 26 The data grid displays the values of the signals NOVA Getting started Using the data grid it is possible to export the measured data points to other software s for data analysis Excel Origin SigmaPlot This can be done by right clicking the data grid and by choosing the Export ASCII data option from the context menu see Figure 2 27 E Potential applied V WE 1 Potential V WE 1 Current A Time s Scan Index b IPUNE eet 5S i Ss 3 8 0 00976563 Cell 0 012207 File name Column delimiter Semicolon Decimal separator v File mode Overwrite A Write column headers PAANBAAARHAHF JE SSSA AHHH 0 0447021 4 144
79. 3 Connections for analog signals ccccccceeeseeeeeeeeeeeaeeeeeeeeeeeaeeeees 208 4 6 4 High stability High speed and Ultra high speed cceeeeeeee ees 209 4 6 5 RE input impedance and stability cc ecccceecceeeneeeeeeeeeeeeeneeeeeaes 211 4 6 6 Galvanostat potentiostat and iR compensation bandwidth 211 4 6 7 Galvanostatic operation and current range linearity c 211 4 6 8 Maximum reference electrode VOltaGe cceeecceceeeeteeeeeeeeeeeeaeeeees 214 A oc oer AVE eee ne ee 214 NOVA Getting started AOA OG OUMOCOSCCUS scecsciasatedassaarsbadaisesnetenusaaainaeen E 214 4 6 11 Environmental conditions ccccccseeeecceeseesceeeeseeseeesseneeesees 214 POs eZ O e E S N E A E EE EE 215 4 6 13 Temperature overload ccccccccseseecceeseesceseesseeeeseeseeeseeneeesees 215 4 7 pAutolab information ecaisseotiecdassreataeraaasecs quatdedauaamaaxsded eieuacoaeaeneouGuuiameens 216 4 7 1 Front panel and cell cable CONNECTION sssnnsesnnnesnnnesnnnennnnnenennns 216 aP E E reese A E E EEE E 217 4 7 3 Connections for analog signals cccccceceeeeeeeceeeeeeeaeeeeeeeeeeeneeeees 217 4 7 4 High stability and High speed cece ceeeeeeeeceeeeeeeeeeeeeeeeeaaeeeeees 218 4 7 5 RE input impedance and stability ce ceceecceeeneeeeeeeeeeeeeneeeeeans 220 4 7 6 Galvanostat and DANO WOU icisssicinstsendsiacu
80. 3 8 Galvanostatic operation and current range linearity For galvanostatic experiments automatic current ranging is not possible The measurements are performed in a fixed current range Each current range on the instrument is characterized by a specific linearity limit and this specification determines the maximum current that can be applied in galvanostatic mode The linearity limitation also applies on measurements performed in potentiostatic mode in a fixed current range Table 4 2 provides an overview of the current range linearity for the different PGSTAT instruments 174 NOVA Getting started PGSTAT12 Current range PGSTAT100 PGSTAT128N PGSTAT30 deepal PGSTAT100N 1A n a 0 8 1 2 100 mA 2 5 3 3 3 10 1 mA 3 3 3 3 100 1 uA 3 3 3 3 100 10nA 3 3 3 3 Table 4 2 Linearity limit for the different instruments For example in the 100 mA current range the maximum current that can be applied galvanostatically using the PGSTAT302N is 300 mA The maximum current that can be measured in the 100 mA current range using the same instrument is 1000 mA although currents exceeding 300 mA will be measured outside of the linearity limit of this current range In galvanostatic operation the applied current values are checked during the procedure validation step When the applied current exceeds the linearity limit for the specified current range an error message will be shown in the procedure validation screen see Figure 4
81. 9E 5 7 11066 to 00471252 iors po o Figure 2 27 Exporting the data to ASCII or Excel It is also possible to create new signals based on calculations performed on the existing signals For example it can be useful to calculate the logarithm of the measured current The data grid can be used like a spreadsheet It comes with a signal calculator which can be used to create a new signal based on an existing signal and a mathematical operation To create a new signal click the CV staircase item in the data explorer frame and select the Calculate signal tool from the quick access toolbar by clicking the button see Figure 2 28 E Quick start cyclic voltammetry m CV staircase a ivsE pe VX FAW TH B mA e Y WC Curren hAg E WE 1 Current alculate signal Figure 2 28 Adding a calculate signal to the CV staircase 115 Page NOVA Getting started Alternatively it is also possible to click the button located in the toolbar in the frame on the right hand side of the data grid see Figure 2 29 Potential applied V VWE 1 Potential V VWWE 1 Current A Time s Scan Index E i i Jhal Expression gt D 0000278418 5 09247E 7 5 5693 1 i H Calculate signal y 0 00244141 0 00282898 1E 6 5 59372 1 2 Time s 0 00488281 0 00525818 4 96094E 6 5 61813 1 l3 WE 1 Curr A 0 00732422 0 00771179 7 18597E 6 5 64255 1 4 es 0 00976563 0 0101583
82. A 1mA gt 500kHz gt 500 kHz 100 UA 125 kHz 500 kHz 10 pA 100 kHz 100 kHz 1 UA 10 kHz 10 kHz 100 nA 1 kHz 1 kHz 10 nA 100 Hz 100 Hz Table 4 4 Bandwidth overview for the PGSTAT302F At the same time the iR compensation bandwidth limits indicate up to which frequency current measurements can be made in potentiostatic mode either with or without iR compensation 3 Empirical value 188 NOVA Getting started 4 4 8 Galvanostatic operation and current range linearity For galvanostatic experiments automatic current ranging is not possible The measurements are performed in a fixed current range Each current range on the instrument is characterized by a specific linearity limit and this specification determines the maximum current that can be applied in galvanostatic mode The linearity limitation also applies on measurements performed in potentiostatic mode in a fixed current range Table 4 5 provides an overview of the current range linearity for the PGSTAT302F Current range Linearity 1A 2 100 mA 3 10 1 mA 3 100 1 pA 3 100 10 nA 3 Table 4 5 Linearity limit for the PGSTAT302F For example in the 100 mA current range the maximum current that can be applied galvanostatically using the PGSTAT302F is 300 mA The maximum current that can be measured in the 100 mA current range using the same instrument is 1000 mA although currents exceeding 300 mA will be measured outside of the linearity limit of
83. I20 Filter FI20 Integrator Booster20A Boosterl0A External External cable wAutolab IME303 IME663 MUX Power Supply Frequency 50 Hz Import FRA Calibration FRAZ offset DAC range 5V C Program Data Metrohm Autolab 11 0 HardwareSetup xml EE SASE 4 Misc 0 00E 00 tie 0 00E 00 Cl OK Auto Cancel Figure 1 23 The hardware setup in Nova Note Adjust the Power Supply Frequency according to your regional settings 50 Hz 60 Hz Click the OK button to close the hardware setup You will be prompted to confirm the hardware setup see Figure 1 24 30 Page NOVA Getting started Save changes G Changes are not saved save changes No Cancel Figure 1 24 Confirmation of the hardware setup The hardware setup is saved on the computer using the identifying serial number of the instrument This hardware configuration will be used automatically whenever the instrument is connected to the computer 1 4 FRA2 calibration file In order to perform electrochemical impedance spectroscopy measurements the FRA2 module must be installed and the hardware setup in NOVA must be setup accordingly see Figure 1 23 Each FRA2 module is calibrated in order to operate correctly inside the Autolab instrument Before the FRA2 can be used for impedance measurements the calibration file must be added to the hardware configuration in NOVA When NOVA is installed from the
84. IOM TestADC10M Measured data em ive t Measured data i E yst Measured dataj d TestADC10M Reference data j vs t Reference data E vs t Reference data Figure 1 58 The data obtained with the TestADC10M procedure The data for the TestADC750 is displayed in a similar way The first group located under TestADC10M Measured data contains the measured current and measured potential plotted versus corrected time The second group contains data from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 59 Small deviation can be observed between the measured data points and the reference data because of the tolerance of the capacitance included in the dummy cell 5 56 NOVA Getting started 0 003 0 002 0 001 0 001 0 002 WET Current tA WE 11 Potential V4 0 003 0 004 0 009 J 0 005 0 01 DOTS 0 02 Corrected time 3 Figure 1 59 The expected result of the TestADC10M or the TestADC750 procedure red curve WE 1 Current brown curve WE 1 Potential The test is successful if the measured data can be compared to the reference data 1 6 3 Test of BA The TestBA procedure can be used to test the correct functionality of the BA module The BA module is a dual mode module that works both as a bipotentiostat and as
85. NOVA Getting started NOVA Getting started Table of contents WIPRO Cl i essnee E sect shared ee tetes aint semne ese eet wie ttes pase EN 7 TTS MOS ODI OR IN OV Tesien E E E EN 8 1 Nova installation cette cute crerctitne dcincetesetceme oc ee eingue te reve teea dckanecaieuceecveednavinecussheee denaes 11 Td RS MN SAIS ES gecesi senescent naaa a EEE E E EE 11 1 2 Software Installation cccececceccecceceececceceecececeeeeeeecaeeueeesaeeueeeeaeeereeeaeees 11 1 2 1 NET 4 0 framework installation c cccccceceececcecceceececeeceeeeeeeaeeees 11 1 2 2 Nova installation sos cece vocceenadvccsncs vaousydeiniatenseieaucuntecadoua yous yeeaolesanseoeee 13 1 2 3 USB Drivers installation cccccceccececcececceceeeececeececuececeeeeeeaeeeeaeeeeaes 15 1 2 4 GPES FRA and older NOVA versions compatibility ceeee 19 V2 TUS ms UMEN TS s nen crores senna cnencisenumevayisaemuncivanndsanadeauk tlogsmomiaeiacn cee 22 1 3 Connection to the INStrUMENt S cceceecececeecececececcececececeeeececeeaeeereeaeaes 25 1 3 1 Connection and identification of individual instruments 27 1 3 2 Connection and identification of the Multi Autolab ee 28 138 ROW are SU EE E AET 29 1 4 FRA2 calibration file cccccceccecceccececceececeeceececeeeeeeceeeeeeeeaeeeeeeeeeesaeeanees 31 deg DIGGIN OS UGS corer EE events E E antares aawnsiee 35 1 5 1 Autolab Firmware Wa
86. Nova will continue 1 2 2 Nova installation If the NET framework is correctly installed on your computer the installation wizard starts the setup of Nova see Figure 1 3 fs Nova 1 10 O Welcome to the Nova 1 10 Setup Wizard The installer will guide you through the steps required to install Nova 1 10 on your computer WARNING This computer program is protected by copyright law and international treaties Unauthorized duplication or distribution of this program or any portion of it may resultin severe chil or criminal penalties and will be prosecuted to the maximum extent possible under the law Cancel lt Back Mest gt gt Figure 1 3 The Nova Setup wizard Click the gt button to continue the installation You will be prompted to enter the location of the installation folder or to validate the default setting see Figure 1 4 Press the button to change the installation folder or press the Next button to accept the default 13 NOVA Getting started fs Nova 1 10 O Select Installation Folder The installer will install Mowa 1 10 to the following folder To install in this folder click Mest To install to a different folder enter it below or click Browse Folder CAProgram Files xob Metrohm Autolab Nowe 1 10 Browse Disk Cost Cancel lt Back Mest gt Figure 1 4 Setting the installation folder Click the button to confirm the i
87. OVA Getting started To make use of the full potentiostat bandwidth High speed mode the impedance between CE and RE has to be lower than 35 kQ This value is derived by testing In galvanostat mode this large impedance between CE and RE will usually not lead to stability problems because of the current feedback regulation 4 4 6 Galvanostatic FRA measurements The capacitive part of the impedance between RE and ground is an important aspect to consider when performing FRA measurements in galvanostat mode Large reference electrode impedance values may introduce a phase shift at low frequencies The origin of the phase shift between the CE and the RE cannot be determined from the FRA data Galvanostatic FRA measurements at 1 MHz require a maximum of 3 kQ reference electrode impedance to keep phase errors within the 5 limit 4 4 7 Galvanostat potentiostat and iR compensation bandwidth For galvanostatic measurements on low current ranges the bandwidth limiting factor becomes the current to voltage circuit rather than the control amplifier For stability reasons it is not recommended to use the High speed mode for current ranges lt 10 pA As the current measurement circuit plays an important role in the iR compensation technique its use is also subject to bandwidth limitations A general indication of the maximum available bandwidth for GSTAT and for iR compensation can be found in Table 4 4 Mode GSTAT IR C PSTAT 1
88. Quick access toolbar E Quick start cyclic eu TY amp 0 001 T i x na i X l Signal Expression Unit livs E J s ae 0 0008 Potential applied V 0 0006 Time s WE 1 Current A T 0 0004 Scan ES 0 0002 Index i WE 1 Potential V Data explorer frame 0 0 0002 W 0 0004 0 0006 0 0008 Plot area Analysis frame 0 001 1 0 5 0 0 5 1 Potential applied V User log message Time Date Command i Autolab USB connected AUT40008 10 20 35 AM 1 15 2013 p Start amp Overload occurred in 1 pA current range use a higher current range 10 23 18 AM 1 15 2013 CV staircase User lo Start Stop button Intermediate Figure 2 15 The analysis view The analysis view has several noteworthy features the most important of which is the database Every measurement is stored in the database automatically Each entry of the database corresponds to a measurement and is logged together with the time and date as well as a Remarks field and the serial number of the instrument used in the experiment An additional field Instrument description can be used to provide a description of the instrument see Figure 2 16 Procedure name Time stamp Remarks Instrument Instrument description Quick start cyclic voltammetry 1 15 2013 10 22 29 AM Cyclic voltammetry potentiostatic AUT40008 Figure 2 16 Database entries are logged by Procedure name Time stamp Remarks Instrument and Instrumen
89. TestCV procedure requires connection to the dummy cell a 2 This test is also used to test earlier Autolab instruments PGSTAT10 20 12 30 302 100 and the pAutolabll 13 A specific test for the PGSTAT101 and the M101 is provided see section 1 6 1 2 14 A specific test for the PGSTAT302F in floating mode is provided see section 1 6 1 3 46 NOVA Getting started A message will be displayed when the measurement starts see Figure 1 44 TestCv This testis designed to verify the basic functionality of the Autolab potentiostat Connect dummy cell a and press OK to continue Data evaluation should be cared out in the Analysis view Figure 1 44 A message is displayed at the beginning of the measurement The test uses the cyclic voltammetry staircase method and performs a single potential scan starting from O V between 1 V and 1V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes three groups of data points see Figure 1 45 Testy Testy Measured data H j vs E Measured data E Residual plot Measured dataj Testy Reference data E vs E Reference data E Residual plot Reference data S S Limits E Upper limit a Lower limit A Upper limit E Lower limit Figure 1 45 The data obtained with the TestCV procedure The first group located under TestCV Measured data contains the measu
90. V and 1 V The recorded data points for Channel 1 are displayed on plot 1 and the data points for Channel 2 are displayed on plot 2 Switch the measurement view to 7wo plots vertically tiled mode by pressing the ll button in the toolbar At the end of the measurement switch to the Analysis view and load the data for evaluation 78 NOVA Getting started The data set includes four groups of data points see Figure 1 89 a TestMUe d Tests Measured data Channel 1 gemeiveE MU channel 1 Measured a TestMU Measured data Channel oe ivs E MUX channel 2 Measured i Teste Reference data Channel 1 ge ivsE MMU channel 1 Reference Testhillx Reference data Channel 2 a ive E MUS channel 2 Reference J H Figure 1 89 The data obtained with the TestMUX procedure The first two groups contain the measured on Channel 1 and on Channel 2 The other two groups contain data points for the WE 1 Current from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 90 0 001 1E 6 0008 J006 5E 7 Sie t 0 0002 E P J002 7 gt 5E 7 0 0004 JOO 0 0008 1E 6 _ 0 001 1 0 5 0 0 5 1 r D5 7 05 Potential applied W Potential applied V Figure 1 90 The expected re
91. a Safety precaution the PGSTAT is equipped with a circuit that monitors the temperature of the internal power electronics A temperature overload will be displayed as a blinking indicator in the manual cell switch with the cell 178 NOVA Getting started automatically turned off You will not be able to turn the cell back on until the temperature inside the instrument has fallen to an acceptable level It can then be switched on again by pressing the manual cell switch button on the front panel During normal operation the temperature should never become extremely high and no temperature overload will occur If this does happen the origin of the temperature overload should be identified Is the room temperature unusually high Was the PGSTAT oscillating Is the voltage selector for mains power set to the right value Is the fan turning and are all the ventilation holes unobstructed Was the cell delivering a considerable amount of power to the PGSTAT Are the WE and CE cables shorted in PSTAT mode ott S be If a temperature overload takes place repeatedly for no obvious reason Metrohm Autolab recommends having the instrument checked by their service department 4 3 15 Noise When measuring low level currents some precautions should be taken in order to minimize noise The personal computer must be placed as far away as possible from the electrochemical cell and the cell cables The cell cables should not cross other el
92. a can be compared to the reference data the current recorded during a measurement with the SCANGEN or the SCAN250 module strongly depends on the value of the capacitance included in the circuit of dummy cell a This capacitance has a tolerance of 5 The measured data points should therefore be qualitatively compared to the reference data provided with the test 1 6 16 Test of the SCANGEN or the SCAN250 in combination with the ACD750 or the ADC10M The TestADC SCAN procedure can be used to test the correct functionality of the linear scan generator module SCANGEN or SCAN250 in combination with the fast sampling ADC module ADC750 or ADC10M for high speed linear scan cyclic voltammetry measurements Load the TestADC SCAN procedure connect dummy cell a and press the start button A message will be displayed when the measurement starts 83 NOVA Getting started No data points can be shown real time during measurements with the fast sampling ADC module The test uses the cyclic voltammetry linear scan high speed method and performs a potential scan starting from 0 V between an upper vertex potential of 1 V anda lower vertex potential of 1 V After the first potential scan the measurement stops at the upper vertex potential 1 V at 100 V s At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 96 a TestADl
93. a scanning bipotentiostat Load the TestBA procedure connect WE 1 to dummy cell a and WE 2 to dummy cell 6 as shown in Figure 1 60 and press the start button 57 NOVA Getting started WE S e sA 24 o WE S d 1uF 5KQ DUMMY CELL2 1 Figure 1 60 Overview of the connections to the dummy cell required for the TestBA TestBIPOT and TestARRAY procedures A message will be displayed when the measurement starts Two measurements are performed during the test The test uses the cyclic voltammetry staircase method and performs a total of two potential scans During the first scan the BA is set to Bipotentiostat mode potential of WE 2 is expressed relative to the potential of the reference electrode During the second scan the BA Is set to scanning bipotentiostat mode potential of WE 2 is expressed relative to the potential of WE 1 In both measurements the offset potential used for WE 2 Is 1 V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes four groups of data points see Figure 1 61 58 NOVA Getting started i TestbA CY staircase Bipot mode WE 2 vs E Bipot mode Measured data I CY staircase Scanning bipot mode oe IME vs E Scanning bipot mode Measured data Ga C staircase Bipot mode WE 2 vs E Bipot mode Reference dataj a C staircase Scanning bipot mode a ivWwE2
94. ance is 200 Q Ew This is an analog voltage input that can only be used after it has been enabled in software using the Auto ab control command see Figure 4 20 Do not leave it enabled unnecessarily to prevent noise pickup by the system This input is directly connected to the summation point of the PGSTAT In PSTAT mode a The Eout value corresponds to WE 1 Potential gt The iout value corresponds to WE 1 Current NOVA Getting started 1 V signal will add 1 V to the cell voltage while in GSTAT mode a 1 V signal adds an extra current of 1 x the selected current range to flow In both cases the external signal adds to any pre defined voltage or current The input voltage range is 10 V Input impedance is 1 kQ only when input is activated so a correction should be made when the source impedance is gt 1 Q Autolab control 0 J PGSTAT302F lt v Basic DIO A Advanced Summary External input On E Oscillation protection m Off Reference potential 0 V Offset potential 0 V DAC164 1 0 V Figure 4 20 The external input is enabled in the Autolab control window 4 4 4 High stability and High speed The PGSTAT302F is equipped with two different bandwidth settings High stability HSTAB and High speed The bandwidth can be defined using the Autolab control command see Figure 4 21 185 NOVA Getting started i 3 i hers Autolab control 0 J PGSTAT302F lt Basic ae
95. arcdonnastacadchneuheraaaeatnemeraben 220 4 7 7 Galvanostatic operation and current range linearity 0cc 221 4 7 8 Maximum reference electrode voltage nnnnssssnnnnnnersnnenrerrrrren 222 AF ANE CONS eaa E E AEE A E 223 A7 10 Grounded CENS area searencrcs sere cctetscongss a E 223 4 7 11 Environmental conditions sccasasoicnadesindesvadoicaneniedeasaignasadeaandesaedden 223 ed sake NO eE E O 223 4 8 Noise considerations sa sicscnicnasecnsssandsanmtendseomadbonsbanenaiespondidalnienasstataaendstonienes 224 4 8 1 Problems with the reference electrode snnnnnensnnnnnssrinrssrrnnnen 224 4 8 2 Problems with unshielded cables ccccccssseesssseeeseeseeeseeseeesees 224 AO Fa AN E ea E AA ee ee 224 4 8 4 Grounding of the instrument cc eeeeccccee ee teeeeeeeeeeeaeeeeeeeeeeaaeeees 224 op o megs E 9 all Gall gio een ee eee eer E eer ner rt aeeee tere ere tee 224 4 8 6 Position of the cell Autolab and ACCESSOMIES ceeeeeeeeeeeeteeeees 224 4 8 7 Measurements in a glove 10 OX accra gurSteigseseuoncareatoledanecesemaaetdenieans 225 49 Cieanmng and MspECHON st sancasceasrct asacancisetoseceesoacaaecciendacanseonesecoseeesrseed 225 5 Warranty and conformity 04 caine siccs icntccacidind festanistonndinn sith pomdande caatdiastadadakstacensaletasiondd 227 De Eae EE E E E E E 227 5 2 General Specifications ccccccccccssescecceesececcceesececs
96. are for your device gt Install this driver software anyway Only install driver software obtained from your manufacturer s website or disc Unsigned software from other sources may harm your computer or steal information X v See details Figure 1 12 A warning is provided when the GPES compatible driver is installed Select the nsta this driver software anyway option to proceed with the installation At the end of the installation a message will be displayed indicating that the driver has been successfully installed see Figure 1 13 Done The used driver has successfully been updated Figure 1 13 A message is displayed at the end of the driver update process The status of the drivers used to control the connected devices displayed at the bottom of the driver manager window is updated automatically see Figure 1 14 21 Page NOVA Getting started gt Driver Manager O ES Select the driver used to control your Autolab instrument Nova only recommended setup Select this driver when you only use Nova 1 7 or higher on your PC Advantages Faster USB data exchange Connect a maximum of 16 Autolab instruments Supports 64 bit Windows Ready for future applications GPES compatible Select this driver when you want to use Nova 1 7 or higher together with Nova 1 6 or lower and or GPES on this PC Restrictions Slower USB data exchange Connect a maximum of 8 Autolab instrum
97. asurement at frequencies gt 10 kHz It is possible to switch from High stability to High speed by clicking the HSTAB label in the Autolab display In High speed mode this label will be unlit both on the front panel of the PGSTAT and on the Autolab display Clicking the HSTAB label again switches the bandwidth back to High stability The High speed mode is automatically selected during impedance measurements at frequencies gt 10 kHz while the High stability mode is selected for frequencies below 10 kHz see Figure 4 23 High stability High speed 10 kHz Figure 4 23 Bandwidth limits in the Autolab PGSTAT302F A Warning The higher the bandwidth the more important it is to pay attention to adequate shielding of the cell and the electrode connectors The use of a Faraday cage is recommended in this case 4 4 5 RE input impedance and stability The electrometer RE input contains a small capacitive load If the capacitive part of the impedance between CE and RE is comparatively large phase shifts will occur which can lead to instability problems when working in potentiostatic mode If the impedance between the CE and the RE cannot be changed and oscillations are observed it is recommended to select the High stability mode to increase the system stability In general the use of High stability leads to a more stable control loop compared to High speed or Ultra high speed and a significantly lower bandwidth 187 N
98. ata Galvanostatic FRA measurements at 1 MHz require a maximum of 3 kQ reference electrode impedance to keep phase errors within the 5 limit 4 3 7 Galvanostat potentiostat and iR compensation bandwidth For galvanostatic measurements on low current ranges the bandwidth limiting factor becomes the current to voltage circuit rather than the control amplifier For stability reasons it is not recommended to use the High speed mode for current ranges lt 10 pA The Ultra high speed mode is also not recommended for current ranges lt 1 MA As the current measurement circuit plays an important role in the iR compensation technique its use is also subject to bandwidth limitations 4 Empirical value 173 NOVA Getting started A general indication of the maximum available bandwidth for GSTAT and for iR compensation can be found in Table 4 1 Instrument PGSTAT12 128N 100 100N PGSTAT30 302 302N Mode GSTAT IR C PSTAT GSTAT IR C PSTAT 1A 1mA gt 500 kHz gt 500 kHz gt 1 25MHz gt 1 25 MHz 100 pA 125 kHz 500 kHz 125 kHz 1 MHz 10 pA 100 kHz 100 kHz 100 kHz 100 kHz 1 pA 10 kHz 10 kHz 10 kHz 10 kHz 100 nA 1 kHz 1 kHz 1 kHz 1 kHz 10 nA 100 Hz 100 Hz 100 Hz 100 Hz Table 4 1 Bandwidth overview for the different instruments At the same time the iR compensation bandwidth limits indicate up to which frequency current measurements can be made in potentiostatic mode either with or without iR compensation 4
99. ation Disconnect the dummy cell and leave the leads open inthe Faraday cage CE and RE must be connected together as well as WE and Be sure CE RE and WE S are NOT connected together Figure 1 112 A reminder message is shown at the beginning of the measurement 5 During the measurement the measured data will be plotted as a Bode plot should be similar to the example shown in Figure 1 113 1E 10 lees 100 1000 10 Frequency Hz Figure 1 113 Typical Bode plot obtained during the C2 calibration 6 The data is automatically fitted and the results of the fitting are reported in a Message box at the end of the measurement see Figure 1 114 96 C2 calibration factor C2 5 43E 13 F ok NOVA Getting started W Figure 1 114 The experimentally determined value of C2 is reported in a Message box at the end of the measurement 7 Open the Hardware setup of Nova Tools Hardware setup Select the instrument type in the Main Module frame in the hardware setup window and adjust the value of C2 to the value reported in the Message box see Figure 1 115 Hardware setup AUT84530 0 File Tools Kain Module POST AT W024 Import FRA Calibration Additional Modules FRAIZM W FRA _JADC10M _JADC750 JADC 5Or4 SCAN250 SCANGEN amp L_ BA BIPFOT ARRAY JEcD Fl20 Filter Fl20 Integrator Booster204 Booster tA JEQCM Jpx1000 px
100. atively compared to the reference data provided with the test 1 6 12 Test of FRA The TestFRA procedure can be used to test the correct functionality of the FRA32M and the FRA2 module 18 When the FRA32M or FRA2 is installed in a PGSTAT302F make sure that the PGSTAT302F is set to Normal mode 73 NOVA Getting started A Warning For the FRA2 module make sure that the FRA2 offset DAC range property is set properly in the hardware setup For FRA2 modules the correct value is 5 V For FRA2 V10 modules the correct value is 10 V Failure to set this value properly may result in faulty data at frequencies of 25 Hz and lower refer to front panel labels of the FRA2 module on the instrument Load the TestFRA procedure connect dummy cell c and press the start button A message will be displayed when the measurement starts The test uses a potentiostatic frequency scan from 10 kHz to 0 1 Hz with a 10 mV amplitude The frequency scan contains 50 frequencies with a logarithmic distribution The measurement takes about four minutes to finish Click the OK button to continue with the measurement During the experiment four plots are shown in the measurement view see Figure 1 83 Plot 1 corresponds to the Nyquist plot Z vs Z plot 2 corresponds to the Bode plot z and vs frequency plot 3 corresponds to the resolution plot i resolution vs t and E resolution vs t and plot 4 corresponds to the Lissajous plot
101. can be used to plug to the earth bulkhead for shielding purposes Finally a monitor cable can be connected to a dedicated connector see Figure 4 4 44 For information on the PGSTAT302F please refer to Section 4 4 For information on the PGSTAT101 and the Multi Autolab with M101 module please refer to Section 4 5 For information on the pAutolab type Il and Ill please refer to Section 4 6 164 NOVA Getting started i Note The Series 7 instruments and early Series 8 instruments are provided with an additional ground cable which should be connected to the plug provided above the connector for the monitor cable This ground connector should be used for grounding purposes On Off button Digital display Cell On Off switch o ON mi OFF e O penae ADC164 DAC164 Monitor cable input RE S socket WE CE Ground socket On Off button Digital display Cell On Off switch Ground connection ADC164 DAC164 Monitor cable input RE S socket WE CE socket Figure 4 4 Overview of the Autolab PGSTAT top Series 8 PGSTAT bottom Series 7 PGSTAT 165 Page NOVA Getting started The Series 8 instruments are provided with an additional ground cable embedded into the CE WE cable This ground connector should be used for grounding purposes The cell cables are labelled as follows e Working or indicator electrode WE red e Sense electrode S red e Reference electrode RE blue e Auxiliary or counter ele
102. can generators The procedure can be used to perform a cyclic voltammogram using a true linear scan potential profile rather than a staircase potential profile More information about the use of these modules is provided in the Cyclic voltammetry linear scan tutorial available from the Help menu in NOVA 3 5 Cyclic voltammetry linear scan high speed Hardware Tags SCAN250 or SCANGEN in combination with ADC10M or ADC750 module Profile Tags Basic Application Tags None This procedure requires the optional SCAN250 or SCANGEN module and the optional ADC10M or ADC750 module The SCAN250 and the SCANGEN are both linear scan generators The ADC10M and the ADC750 are fast sampling analog to digital converters The procedure can be used to perform a cyclic voltammogram using a true linear scan potential profile rather than a staircase potential profile at high scan rate More information about the use of these modules is provided in the Cyclic voltammetry linear scan tutorial available from the Help menu in NOVA 30 Up to 10 kV s with the SCANGEN ADC750 or ADC10M and the SCAN250 ADC750 up to 250 kV s with the SCAN250 ADC10M 131 NOVA Getting started 3 6 Linear sweep voltammetry potentiostatic Hardware Tags Profile Tags Application Tags None Basic Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors This procedure is a typical example of a staircase linear sweep voltammetry exper
103. cation is ready a series of tests can be performed on the selected instrument In order to perform the tests properly the hardware setup for the connected instrument must be defined Select the Hardware option from the Select menu to define or verify the hardware configuration see Figure 1 33 37 Page NOVA Getting started Diagnostics AUT83071 O Die Select All Tests Results Deselect Optional Tests Hardware setup X Select instrument W Autolab Test AD Converter Test DA Converter Test Potentiostat Test Noise Test Galvanostat Test Progress start Figure 1 33 Adjusting the hardware setup for the connected instrument 1 2 The hardware setup window will be displayed Adjust the hardware configuration for the connected instrument and press OK to save the changes A specific hardware setup file is created and stored on the computer for each instrument e f the hardware setup for the connected instrument has already been defined in NOVA or in a previous diagnostics test the hardware configuration file for the instrument will be automatically recovered and no adjustments will be necessary e f no hardware setup file is found for the connected instrument the default setup is used default PGSTAT302N no additional modules Pressing the start button will initiate all the selected tests A visual reminder will be displayed at the beginning of the test illustrating
104. cell is used will be shown during validation see Figure 1 79 This warning is provided as a reminder and the OK button can be clicked to proceed with the measurement Validation results Oo The following problems were encountered during validation Message Command AUT40008 amp The internal dummy cell is on Autolab control The internal dummy cell is on Set potential amp The internal dum Ilis on Set cell Ilis on TestFl20 Integrator PGSTAT101 Measured data amp The internal dummy t Time remaining 15 seconds Cancel Figure 1 79 A warning is displayed at the beginning of the procedure A message will be displayed when the measurement starts see Figure 1 80 71 Page NOVA Getting started TestFl20 Integrator PGSTAT101 This procedure ts designed to test the basic A functionality of the on board integrator module of the PGSTAT101 In this experiment an integrator time constant of 0 01 s is used The internal dummy cell is used Connect CE to RE and to WE Make sure that the cell cable is not connected to an external cell Click OK to continue Analyze the data in the Analysis VIEW nf Figure 1 80 A message is displayed at the beginning of the test The test uses the cyclic voltammetry current integration staircase method and performs a single potential scan During this scan the potential of the working electrode is scanning between 1 V and 1 V Du
105. cells showing an absolute voltage Vel of less than 10 V between WE and CE are intrinsically safe They may drive the PGSTAT output stage into current limit but will not overload the amplifier On the other hand cells that have an absolute voltage higher than 10 V between WE and CE may only deliver a maximum current Imax given by i _ Puax MAX wm Vmax 192 NOVA Getting started 4 4 12 Grounded cells and grounded working electrodes The PGSTAT302F can be operated in two different modes e Normal mode this mode corresponds to the operating mode using in all the PGSTAT instruments For more information on the restrictions applying to this mode please refer to section 4 3 12 e Floating mode this mode is only available on the PGSTAT302F In this mode measurement circuitry of the Autolab is internally disconnected to protective earth P E This allows the instrument to be used in combination with a grounded working electrode or a grounded cell The PGSTAT302F can be set to either normal mode or floating mode using a dedicated short circuit plug on the back plane of the instrument see Figure 4 28 When the short circuit plug is connected as shown in Figure 4 28 the instrument operates in normal mode When the short circuit plug is disconnected from the back panel the instrument operates in floating mode Figure 4 28 The PGSTAT302F can be set to normal mode left or to floating mode right using the provided short c
106. ctrode CE black In a four electrode setup each of the cell cable connectors is used independently In a three electrode set up the working electrode and sense lead are both connected to the working electrode In a two electrode set up the counter and reference electrode lead are both connected to the same electrode see Figure 4 5 RE CE WE S RE CE WE S RE S CE WE Figure 4 5 Overview of the possible cell connections with the Autolab PGSTAT from top to bottom two electrode three electrode and four electrode setup 166 NOVA Getting started 4 3 2 Power up The settings of the PGSTAT on power up are pre defined The following settings are used e Cell off e Mode Potentiostatic e Bandwidth High stability e iR Compensation off e Current range 10 mA e ECD mode off if applicable 4 3 3 Connections for analog signals The Autolab PGSTAT provides connections for analog signals through two different types of connectors e BNC connectors directly located on the front panel of the instrument e BNC connectors located on the monitor cable 4 3 3 1 Connections for analog signals front panel The ADC164 module and the DAC164 module are fitted with two analog inputs and two analog outputs respectively see Figure 4 6 Ol AUTOLAB I 00900009000 ADC164 DAC164 Figure 4 6 Overview of the connections for analog signals provided on the front panel of the Autolab PGSTAT ADC
107. cy range Amplitude DC potential Method 5 Impedance Automatic current ranging Potentiostat Set E DC ee Wait ON Apply Set cell frequency EAE OFF Repeat for each frequency Figure 1 Schematic overview of a method based software In a method based application the user chooses one of the 7 available methods and defines the available parameters for the method When the measurement Starts the whole method is uploaded to the instrument where it is decomposed into individual low level instructions These are then executed sequentially until the measurement is finished If the method required by the user is not available the user will have to wait until the method is implemented in a future release NOVA Getting started Nova has been designed with a completely different philosophy Rather than implementing well defined methods in the software Nova provides the users with a number of basic Objects corresponding to the low level functions of the electrochemical instrument These objects can be used as building blocks and can be combined with one another according to the requirements of the user in order to create a complete experimental method In essence the scientist uses Nova as a programming language for electrochemistry building simple or complex procedures out of individual commands The instructions can be combined in any way the user sees fit Rather than providing specific electrochemical methods to
108. description Control Autolab RDE Autolab control Set potential Set cell Wait time s Repeat for each value Number of repetitions Parameter link Set potential Control Autolab RDE DAC channel Rotation rate Wd i Calculate w H Wait time s Optimize current range E LSV staircase Start potential V Stop potential V Step potential V Scan rate V s Estimated number of points Interval time Signal sampler Options Potential applied Time WE 1 Current WE 1 Potential Index t ivs E lt gt Switch Autolab RDE off Set cell Hydrodynamic i vs vw T DE EE EE E E E Figure 3 14 The standard Hydrodynamic linear sweep procedure Farameters Time WE 1 Potential WE 1 Current 1 Options AUT40008 0 1 000 On 15 500 31 92 1247 9 1747 9 2331 9 3000 6 1 000 500 3 lt array gt rad s 2 0 Pl RPM 60 0 15 5 1 000 0 000 0 1000000 1 000 0 000 0 00244 0 1000000 422 0 024400 Time WE 1 Potential WE 1 Current 1 Options lt _amay gt V aray Ss _ array A _array gt WV _ array gt A A A A The signals sampled during this procedure are e Potential applied e Time e WE 1 Current e WE 1 Potential e Index 140 Page NOVA Getting started The step value used in the Hydrodynamic linear sweep voltammetry procedure is negative because the sweep goes from 1 V to O V 3 10 Differential pulse voltammetry
109. dule test in NOVA Nova includes a number of procedures designed to verify the basic functionality of the different hardware modules installed in the instrument These tests can be performed at any time using the Autolab dummy cell These procedures are located in the Module test database located in the C Program Files Metrohm Autolab Nova 1 10 Shared DataBases folder To use these procedures define the location of the Module test folder as the Standard database using the Database manager available from the Tools menu see Figure 1 41 Database management Browse For Folder Standards 4 Metrohm Autolab a Nova 1 10 config Metrohm 4 Shared DataBases l Demo Database Module test gt Tutorials Make New Folder Cancel ncel Figure 1 41 Loading the Module test database A total of 25 procedures are provided in the Module test database see Figure 1 42 11 Except for the Autolab PGSTAT101 the Autolab M101 module and the Autolab EQCM module 44 NOVA Getting started Commands Procedures gt AUtolab standards PGSTAT C1 calibration PGSTAT C2 calibration TastADC SCAN TastADC1OM TestADC750 m TastARRAY TastBA TastBIPOT TastBooster 104 TastBoosterZ04 THI TestO PGSTATION TestO PGSTAT302F TastECD TestECN TastE QCM TastFl20 Filter TestFl20 Integratar TastFl20 Integrator PGSTAT1O1 TestFRA Teast Testo 1000 TastSCAN250
110. dummy cell The purpose of this quick start is to perform staircase cyclic voltammetry on the Autolab dummy cell In the example discussed below the dummy cell c is used The cell cables should therefore be connected to the dummy cell as displayed in Figure 2 3 101 Page NOVA Getting started The PGSTAT101 is not equipped with the Autolab dummy cell An optional external dummy cell can be obtained Contact your Autolab distributor for more information For the PGSTAT101 use the procedure TestCV PGSTAT101 available in the Module test database Refer to the Module test with Nova document available from the Help Tutorials menu CE RE WE S e WE S d 1pF 5k MI DUMMY CELL2 Figure 2 3 Dummy cell connections 2 2 1 Setting up the experiment To perform a cyclic voltammetry experiment the default Cyclic voltammetry potentiostatic procedure must be loaded into the Procedure editor Right clicking the Cyclic voltammetry potentiostatic procedure in the browser brings up a context menu displaying the Open for editing option see Figure 2 4 File View Profile Run Tools Help Oe Sh eh PT 8 eo 2 En cr Commands Parameters New procedure E Autolab BIA cyclic voltammetry potentostai aa 3 Cyclic voltammetry galvanosta Hide Cyclic voltammetry current integ i Open for editing Cyclic voltammetry linear scan fee Cyclic voltammetry linear scan Linear sweep voltamm
111. e Eour This output corresponds to the differential potential of RE versus S The output voltage will vary between 10 V The output impedance is 1 kQ so a correction should be made if a load lt 2 MQ is connected The maximum bandwidth is 300 kHz lour This signal corresponds to the inverted output of the current to voltage converter circuit of the PGSTAT101 A 1 V signal corresponds to 1 x the selected current range The output level varies between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ Is connected The minimum load impedance is 200 Q Vour This output corresponds to the DAC output It is controlled by software and is meant to be used to control external devices like the rotating speed of a The Eout value Corresponds to WE 1 Potential gt The iout value Corresponds to WE 1 Current Current range 199 Page NOVA Getting started Rotating Disc Electrode RDE The output level varies between 10 V and the output impedance is very low lt 1 Q The output amplifier is capable of providing 5 mA at full scale so load impedance should be gt 2 kQ Vin This input corresponds to the ADC input This input can be used for measuring a second signal The input range is 10 V and the input impedance is 50 Q 4 5 5 High stability High speed and Ultra high speed The PGSTAT101 is equipped with three different bandwidth settings High stability
112. e cells that cause ringing when switching the cell on or changing the current range can falsely trigger the oscillation detector If this happens the Oscillation protection may be switched off in the software in order to prevent an accidental disconnection of the cell 4 3 10 Maximum reference electrode voltage The differential electrometer input contains an input protection circuitry that becomes active after crossing the 10 V limit This is implemented to avoid electrometer damage Please note that the Vow indicator will not light up for this type of voltage overload The measured voltage will be cutoff at an absolute value of 10 00 V Depending on the cell properties galvanostatic control of the cell could lead to a potential difference between the RE and the S WE larger than 10 V This situation will trigger the cutoff of the measured voltage to prevent overloading the differential amplifier 177 NOVA Getting started 4 3 11 Active cells Some electrochemical cells such as batteries and fuel cells are capable of delivering power to the PGSTAT This is allowed only to a maximum cell power Pmax This value depends on the instrument see Table 4 3 Instrument Maximum power Pmax W PGSTAT12 2 5 PGSTAT128N 8 PGSTAT30 10 PGSTAT302 302N 20 PGSTAT100 100N 2 5 Table 4 3 Maximum power rating for the different PGSTAT models This means that cells showing an absolute voltage Vel of less than 10 V between WE
113. e data 69 NOVA Getting started The current recorded during current integration cyclic voltammetry strongly depends on the value of the capacitance included in the circuit of dummy cell a This capacitance has a tolerance of 5 The measured data points should therefore by qualitatively compared to the reference data provided with the test 1 6 11 Test of FI20 Integrator PGSTAT101 The TestFl20 Integrator PGSTAT101 procedure can be used to test the correct functionality of the on board integrator of the PGSTAT101 and the Autolab M101 potentiostat galvanostat module The Fl20 Integrator needs to be properly calibrated before the test Integrator calibration is performed in the Diagnostics application Please refer to Section 1 5 of the Getting Started manual or the FI20 tutorial for more information i Warning This test is designed for the PGSTAT101 and M101 only For all the other Autolab instruments fitted with a FI20 module please use the TestFl20 Integrator procedure see Section 1 6 10 Load the TestFl20 Integrator PGSTAT101 procedure This test uses the internal dummy cell of the instrument Connect the CE and the RE electrode leads and the WE and S from the cell cable as shown in Figure 1 78 and press the start button 70 NOVA Getting started Figure 1 78 The connections required for the TestFl20 Integrator PGSTAT101 procedure A warning message indicating that the internal dummy
114. e depending on the module to test from the Standards database connect dummy cell a and press the Start button A message will be displayed when the measurement starts The test uses the cyclic voltammetry linear scan method and performs a potential scan starting from O V between an upper vertex potential of 1 V and a lower vertex potential of 1 V After the first potential scan the measurement stops at the upper vertex potential 1 V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 94 a TestsCaAne5t a TestsCAN 250 Measured data 7 a j vs E Measured data il TestSCAN250 Reference data gem ives E Reference data Figure 1 94 The data obtained with the TestSCAN250 procedure The data for the TestSCANGEN Is displayed in a similar way The first group located under TestSCAN250 Measured data contains the measured current plotted versus the measured potential The second group contains data from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 95 82 NOVA Getting started 1E 6 SE f E WELT Potential V Figure 1 95 The expected result of the TestSCAN250 or the TestSCANGEN procedure The test is successful if the measured dat
115. e digital base of the Autolab It is clear that the digital nature of the instrument has consequences for the measurements The consequences for the different techniques are e The minimum potential step or pulse in all techniques is 150 uV 16 Bit DAC164 e All potential steps are rounded up or down to the nearest possible multiple of 150 yV e In cyclic voltammetry staircase the interval time At or time between two consecutive steps is given by ie Vv Where Estep is the potential step and v is the scan rate in V s The response of the electrochemical cell is recorded digitally Therefore the resolution of the measurements is also limited The actual resolution depends on the technique and on the amplitude of the signal Since the A D converter is equipped with a software programmable amplifier the absolute resolution depends on the gain of the amplifier The gains used are 1 10 and 100 times the input signal NOVA automatically selects the best possible gain during a measurement Gain 10 and 100 are used when the signal is small enough When the absolute value of the current is higher than 0 5 current range the resolution of the current measurement equals C R 20 216 4 C R 0 0003 When the absolute value of the current is lower than 0 5 current range the resolution equals 3 The same applies for Galvanostatic control of the instrument 163 NOVA Getting started C R 20 _ C R
116. e discharge e Hnterrupt Hnterrupthigh speed Positive feedback be FRA impedance potentiostatic FRA impedance galvanostatic be FRA potential scan Standards My procedures User log message Time Date i Created hardware setup for AUT40008 12 13 10 1 14 2013 p Start 4 Autolab USB connected AUT40008 12 13 13 1 14 2013 Command Ready Intermediate Figure 1 22 The Setup view of Nova Locate the Tools menu in the toolbar and select the Hardware setup from the menu see Figure 1 22 This will open the Hardware setup window Check the boxes that correspond to your hardware configuration see Figure 1 23 Note This version of Nova supports all the Autolab instruments except the uAutolab type and the PSTAT10 with a USB interface either internal or through a USB interface box All the Autolab modules are supported except the ADC124 DAC124 DAC168 and the first generation FRA 29 Page NOVA Getting started File Tools Main Module PGSTAT302N _ PGSTAT302F PGSTAT302 PGSTAT30 _ PGSTAT30 AUTQ PGSTAT128N _ PGSTAT12 PGSTATIO0ON PGSTAT100 PGSTAT100 AUT PGSTAT101 M101 pAutolab III pAutolab II PGSTAT204 PGSTAT20 PGSTAT10 Hardware setup Additional Module s FRA32M _ FRA2 ADCIOM JADC 750 JADC 50r4 SCAN250 SCANGEN IBA BIPOT ARRAY JECD _ F
117. e embedded PC is 1 us When a procedure is started in NOVA the procedure is first uploaded from the host PC to the embedded PC through the USB connection The measurement can then be started Depending on the type of command that NOVA encounters during the measurements two timing protocols are used 1 Measurement commands all measurement commands in NOVA are Timed commands Whenever NOVA encounters a measurement command it will be executed using the timing provided by the embedded computer of the Autolab If several measurement commands are located in sequence the sequence is executed without interruption This ensures that the measurement commands in the sequence are executed with the smallest possible time gap The actual time difference between two consecutive commands depends on the hardware changes required during the transition between the two commands Switching current ranges or using the cell switch are time consuming steps since they involve mechanical relays which require a fixed settling time Taking into account these hardware defined interval times the effective time gap between two consecutive commands in a Timed procedure will be lt 10 ms Measurement commands are identified by a green line on the left hand side of the procedure editor 2 Host commands all the other commands in NOVA are host commands These commands are executed by the host PC using the timing provided by this computer Since the host PC is also in
118. e of these procedures are illustrated using the Autolab dummy cell Procedures requiring additional hardware are not detailed More information regarding the use of the optional modules is provided in the dedicated tutorials available from the Help Tutorials menu Each sub section provides information on a specific procedure A table is provided for each procedure listing the profile tags and hardware requirements see Table 3 1 Hardware Tags None Profile Tags Basic Application Tags Energy Table 3 1 Table used to indicate the tags for an Autolab procedure Cyclic voltammetry galvanostatic Table 3 1 shows the tags for the Autolab Cyclic voltammetry galvanostatic procedure This procedure normally appears in the Basic profile and is also used in the Energy application profile Furthermore this procedure does not require additional hardware 125 NOVA Getting started 3 1 Cyclic voltammetry potentiostatic Hardware Tags None Profile Tags Basic Application Tags Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors The standard Cyclic voltammetry potentiostatic procedure is the first procedure located in the Autolab group of procedures It is a typical potentiostatic staircase cyclic voltammetry procedure The procedure has the following parameters e Preconditioning potential O V e Duration 5 s e CV Staircase o Start potential 0 V Upper vertex potential 1 V Lower vert
119. eccssseeeeseeesseesceeeeeesseesseness 161 4 2 Consequence of the digital base of the Autolab ee ceeeeeeeeeeees 163 4 3 Autolab PGSTAT information ccccccececeeeeeeeteeeeeeeeeseaeeeeeeeeeeaaeeeeeeeees 164 4 3 1 Front panel and cell cable CONNECTION cccecccseeeceeeeeeeaeeeesaeeees 164 i OV ST UND ales cer seat E E 167 4 3 3 Connections for analog signals ccccecceeeseeeeeeeeeeeeeeeeeeeeeeeeaeeeees 167 4 3 3 1 Connections for analog signals front panel ceeeeeeeeeees 167 4 3 3 2 Connections for analog signals monitor cable c c cece 168 4 3 4 High stability High speed and Ultra high speed cceeeeeeee ees 170 4 3 5 RE input impedance and stability ce ceeceeeeeeeeeeseeeeeeeeeeeeeans 172 4 3 6 Galvanostatic FRA measurements cccceeceeeeeeeeeeeeeeeeeeeeeeaaeeeeees 173 4 3 7 Galvanostat potentiostat and iR compensation bandwidth 173 4 3 8 Galvanostatic operation and current range linearity 174 4o JOS CIAO MO CHSC OM erore E ean acteemtaddeeuaien 176 4 NOVA Getting started 4 3 10 Maximum reference electrode VOItaGe ceecceceeeseseeeeeeeeeeaneeeees 177 BB AC CGMS a saucer capecsacsandtereacelssusantio E E E eE 178 43 12 Grounded CCUG siape EE EENE 178 4 3 13 Environmental conditions ssnnussnnsssninssnrnesrrnrsrrrrsrrrrerrrresrrre gt 178 4 3 14
120. ecseseeecseseeessaseeeseaaes 141 3 13 Chrono amperometry At gt 1 MS ccccccsececsesseecseseeeceseeeseeseeeseaaes 142 3 14 Chrono potentiometry At gt 1 MS cceccceeseeeceeeeeeeeeaeeeeesaeeeeesaeees 144 3 15 Chrono amperometry fast ccccccccssssceccessseescesecesseueseesseeaeeesseaas 145 3 16 Chrono potentiometry fast cccccccssssseeeeeceeesseeeeecceeessesenesseeesseees 149 3 17 Chrono coulometry FAG sohatacencsncetndsicesnetedeqateasiecatensiceatedaneasaetnrecebaiaiens 151 3 18 Chrono amperometry high speed cece ceeeeceeeeeteeeeeeeeeeeeeeesaeeeeeeeeaes 151 3 19 Chrono potentiometry Nigh SPeed ceeceeceeeeeeeeeeeeeeeeeeeeesaeeeeeeeeaes 152 320 COMO Cai discharge gs eccreitacacieecteansigp iaaa i Ea as 152 e SIU E I E PAP TA A T E 154 3 22 IME nup ENIN SPECO EA ES 154 Bid a PO IVE TEDA nean E A E E 155 3 24 FRA impedance potentiOstatic ccccccsesscecseseeecsesseecseseeecseseesseaaes 155 3 25 FRA impedance galvanostatic ccceeceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeaes 156 3 260 FRA potential SCAM ssoseastecccntcncnotacesaanuareqsnectasonsenaseaaeeesntassnicedinseteneases 156 4 Autolab Hardware information cc ccccssccecccceessseeeecceeaeseeeeeseeeessesenesseeeas 157 4 1 Overview of the Autolab InstrUMent cccccececceceeeeteeeeeeeeeeaaeeeeeeeees 157 4 1 1 Event timing in the Autolab ccccc
121. ected data points will be displayed in real time At the end of the measurement the data points will be available for further analysis i Note GPES users are used to start a measurement by selecting a pre defined method from a list of available techniques Nova is designed to perform complex measurements seamlessly switching from one electrochemical method to another in a single procedure see Chapter 2 of the User manual for further information Therefore the electrochemical method selection becomes obsolete ready to use template procedures are included see Chapter 3 for more information For this quick start the Autolab is used in conjunction with the dummy cell 2 1 Starting up the software installation required see Chapter 1 Nova can be started by double clicking the Nova shortcut on the computer desktop If an Autolab is already connected to the computer through the USB connection and turned on the software will automatically identify the instrument and upload the required control software If no instrument is connected after starting Nova connecting the Autolab to the computer using the USB and turning it on will trigger the initialization process automatically see Chapter 1 for further details on the USB communication with the instrument By default Nova will start in the Setup view The Setup view is one of the four views the user can select while operating Nova The other three are the Measurement view used to di
122. ectrical cables Other equipment with power supplies can also cause noise For instance the interface for mercury electrodes IME should also be placed with some care If possible place the computer between the PGSTAT and other equipments Avoid using unshielded extension cables to the electrodes The use of a Faraday cage is also advised If the cell system has a ground connector it can be connected to the analog ground connector at the front of the PGSTAT If a Faraday cage is used it should be connected to this ground connector Some experiments concerning optimization of the signal to noise ratio can readily indicate whether or not a configuration is satisfactory More information on noise is provided in section 4 8 48 This must never occur 179 NOVA Getting started 4 4 Autolab PGSTAT302F information This section provides specific information for the Autolab PGSTAT302F The PGSTAT302F is a special version of the Autolab PGSTAT302N which can be operated in so called floating mode In floating mode the PGSTAT302F can be used to control the potential of grounded working electrodes In this configuration the Autolab is floating with respect to the working electrode sample Additionally the PGSTAT302F can be operated in non floating mode in combination with working electrode disconnected from ground i Warning The floating mode of the special PGSTAT302N must only be used on grounded working electrodes The working electr
123. ectrode connections from the pAutolab are linked to the cell and measurements will not be possible Please note that not only a short circuit or a resistance can make a connection to earth but also a capacitance is capable of providing a conductive path for AC signals The earth connection between the cell and P E should always be broken If there is no possibility of doing this please contact Metrohm Autolab for custom solution if available 4 7 11 Environmental conditions The pAutolab may be used at temperatures of O to 40 degrees Celsius The instrument is calibrated at 25 degrees Celsius and will show minimum errors at that temperature The ventilation hole on the rear panel may never be obstructed nor should the instrument be placed in direct sunlight or near other sources of heat 4 7 12 Noise When measuring low level currents some precautions should be taken in order to minimize noise The personal computer must be placed as far away as possible from the electrochemical cell and the cell cables The cell cables should not cross other electrical cables Other equipment with power supplies can also cause noise For instance the interface for mercury electrodes IME should also be placed with some care If possible place the computer between the pAutolab and other equipments Avoid using unshielded extension cables to the electrodes The use of a Faraday cage is also advised 223 NOVA Getting started If the cell syste
124. einitialized using the updated Hardware setup 94 Page NOVA Getting started 1 6 18 2 Determination of C2 Follow the steps described in this section to determine the value of the C2 parameter 1 Load the procedure PGSTAT C2 calibration from the Module test database 2 Disconnect the Dummy cell and leave the leads open in the Faraday cage CE and RE must be connected together as well as WE and S as shown in Figure 1 110 Make sure RE CE and WE S are not connected together Connect the ground lead from the PGSTAT to the Faraday cage Figure 1 110 Overview of the connection required for the determination of C2 3 Start the measurement and wait until it has been finished Ignore the warning displayed during the procedure validation see Figure 1 111 Validation results _ oOo Bg The following problems were encountered during validation Message Command AUT84842 Bandwidth of selected current range 100 nA is not sufficient for selected frequency 1000 Hz FRA single frequency Bandwidth of selected current range 100 nA is not sufficient for selected frequency 1000 Hz It is possible to continue but the measured data could be invalid Time remaining 10 seconds OK Cancel Figure 1 111 Ignore the warning shown during the validation of the procedure 4 A reminder message is shown at the beginning of the measurement see Figure 1 112 95 Page NOVA Getting started PGSTAT C2 calibr
125. ell in the Faraday cage 20 Please contact your Autolab distributor if you need assistance 91 Page NOVA Getting started Why C1 1yF CE WE S a WE S RE b WE S WE S e c WE S d 1uF 5KQ DUMMY CELL2 Figure 1 104 Overview of the connections required for the determination of C1 4 Start the measurement and wait until it has been finished Ignore the warning displayed during the procedure validation see Figure 1 105 The following problems were encountered during validation Message AUT64642 Time remaining 10 seconds Validation results Bandwidth of selected current range 100 nA is not sufficient for selected frequency 1500 Hz It is possible to continue but the measured data could be Invalid OK Cancel Figure 1 105 Ignore the warning shown during the validation of the procedure 5 A reminder message is shown at the beginning of the measurement see Figure 1 106 92 Page NOVA Getting started PGSTAT C1 calibration Connect the dummy cell e 10 kOhm and place the dummy cell inside a Faraday cage Connectthe green ground lead to the Faraday cage Do NOT connectthe ground lead to the dummy cell Figure 1 106 A reminder message is shown at the beginning of the measurement 6 During the measurement the measured data will be plotted as a Bode plot should be similar to the example shown in Figure 1 107 Phase 10000
126. en the instrument reaches the maximum operating temperature the protection circuit will trigger and the cell will be disconnected The instrument will then enter in predefined safe mode and it will no longer be possible to switch the cell on To reset the instrument the device must be switched off allowed to cool and then switched on again When the temperature overload circuit is triggered the status LED on the front panel of the PGSTAT204 will be lit red and the corresponding indicator in the Autolab display will also be lit see Figure 4 45 Autolab display x a Autolab manual control AUT50001 Status current range Figure 4 45 The T ovl indicator is let when the temperature overload circuit is triggered 215 NOVA Getting started 4 7 uAutolab information This section provides specific information for the uAutolab 4 7 1 Front panel and cell cable connection There is a single connector on the front panel of the pAutolab used to connect the cell cables see Figure 4 46 On Off switch Cell On Off switch Display Cell cable socket Figure 4 46 Overview of the pAutolab The cell cables are labelled as follows e Working or indicator electrode WE red e Reference electrode RE blue e Auxiliary or counter electrode CE black In a two electrode set up the counter and reference electrode lead are both connected to the same electrode see Figure 4 47 64 The yAutolab type
127. ention to adequate shielding of the cell and the electrode connectors The use of a Faraday cage Is recommended in this case 4 3 5 RE input impedance and stability The electrometer RE input contains a small capacitive load If the capacitive part of the impedance between CE and RE is comparatively large phase shifts will occur which can lead to instability problems when working in potentiostatic mode If the 172 NOVA Getting started impedance between the CE and the RE cannot be changed and oscillations are observed it is recommended to select the High stability mode to increase the system stability In general the use of High stability leads to a more stable control loop compared to High speed or Ultra high speed and a significantly lower bandwidth To make use of the full potentiostat bandwidth Ultra high speed mode the impedance between CE and RE has to be lower than 35 kQ This value is derived by testing In galvanostat mode this large impedance between CE and RE will usually not lead to stability problems because of the current feedback regulation 4 3 6 Galvanostatic FRA measurements The capacitive part of the impedance between RE and ground is an important aspect to consider when performing FRA measurements in galvanostat mode Large reference electrode impedance values may introduce a phase shift at low frequencies The origin of the phase shift between the CE and the RE cannot be determined from the FRA d
128. ents Doesn t support 64 bit Windows No further developments are done with this driver Nova only instruments 0 GPES compatible instruments 1 Total number of instruments 1 Figure 1 14 The Driver Manager displays the driver information at the bottom of the window 1 2 5 Multiple instruments When the Driver Manager is used on a computer connected to multiple Autolab devices the drivers will be updated for all the instruments For example Figure 1 15 shows that two instruments are connected to the computer One device is using the NOVA only driver while the other one is using the GPES compatible driver 22 Page NOVA Getting started Select the driver used to control your Autolab instrument Nova only recommended setup Select this driver when you only use Nova 1 7 or higher on your PC Advantages Faster USB data exchange Connect a maximum of 16 Autolab instruments Supports 64 bit Windows Ready for future applications GPES compatible Select this driver when you want to use Nova 1 7 or higher together with Nova 1 6 or lower and or GPES on this PC Restrictions Slower USB data exchange Connect a maximum of 6 Autolab instruments Doesn t support 64 bit Windows No further developments are done with this driver Nova only instruments 1 GPES compatible instruments 1 Total number of instruments 2 Figure 1 15 Using the Driver Manager in combination with multiple instru
129. ep Differential pulse voltammetry square wave voltammetry 2 sampled DC polarography z Chrono amperometry At gt 1 msj gt Chrono potentiometry At gt 1 msj gt Chrono amperometry tast z Chrono potentiometry fast Chrono coulometry fast Chrono amperometry high speed Chrono potentiometry high speed Chrono charge discharge Interrupt Interrupt high speed gt Fositive feedback FRA impedance potentiostatic z FRA impedance qalvanastatic FRA potential scan z standards Fl My procedures vcelie voltammetry potentiostatic 11 3 2011 5 18 49 PM Figure 2 8 Adding the quick start cyclic voltammetry procedure The procedure can now be started Click the Start button located at the bottom of the screen to begin the experiment The procedure is first validated which can take a few seconds depending on the amount of commands in the procedure If no errors are detected the measurement starts The software will automatically switch to the Measurement view where the measured data points are displayed in real time You can also switch to the Measurement view at any time by clicking the measurement view button in the toolbar see Figure 2 9 File View Profile Run Tools Help mE ie S a la MW ale S oe Ee ae co Measurement View Figure 2 9 Switching from the setup view to the measurement view 105 Page NOVA Getting started 2 2 2 Viewing the measured data The measurement vi
130. es may not be connected to safety ground 183 NOVA Getting started Avoid creating ground loops as this will often degrade the performance of the PGSTAT302F 4 4 3 2 Connections for analog signals monitor cable With the supplied monitor cable there are a number of BNC connectors to the PGSTAT analog circuits see Figure 4 19 All the signals are with respect to Autolab ground and indirectly to protective earth when the PGSTAT302F is operated in normal mode These signals are floating when the PGSTAT302F is operated in floating mode Connected equipment may not be connected to ground and the shield of the BNC cables may not be connected to safety ground Avoid creating ground loops as this will often degrade the performance of the PGSTAT302F Figure 4 19 The monitor cable for the PGSTAT302F The following signals are available Eour This output corresponds to the differential potential of S versus RE The output voltage will vary between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load impedance is 200 Q lour This signal corresponds to the output of the current to voltage converter circuit of the PGSTAT A 1 V signal corresponds to 1 x the selected current range The output level varies between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load imped
131. est driver All USE addresses are in use Try using latest driver All USE addresses are in use Try using latest driver All USE addresses are in use Try using latest driver DaAutolab USB connected U3MUT 70530 DAutolab USB connected U3A4UT 70538 i Autolab USB connected u34UT 70532 i Autolab ISB connected u34UT 70534 i Autolab USB connected 4UT83549 4 Autolab USB connected ALT83548 J Autolab USB connected AUT 3547 41 Autolab USB connected ALT83543 NOVA Getting started Time 2 14 42 PH 2 14 43 FM 2 14 43 FM 2 14 43 FM 2 14 47 PH 2 14 46 PR 2 14 48 PR 2 14 48 PR 2 14 49 PR 2 14 49 PR 2 14 50 PR 2 14 52 Pha Date Biegen Bean Bean Biegen Bean bfeafelll 1 Biegen Bean Beal Bean Bf safe 1 Biegen Figure 1 17 Error messages are provided when more than 8 instruments are connected to the same computer using the GPES compatible driver The available instruments will be selected randomly depending on the initialization speed of each Autolab The excess instruments will not be available for measurements More information on the control of multiple instruments in NOVA can be found in the Multi Autolab tutorial available from the Help menu 1 3 Connection to the instrument s When the installation of Nova is finished start the software by double clicking on the Nova shortcut located on the desktop or by clicking the Nova shortcut located in the Start menu Start Al
132. etry galvanostatic e S 0 000 Linear polarization r oe me s Hydrodynamic linear sweep i a Differential pulse voltammetry Her s 5 b Square wave voltammetry i pain iia Sampled DC polarography CV staircase 0 000 1 000 1 000 0 000 2 0 1000000 Chrono amperometry At gt 1 ms i i Chrono potentiometry At gt 1 ms Figure 2 5 Loading a procedure in the Editor frame part 2 Once the procedure is loaded in the procedure editor frame it can be executed This procedure will perform a single potential scan between 1 V and 1 V on the dummy cell starting at a potential of O V with a scan rate of 100 mV s Note In Nova a procedure is defined as the combination of a signal sampler and a series of commands The signal sampler defines which signals current potential time pH will be sampled during the measurement and the commands define how these signals will be sampled When the procedure is loaded in the procedure editor frame it can be modified and started It is convenient to name each experiment in a unique way for bookkeeping purposes To change the name of the cyclic voltammetry potentiostatic procedure to a custom name click the cyclic voltammetry potentiostatic name in the procedure editor and change it to Quick start Cyclic voltammetry see Figure 2 6 NOVA Getting started Commands Parameters Links W Quick start cyclic
133. etry pote X Delete procedure s Linear sweep voltammetry galv x Linear polarization Hydrodynamic linear sweep Differential pulse voltammetry Square wave voltammetry Commands Procedures Time WE 1 Current No Options 7 AUT40008 Load the selected procedure in the procedure setup Export procedure Show in Windows Explorer Figure 2 4 Loading a procedure in the Editor frame part 1 102 Page NOVA Getting started Clicking this instruction will load the procedure in the editor frame The name of procedure will change from New procedure to Cyclic voltammetry potentiostatic Aseries of commands will be displayed under the Cyclic voltammetry potentiostatic procedure in the editor frame see Figure 2 5 These commands form the procedure and will be executed sequentially when the procedure is started File View Profile Run Tools Help DS SR ah P REE co ot ow Commands Procedures Commands Parameters Links Autolab gt Cyclic voltammetry potentiostatic Pony Cyclic voltammetry potentiostatic MAMAI a Remarks Cyclic voltammetry potentiostatic z L Cyclic voltammetry galvanostatic Be enn PL Cyclic voltammetry current integration Signal sampler Time WE 1 Potential WE 1 Current a Cyclic voltammetry linear scan i i nid gt Cyclic voltammetry linear scan high speed spec descrnt Linear sweep voltammetry potentiostatic di pees ates on fe Linear sweep voltamm
134. euseeeesseueeeessaaaeeenes 228 I A E rage ee eects ere serene cesses 229 S4 EU Declaration Of COnTOrMITY au cosidchscadouacnx ss aronanalnensenccueetaradonacextoacuesttes 231 6 NOVA Getting started Introduction Nova is designed to control all the Autolab potentiostat galvanostat instruments with a USB connection It is the successor of the GPES FRA software and integrates two decades of user experience and the latest NET software technology Nova brings more power and more flexibility to the Autolab instrument without any hardware upgrade Nova Is designed to answer the demands of both experienced electrochemists and newcomers alike Setting up an experiment measuring data and performing data analysis to produce publication ready graphs can be done in a few mouse clicks Nova is different from other electrochemical software packages As all electrochemical experiments are different and unique Nova provides an innovative and dynamic working environment capable of adapting itself to fit your experimental requirements The design of Nova is based on the latest object oriented software architecture Nova is designed to give the user total control of the experimental procedure and a complete flexibility in the setup of the experiment This getting started manual provides installation instructions for the Nova software and the Autolab hardware It also includes a quick walkthrough tutorial and a description of the Autolab procedure
135. ew displays the measured data in real time The default display settings for a cyclic voltammetry experiment are the potential Potential applied on the X axis and the measured current on the Y axis WE 1 Current The scale of the plot is automatically adjusted during the measurement When the measurement is running the start button is replaced by a stop button that can be pressed to abort the experiment Figure 2 10 shows the measurement view during the Quick start experiment NOVA o be Toolbar Quick access toolbar E File un Tools Help MeN FE ea mm am a EEEE EE x cu E Quick start cyclic voltammetry 0 001 Autolab control i Set potential 0 0009 Setccell Measurement frame l Wait time s 0 0008 Optimize current range BCV staircase 0 0007 i Set cell 0 0006 Procedure progress z 00005 0 0004 5 Q mi z CV staircase Upper vertex potential V 1 000 Lower vertex potential V 1 000 Stop potential V 0 000 Number of stop crossings 2 Step potential V 0 0022 Parameter editor QUU Scan rate V s 0 2 0 4 0 8 Potential applied V 0 6 User log message Time Date Command i Autolab USB connected AUT40008 10 13 22 1 15 2013 a Stop User log Start Stop button Measuring Intermediate _ Figure 2 10 The Measurement view It is possible at any time to pick the Autolab display option from the View menu or to press the F10
136. ex potential 1 V Stop potential 0 V Number of stop crossings 2 Step potential 2 44 mV Scan rate 100 mV s 9 O 2 Figure 3 3 shows an overview of the Cyclic voltammetry potentiostatic procedure 126 NOVA Getting started Commands Parameters Links Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry potentiostatic m End status Autolab m Signal sampler Time WE 1 Potential WE 1 Current m Options 1 Options al Instrument AUT40008 Instrument description Autolab control z Set potential 0 000 Set cell On Wait time s 5 Optimize current range 5 E CV staircase 0 000 1 000 1 000 0 000 2 0 1000000 Start potential V 0 000 Upper vertex potential V 1 000 Lower vertex potential V 1 000 stop potential V 0 000 Number of stop crossings 2 step potential V 0 00244 Scan rate V s 0 1000000 Estimated number of points 1650 Interval time s 0 024400 Signal sampler Time WE 1 Potential WE 1 Current m Options 1 Options Potential applied lt _array gt V Time lt _ amay gt 5 WE 1 Current lt _ array gt A Scan lt aray WE 1 Potential lt _ array gt V Index lt aray E i vs E z Set cell Off lt _ gt Figure 3 3 The Cyclic voltammetry potentiostatic procedure The signals sampled during this procedure are e Potential applied e Time e WE 1 Current e Scan e WE 1 Potential e Index The procedure uses the Automatic current ranging optio
137. f the instrument and the OK button in the Nova options window to complete the installation of the FRA2 module calibration file If a calibration file was previously imported in Nova an overwrite warning will be displayed Click the Yes button to confirm the replacement of the file see Figure 1 28 Import FRA2 Calibration FRA2 calibration data has been imported before If you overwrite the previous FRA2 calibration data will be lost Do you want to overwrite Figure 1 28 Replacement of a previously defined fra2cal ini file 8 See the front panel of the instrument NOVA Getting started i Note The FRA2 calibration file is saved in the hardware setup file of the connected instrument This calibration data will be automatically whenever the instrument is connected to the computer A Warning Depending of the type of FRA2 module the FRA offset DAC range needs to be adjusted to the correct value FRA2 modules labeled FRA2 V10 on the front panel must be set to 10V offset DAC range FRA2 modules labeled FRA2 on the front panel must be set to 5V see Figure 1 36 This does not apply to FRA2 modules installed in the pAutolab type Ill for which this field is greyed out i Note Some FRA2 modules originally fitted with a 5V range have been modified to the 10V range for special applications Hardware setup AUT84530 _ O Eg File Tools Main Module Additional Module s E2 _ PGSTAT3
138. g electrode is scanning between 1 V and 1 V The potential between the counter electrode and the working electrode is recorded by the pX pX1000 module At the end of the measurement switch to the Analysis view and load the data for evaluation 80 NOVA Getting started The data set includes two groups of data points see Figure 1 92 Testox1000 B Testp1000 Measured data H p lt 000 Voltage vs E Measured data TestpX1000 Reference data px 000 Voltage vs E Reference data Figure 1 92 The data obtained with the TestpX TestpX1000 procedure The data for the TestpX is displayed in a similar way The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 93 pall Voltage vy 1 0 5 J Tis Fotential applied W Figure 1 93 The expected result of the TestpX or the TestpX1000 procedure The test is successful if the measured data can be compared to the reference data 81 NOVA Getting started 1 6 15 Test of the SCANGEN or the SCAN250 Two procedures TestsCANGEN and TestSCAN250 can be used to test the correct functionality of the linear scan generator module SCANGEN or SCAN250 respectively Load the TestSCANGEN or the TestSCAN250 procedur
139. ger application see Figure 1 7 gt Driver Manager O Select the driver used to control your Autolab instrument Nova only recommended setup Select this driver when you only use Nova 1 7 or higher on your PC Advantages Faster USB data exchange Connect a maximum of 16 Autolab instruments Supports 64 bit Windows Ready for future applications GPES compatible Select this driver when you want to use Nova 1 7 or higher together with Nova 1 6 or lower and or GPES on this PC Restrictions Slower USB data exchange Connect a maximum of 8 Autolab instruments Doesn t support 64 bit Windows No further developments are done with this driver Nova only instruments 0 GPES compatible instruments 0 Total number of instruments 1 Figure 1 7 The driver manager application ry an P DAANA allie Gadauyt NOVA Getting started The Driver Manager can be used at any time to select the driver to use to control the Autolab Two drivers are available e NOVA only recommended setup this is the latest driver for the Autolab allowing up to 16 instruments to be connected to the computer and faster data transfer This driver is compatible with 64 Bit versions of Windows e GPES compatible this is an older driver version No further developments are planned for this driver The maximum number of devices connected to the same c
140. ggestion is shown in the user log 4 4 9 Oscillation detection The PGSTAT302F has a detector for large amplitude oscillation The detector will spot any signal swing that causes the control amplifier to produce both a positive and a negative Voltage overload within 200 us Thus large oscillations at frequencies gt 2 5 kHz will be detected Upon oscillation the OSC indicator on the PGSTAT front panel will be activated The Vow warning will also be shown in the Autolab display An oscillation protection feature can be enabled or disabled in the software using the Auto ab control command see Figure 4 26 190 NOVA Getting started i here Autolab control 0 J PGSTAT302F lt Basic DIO AJ Advanced ay External input m Off Oscillation protection on a an Reference potential Offset potential 0 V DACI64 1 O0 V Figure 4 26 The Autolab control window can be used to switch the oscillation protection on or off If the oscillation protection is enabled the occurrence of oscillation will also immediately turn off the manual cell switch of the Autolab When this happens both the OSC indicator and the manual cell switch start blinking The Autolab display will show the message Cell manually off see Figure 4 27 Autolab display x a Autolab manual control AUT85189 status cell manually off current range es ee Figure 4 27 The cell manually off is displayed when the oscillation protection c
141. h extended with one decade up to 125 kHz Some cells can show ringing or oscillation using this setting particularly highly capacitive cells in PSTAT mode Increasing the bandwidth also increases the noise levels for the i and E signals The High speed mode is automatically selected during impedance measurement at frequencies gt 10 kHz It is possible to switch from High stability to High speed by clicking the HSTAB label in the Autolab display In High speed mode this label will be unlit both on the front panel of the PGSTAT and on the Autolab display Clicking the HSTAB label again switches the bandwidth back to High stability For applications requiring very high bandwidth the Ultra high speed mode can be selected In this mode the control amplifier bandwidth is extended to 500 kHz PGSTAT12 PGSTAT128N PGSTAT100 and PGSTAT100N or 1 25 MHz PGSTAT30 PGSTAT302 and PGSTAT302N There is a significant oscillation risk using this setting and the noise levels will generally show an increase relative to the High speed or High stability mode The Ultra high speed mode is automatically selected during impedance measurements at frequencies gt 100 kHz while the High stability mode is selected for frequencies below 10 kHz see Figure 4 11 High speed 10 kHz 100 kHz High stability Ultra high speed Figure 4 11 Bandwidth limits in the Autolab PGSTAT i Warning The higher the bandwidth the more important it is to pay att
142. he inputs of the summation point 36 This input is connected to the FRA32M or the FRA2 module 37 Or earlier version SCANGEN 3 Offset DAC SCAN250 SCANGEN and Ej are not available on the wAutolab _ il SCAN250 SCANGEN FRA DSG and En are not available on the PGSTAT101 SCAN250 SCANGEN and Ein are not available on the M101 module 158 Page NOVA Getting started The control amplifier provides the output voltage on the counter electrode CE with respect to the working electrode WE required to keep the potential difference between the reference electrode RE and the sense S at the user defined value in potentiostatic mode or the user required current between the counter electrode CE and the working electrode WE in galvanostatic mode The output of the control amplifier can be manually or remotely disconnected from the electrochemical cell through a cell ON OFF switch The voltage follower VF is used to measure the potential difference between the reference electrode and the sense and the current follower CF The current follower has several current ranges providing different current to voltage conversion factors The output of the CF and the VF are fed back to the analog to digital converter modules of the Autolab e ADC164 e FRA ADC e ADCIOM e FI20 Furthermore the output of the VF or the CF is fed back to the summation point to close the feedback loop in potentiostatic or galvanostatic mode respectively The ADC
143. he list of functions to locate the 10LOG function and double click it to add it to the expression builder see Figure 2 31 117 NOVA Getting started Fil Calculate signal 9 Name log l L Single value Unit v Expression Parameters signals Full CV staircase ASINH Clear OK Cancel Figure 2 31 Creating the log i signal part 1 Defining the expression Next double click the ABS function located under the 10LOG function in order to add it to the expression Finally in the expression change the parameter 1 text to i and click the parameters frame in the expression builder The expression builder will identify the parameter i as the only parameter of the expression This parameter will be displayed in the Parameters frame see Figure 2 32 118 Page NOVA Getting started El Calculate signal Oo Name log i Single value Unit v Expression 10LOG ABS i Parameters Functions Ces signals Full CV staircase Clear Figure 2 32 Creating the log i signal part 2 Identifying the parameters of the expression The final step in the expression building process consists in linking the parameter s of the expression to existing signal s Expand the CV staircase list of available signals and double click the WE 1 Current signal t
144. he result of an automatic fit of the impedance data with the R RC equivalent circuit see Figure 1 85 NOVA Getting started al ai TestFRA la FRA measurement potentiostatic G FRA frequency scan O Nyquist 2 vs 2 H Bode modulus H Bode phase Test FRA Results B Fitand Simulation Gl Myquist 2 vs Z H Bode modulus H Bode phase He Residual 2 H Residual 2 Convergence Yes Number of iterations 23 2 ve 0 00026901 2 ve Circuit RRC 2 ve Rp R 994 050 9 2 ve CdlC 955 700 nF an Rs R 99 9940 EH H I Figure 1 85 The data obtained with the TestFRA procedure The value of Rs Rp Cdl and x displayed in the explorer frame Select the Fit and Simulation item in the data explorer and click the button located on the left hand side of the plot area to open the Equivalent Circuit Editor window see Figure 1 86 Maximum number of iterations Circuit RRC Maximum change in x scaled 0 001 Max iterations without improvement 50 Fitting style Impedance W Use weightfactor Fit or Simulation Fit w Measurement data format Impedance a Number of significant digits 5 Figure 1 86 Opening the results of the Fitting of the data The results of the calculation are graphically shown in the Equivalent Circuit Editor Select the Generate Report option from the Tools menu to display a short report table for the fitted data see Figure 1 87 The values shown in the last column c
145. his device software Name Metrohm Autolab B V Universal Serial Bu a Publisher Metrohm Autolab B W Always trust software from Metrohm Autolab Install Don t Install BV p P You should only install driwer software from publishers you trust How can decide which device software is safe to install Figure 1 9 Click the stall button to install the driver software When the driver installation is completed a message will be displayed see Figure 1 10 Done The used driver has successfully been updated ok Figure 1 10 A message is displayed when the installation of the driver is finished 1 2 4 GPES FRA and older NOVA versions compatibility The driver installation description provided in the previous section installs NOVA only drivers on the computer These drivers are not compatible with the old Autolab GPES or FRA software and with previous versions of NOVA NOVA 1 6 and older If no connection can be established with the Autolab when using GPES FRA or older versions of NOVA check the selected driver using the Autolab Driver Manager If necessary it is possible to use the GPES compatible driver This driver can be selected at any time using the Autolab Driver Manager installed on the computer gt Read this section carefully if you are using GPES FRA or older versions of NOVA on the same computer 19 NOVA Getting started The Driver Manager is displayed in Figure 1 11
146. his signal corresponds to the output of the current to voltage converter circuit of the PGSTAT A 1 V signal corresponds to 1 x the selected current range The output level varies between 10 V The output impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load impedance is 200 Q Ew This is an analog voltage input that can only be used after it has been enabled in software using the Auto ab contro command see Figure 4 8 Do not leave it enabled unnecessarily to prevent noise pickup by the system This input is directly connected to the summation point of the PGSTAT In PSTAT mode a 4 gt The Eout value corresponds to WE 1 Potential 169 Page NOVA Getting started 1 V signal will add 1 V to the cell voltage while in GSTAT mode a 1 V signal adds an extra current of 1 x the selected current range to flow In both cases the external signal adds to any pre defined voltage or current The input voltage range is 10 V Input impedance is 1 KQ only when input is activated so a correction should be made when the source impedance is gt 1 Q Autolab control 0 J PGSTAT302N lt Y Basic DIO A Advanced aioa External input On a Oscillation protection off Reference potential 0 V Offset potential 0 V DAC164 1 O0 V Figure 4 8 The external input is enabled in the Autolab control window 4 3 4 High stability High speed and Ultra high speed The PGSTAT
147. i AC vs E AC Switch the measurement view to Four plots mode by pressing the button in the toolbar 74 NOVA Getting started 400 M 300 md 100 0 100 200 400 E00 1000 10000 Tio Frequency Hz 100 100 2E 5 z iL z T 1E 5 A E N at E a 7 WA gt g 4 D 50 50 z SR 5 5 A 7 2E 5 100 100 0 05 0 1 0 01 0 0 01 Time domain s Potential AC Vv Figure 1 83 The measured values are displayed as a Nyquist plot plot 1 Bode plot plot 2 Resolution plot vs time plot 3 and Lissajous plot plot 4 At the end of the measurement the data is automatically fitted using a R RC equivalent circuit and the calculated values of the circuit elements are displayed in a message box see Figure 1 84 TestFRA results Evaluation Fitted values Reference values R1 99 531 0 100 9 R2 995 3 0 1000 0 C 9 7986E 07 F 1 uF x2 0 00026048 lt 0 001 Figure 1 84 The fitted values are shown in a message box at the end of the measurement the reference values are shown in round brackets Reference values are shown in round brackets in the message box The resistance values should be within 1 of the reference value and the capacitance value should be within 5 of the reference value The calculated y value should be smaller than 0 001 Switch to the Analysis view to inspect the measured and fitted data in detail The data set includes the measured data points and t
148. ial applied W Figure 1 52 The expected result of the TestCV PGSTAT101 procedure The test is successful if the measured data can be compared to the reference data 1 6 1 3 Test of the Autolab PGSTAT302F in floating mode This simple test is designed to verify the basic functionality of the Autolab PGSTAT302F in floating mode only Load the TestCV PGSTAT302F procedure from the Standards database connect dummy cell a as shown in Figure 1 53 and press the start button 1e For testing the PGSTAT101 and the M101 module please refer to Section 1 6 1 2 For testing all the other Autolab instruments including the PGSTAT302F in normal mode please refer to Section 1 6 1 1 52 NOVA Getting started AUTOLAB WE S cE a WE S RE b WE S e WE S c WE S d 1uF OkQ MIF DUMMY CELL2 Figure 1 53 The connections to the dummy cell a required to test the PGSTAT302F in floating mode A message will be displayed when the measurement starts see Figure 1 54 TestCV PGSTAT302F This testis designed to verify the basic functionality of the Autolab PGSTAT302F in floating mode Connect dummy cell a connectthe ground cable to the WE and press OK to continue Data evaluation should be cared out in the Analysis view Figure 1 54 A message is displayed at the beginning of the measurement The test uses the cyclic voltammetry staircase method and performs a single potent
149. ial scan starting from O V between 1 V and 1V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes three groups of data points see Figure 1 55 NOVA Getting started Gal z TestlY PGSTAT302F esty PasTATs0eF Measured data b vs E Measured data H Residual plot Measured dataj E TestC Y PGS TAT 302F Reterence data E v5 E Reference dataj H Residual plot Reference data 5 i Limits i Upper limit ve Lower limit a oper limit EH Lower limit Figure 1 55 The data obtained with the TestCV procedure The first group located under TestCV PGSTAT302F Measured data contains the measured curve and the data after baseline correction The second group located under TestCV PGSTAT302F Reference data contains data from a reference measurement This data can be used for comparison with the data points obtained during the test Two reference curves are provided the i vs E plot and the Residual plot after baseline correction The third group located under Limits contains the absolute maximum and minimum limit allowed for the residual current calculated from the measured data points Figure 1 56 shows an overlay of the residual current calculated from the measured data the residual current plot provided as reference data and the absolute limits allowed for the residual current 54 NOVA Getting started 20 000 n
150. iment in potentiostatic conditions The procedure parameters e Preconditioning potential O V e Duration 5s e CV Staircase o Start potential 0 V Stop potential 1 V O o Step potential 2 44 mV O Scan rate 100 mV s has the following Figure 3 7 shows an overview of the Linear sweep voltammetry potentiostatic procedure Commands Parameters Links Linear sweep voltammetry potentiostatic Remarks End status Autolab Signal sampler Options Instrument Instrument description Autolab control Set potential Set cell Wait time s Optimize current range E LSV staircase start potential V stop potential V step potential Vv Scan rate V s Estimated number of points Interval time s Signal sampler Options Potential applied Time WE 1 Current WE 1 Potential Index ivs E H Set cell gt H H Linear sweep voltammetry potentiostatic Time WE 1 Potential WE 1 Current 1 Options AUT40008 0 000 1 000 0 7000000 0 000 1 000 0 00244 0 1000000 0 024400 Time WE 1 Potential WE 1 Current 1 Options lt _amay gt v lt _amay gt s lt _amay gt A lt _ array gt V lt _amay gt Off ees es Figure 3 7 The Linear sweep voltammetry potentiostatic procedure 132 Page NOVA Getting started The signals sampled during this procedure are e Potential applied e Time e WE 1 Current e WE 1 Potential e Index The procedure
151. ing the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 70 64 NOVA Getting started 1 0 5 J 0 5 Potential applied Vv Figure 1 70 The expected result of the TestECD procedure The test is successful if the measured data can be compared to the reference data 1 6 8 Test of ECN The TestECN procedure can be used to test the correct functionality of the ECN module Load the TestECN procedure connect the ECN cable to the gt E input of the ECN module Connect the red plug of the ECN cable to dummy cell a Connect the black plug of the ECN cable to the CE connector of the dummy cell Connect the RE CE and S and WE from the PGSTAT to dummy cell a see Figure 1 71 65 NOVA Getting started To gt E ECN To gt E ECN HWE S ale pF 5kQ DUMMY CELL2 Figure 1 71 Overview of the connections to the dummy cell required for the TestECN procedure Press the start button to start the measurement A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the working electrode is scanning between 1 V and 1 V The potential between the counter electrode and the working electrode is recorded by the ECN module At the end of the measurement switch to the Analysis view and load the data for evaluation The data
152. instrument Instrument serial number USB serial number Identified as AUT960512 USB70128 USB70128 AUT71024 USB70256 AUT71024 AUT72048 Internal AUT72048 AUT84096 Internal AUT84096 U2AUT70256 USB70512 USB70512 U3AUT70384 Internal U3AUT70384 AUT40064 Internal AUT40064 AUT50450 Internal AUT50450 Table 1 1 Autolab and USB interface serial number identification examples This does not apply to the Multi Autolab cabinet see Section 1 3 2 for more information 27 NOVA Getting started 1 3 2 Connection and identification of the Multi Autolab M101 modules installed in a Multi Autolab cabinet connected to the computer are identified by a unique composite serial number after the initialization process The serial number depends on the position of each module in the cabinet as shown in Figure 1 21 A B Or muoie C D E F 1 2 3 4 5 6 Figure 1 21 Overview of the Multi Autolab with M101 modules the module bay labels are indicated by the arrows Positions 1 to 6 are known as Parent positions Positions A to F are daughter positions Each M101 module in the cabinet is identified by a unique serial number defined by the position of the module and the serial number of the Multi Autolab cabinet see Table 1 2 Instrument serial number USB serial number Identified as MAC80001 1 6 MAC80001 Internal eas Parent positions MAC80001 Internal mcmama Daughter positions Table 1 2 Multi Autolab seria
153. integration Options No Options ma Cyclic voltammetry linear scan n ioi l Instrument AUT40008 Cyclic voltammetry linear scan high speed _ re Instrument description Linear sweep voltammetry potentiostatic ho Linear sweep voltammetry galvanostatic Linear polarization Hydrodynamic linear sweep gt Differential pulse voltammetry Square wave voltammetry j Sampled DC polarography Chrono amperometry At gt 1 ms ho Chrono potentiometry At gt 1 ms Chrono amperometry fast Chrono potentiometry fast Chrono coulometry fast Chrono amperometry high speed Chrono potentiometry high speed Chrono charge discharge Hnterrupt I i Interrupt high speed i Positive feedback FRA impedance potentiostatic gt FRA impedance galvanostatic FRA potential scan Standards i My procedures Figure 2 2 Details of the Setup view The procedures visible in the Autolab group in the browser are standard factory procedures These procedures are always visible and cannot be changed or removed Note The actual number of procedures listed in the Autolab group of procedures in the Setup view depends on the active profile By default the Cyclic voltammetry potentiostatic procedure should be visible in this group unless it has been hidden on purpose Please refer to the User manual for more information on the use of profiles in Nova 2 2 Running cyclic voltammetry on the
154. ion Hardware Tags None Profile Tags Basic Application Tags Corrosion The Linear polarization procedure measures the OCP potential using the OCP determination command for the sample and then uses the Set reference potential command set the potential values of the linear sweep voltammetry relative to the averaged OCP a moving average of 5 seconds is used The Linear polarization procedure has the following parameters e Measure OCP for 120 seconds with cutoff when dOCP dt lt 1 uV s e Preconditioning potential 100 mV vs OCP e Duration 5s e LSV Staircase o Start potential 100 mV vs OCP Stop potential 100 mV vs OCP Step potential 1 mV Scan rate 1 mV s 0O Figure 3 11 shows an overview of the Linear polarization procedure 31 Please refer to the Open circuit potential Tutorial available from the Help menu for more information on the OCP determination command 136 NOVA Getting started Commands Parameters Links Remarks Linear polarization m End status Autolab ax Signal sampler Time WE 1 Potential WE 1 Current Options 1 Options m Instrument AUT40008 Instrument description Autolab control m OCF determination 0 000 7 Set reference potential 0 000 Set potential 0 100 Set cell On m Wait time s S Optimize current range 5 El LSV staircase 0 100 0 100 0 0070000 Start potential V 0 100 stop potential v 0 100 step potential V 0 00700 Scan rate V s 0 0010000 Estimated
155. ion mbedded Processor Test H A Embedded Processor Test icense information License information EProm Test EProm Test imer Test imer Test utolab Test W Autolab Test D Converter Test WW AD Converter Test W K m AAA Pe P RIERREN P P m DA Converter Test DA Converter Test Fotentiostat Test Potentiostat Test Noise Test A Noise Test Galvanostat Test H W Galvanostat Test FR ER ER EE HEE Progress sa SSS Figure 1 36 A failed test will be indicated in the diagnostics tool It is possible to print the test report or to save it as a text file by using the File menu and selecting the appropriate action see Figure 1 37 40 Page NOVA Getting started Diagnostics AUT83071 O ES Edit Tools Save Report As Results Print Report E A Windows Information G WF Embedded Processor Test EW af License information H A FEProm Test Exit EProm Test imer Test utolab Test D Converter Test DA Converter Test Potentiostat Test Noise Test Galvanostat Test 4 A Timer Test m A Autolab Test KIKKI brm H A AD Converter Test H A DA Converter Test W Fotentiostat Test H A Noise Test W Galvanostat Test H H E A E H Progress SS Figure 1 37 It is possible to save or print the diagnostics report At the end of the test it is possible to perform the diagnostics test on another device if applicable Use the Select instrument option from the Edi
156. ircuit is triggered 191 P NOVA Getting started The cell may be switched on again by pressing the manual cell switch button If oscillation resumes the cell switch will be turned off as soon as the button is released Holding the button pressed in provides an opportunity to observe the system during oscillation Some cells that cause ringing when switching the cell on or changing the current range can falsely trigger the oscillation detector If this happens the Oscillation protection may be switched off in the software in order to prevent an accidental disconnection of the cell 4 4 10 Maximum reference electrode voltage The differential electrometer input contains an input protection circuitry that becomes active after crossing the 10 V limit This is implemented to avoid electrometer damage Please note that the Vow indicator will not light up for this type of voltage overload The measured voltage will be cutoff at an absolute value of 10 00 V Depending on the cell properties galvanostatic control of the cell could lead to a potential difference between the RE and the S WE larger than 10 V This situation will trigger the cutoff of the measured voltage to prevent overloading the differential amplifier 4 4 11 Active cells Some electrochemical cells such as batteries and fuel cells are capable of delivering power to the PGSTAT302F This is allowed only to a maximum cell power Pmax of 20 W This means that
157. ircuit plug 193 Page NOVA Getting started 4 4 13 Environmental conditions The PGSTAT302F may be used at temperatures of O to 40 degrees Celsius The instrument is calibrated at 25 degrees Celsius and will show minimum errors at that temperature The ventilation holes on the bottom plate and on the rear panel may never be obstructed nor should the instrument be placed in direct sunlight or near other sources of heat 4 4 14 Temperature overload As a safety precaution the PGSTAT302F is equipped with a circuit that monitors the temperature of the internal power electronics A temperature overload will be displayed as a blinking indicator in the manual cell switch with the cell automatically turned off You will not be able to turn the cell back on until the temperature inside the instrument has fallen to an acceptable level It can then be switched on again by pressing the manual cell switch button on the front panel During normal operation the temperature should never become extremely high and no temperature overload will occur If this does happen the origin of the temperature overload should be identified Is the room temperature unusually high Was the PGSTAT oscillating Is the voltage selector for mains power set to the right value Is the fan turning and are all the ventilation holes unobstructed Was the cell delivering a considerable amount of power to the PGSTAT Are the WE and CE cables shorted in PSTAT mode
158. ise ratio can readily indicate whether or not a configuration is satisfactory More information on noise is provided in section 4 8 205 NOVA Getting started 4 6 Autolab PGSTAT204 information This section provides specific information for the Autolab PGSTAT204 4 6 1 Front panel and cell cable connections The PGSTAT204 potentiostat galvanostat module is installed into the Autolab PGSTAT204 instrument alongside one optional module From the front view the PGSTAT204 module is always installed in the leftmost module bay There are three connectors on the front panel of the PGSTAT204 module see Figure 4 38 POTENTIOSTAT GALVANOSTAT bd N e lt a a x e Figure 4 38 Overview of the PGSTAT204 module front The cell cable should be plugged into the lowest socket labelled by the symbol on the front panel of the PGSTAT204 module The I O socket on the front panel can be used to connect the optional I O cable The DIO cable used to connect to the optional IME663 or IME303 or for TTL triggering can be connected to the DIO connector on the front panel 206 C J C NOVA Getting started The cell cable is labelled as follows e Working or indicator electrode WE red e Sense electrode S red e Reference electrode RE blue e Auxiliary or counter electrode CE black An additional ground connection for shielding purposes e g a Faraday cage is also provided with the cell cable
159. l Programs Autolab Nova or by using the shortcut tile on the Windows 8 Menu see Figure 1 18 Driver Manager Diagnostics 1 10 1 10 Figure 1 18 Use the shortcut tile to start NOVA Upgrade files to Nova 1 10 25 NOVA Getting started The software will start and will initiate communication with all the connected instruments see Figure 1 19 The upload dialog indicates the USB driver used to control the instrument GPES for the GPES compatible driver and NOVA for the Nova only driver Please refer to Section 1 2 5 for more information on the two drivers that can be used to control the Autolab Autolab interface Connected devices 0 NOVA 1 Uploading firmware spun a Autolab interface Connected devices W3AUT 0530 Version 3 1 4 58 19953 Senal no pS3AUT 0530 sp Nag Figure 1 19 Autolab initialization top NOVA only driver in use bottom finished initialization The initialization can take a few seconds When it is completed the serial number of the connected instrument should be displayed together with the version of the control software see Figure 1 19 During the initialization of the instruments Nova will try to automatically configure each device by detecting the installed modules and type of instrument This automatic configuration will be triggered whenever an instrument is connected for the very first time The information about this process is provided in
160. l number identification example gt This applies to the Multi Autolab cabinet only see Section 1 3 1 for more information on the other instruments Please refer to the Multi Autolab tutorial available from the Help menu for more information 28 NOVA Getting started 1 3 3 Hardware setup After the software has started you should see the following screen which is called the Setup view see Figure 1 22 avd NOVA 0 File View Profile Run Tools Help mee TW Siete e ah Options Ee EE Commands Procedures ij Database Manager ommands Parameters Links Autolab EJ Check Procedure Alt F1 Cyclic voltammetry potentio aes i Cyclic voltammetry galvana eae N ee ol Cycli i pH Calibration pler Time WE 1 Current i Cyclic voltammetry current ile S A 3 Options No Options b Cyclic voltammetry linear scan Pog Instrument AUT40008 i Cyclic voltammetry linear scan high speed are a Instrument description Linear sweep voltammetry potentiostatic xI Linear sweep voltammetry galvanostatic p Linear polarization Hydrodynamic linear sweep z Differential pulse voltammetry Square wave voltammetry j Sampled DC polarography s Chrono amperometry At gt 1 ms _ Chrono potentiometry At gt 1 ms z Chrono amperometry fast Chrono potentiometry fast Chrono coulometry fast Chrono amperometry high speed Chrono potentiometry high speed s Chrono charg
161. lectrodes QCM crystals etc are not covered by the warranty If damage of the packaging is evident on receipt of the goods or if the goods show signs of transport damage after unpacking the carrier must be informed NOVA Getting started immediately and a written damage report is demanded Lack of an official damage report releases Metrohm Autolab from any liability to pay compensation If any instruments or parts have to be returned the original packaging should be used This applies to all instruments electrodes cells and other parts If the original packaging is not available it can be ordered at Metrohm Autolab or at your local distributor For damage that arises as a result of non compliance with these instructions no warranty responsibility whatsoever will be accepted by Metrohm Autolab Do not modify the cell cable or the differential amplifier cable connectors These cables are designed for the best possible operation Modifications of these connections i e with other connectors will lead to the loss of any warranty 230 NOVA Getting started 5 4 EU Declaration of conformity Declaration of Conformity This is to certify the conformity to the standard specifications for electrical appliances and accessories as well as to the standard specifications for security and to system validation issued by the manufacturing company Name of commodity Metrohm Autolab B V Utrecht The Netherlands AUTOLAB info metrohm aut
162. lled with respect to the potential of WE 1 with a potential offset of 1 V At the end of the measurement switch to the Analysis view and load the data for evaluation 17 If the BIPOT module is equipped with a switch on the front panel of the instrument the TestBIPOT can be used to test the bipotentiostat mode and the TestARRAY can be used to test the scanning bipotentiostat mode 61 NOVA Getting started The data set includes two groups of data points see Figure 1 65 a Ww TestARRAY a TestARRAY Measured data oe WE vs E Scanning bipot mode Measured data b estARRAY Reference data a EA vs E Scanning bipot mode Reference data Figure 1 65 The data obtained with the TestARRAY procedure The first group contains the measured data points The other group contains data points for the WE 2 Current from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 66 ZE 6 1 5E 6 IEG WE 2 Current tA Ee 1 0 5 J ORs Potential applied Vv Figure 1 66 The expected result of the TestARRAY procedure The test is successful if the measured data can be compared to the reference data 1 6 6 Test of the Booster10A and the Booster20A The TestBooster10A and TestBooster20A procedures can be used to test the correct functionality of the Booster10A a
163. loop 171 186 201 210 Feedthrough 225 FI20 159 Filter 159 Floating 180 Floating mode 52 Forced convection 124 138 Four electrode configuration 166 181 196 198 207 Fourth electrode 166 181 196 198 207 FRA compatibility 19 FRA2 155 158 159 173 188 FRA2 124 FRA2 calibration 31 89 91 95 FRA32M calibration 89 91 95 Frequency scan 156 Gain 159 163 Glove box 225 GPES compatibility 19 Ground 181 Ground loop 168 184 198 208 Grounded cells 178 180 205 214 223 Grounded working electrode 180 Grounding 179 195 205 215 Hardware configuration 29 Hardware setup 25 30 High frequency measurement 164 High scan rate 164 High speed 147 170 172 200 201 209 210 218 High stability 170 172 200 201 209 210 218 Host PC 161 HSPEED 170 200 209 218 HSTAB 170 200 209 218 Hydrodynamic experiments 124 Hydrodynamic linear sweep voltammetry 138 i Interrupt 124 I Interrupt method 154 IME 179 194 205 215 IME303 141 160 IME663 141 160 Impedance 124 155 159 173 188 Interval time 142 144 151 163 lout 169 184 199 209 IR compensation 173 188 202 211 Linear polarization 124 136 Linear scan cyclic voltammetry 124 Linear sweep voltammetry 136 Linear sweep voltammetry galvanostatic 124 134 Linear sweep voltammetry potentiostatic 132 Linear sweep voltammetry staircase 124 Linearity of current range
164. m bandwidth is 300 kHz lour This signal corresponds to the inverted output of the current to voltage converter circuit of the PGSTAT204 A 1 V signal corresponds to 1 x the selected current range The output level varies between 10 V The output 60 The Eout value corresponds to WE 1 Potential 61 The iout Value corresponds to WE 1 Current Current range 208 Page NOVA Getting started impedance is 50 Q so a correction should be made if a load lt 100 kQ is connected The minimum load impedance is 200 Q Vour This output corresponds to the DAC output It is controlled by software and is meant to be used to control external devices like the rotating speed of a Rotating Disc Electrode RDE The output level varies between 10 V and the output impedance is very low lt 1 Q The output amplifier is capable of providing 5 mA at full scale so load impedance should be gt 2 kQ Vin This input corresponds to the ADC input This input can be used for measuring a second signal The input range is 10 V and the input impedance is 50 Q 4 6 4 High stability High speed and Ultra high speed The PGSTAT204 is equipped with three different bandwidth settings High stability HSTAB High speed and Ultra high speed The bandwidth can be defined using the Autolab control command see Figure 4 41 iv Autolab contro 0 PGSTAT204 lt Basic DIO12 cell lof Integrator l 7 Mode Potentiostatic
165. m has a ground connector it can be connected to the analog ground connector at the front of the pAutolab If a Faraday cage is used it should be connected to this ground connector Some experiments concerning optimization of the signal to noise ratio can readily indicate whether or not a configuration is satisfactory More information on noise is provided in Section 4 8 4 8 Noise considerations The high sensitivity of the Autolab potentiostat galvanostat makes it susceptible to noise pickup In particular the noise coming from the mains power can cause severe disturbance in the measurements 4 8 1 Problems with the reference electrode If the reference electrode is not filled properly with electrolyte solution or when it has for other reasons a very high impedance it will be expressed as noise In most cases the applied potential is not the same as the measured potential Refer to the user manual provided by the reference electrode supplier for more information on the proper care of your reference electrode 4 8 2 Problems with unshielded cables It is not advisable to use unshielded electrode cables Make the connections to the electrodes as close as possible to the electrode itself Avoid the use of unshielded extension cables to the electrodes 4 8 3 Faraday cage The use of a Faraday cage is always recommended It protects the cell from external noise interference Connect the cage to the green ground connector of
166. ment switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 74 a TestFl20 Filter EI TestFl U Filter Measured data fem ives E Measured data a TestFlcl Filter Reference dataj a i vs E Reference data Figure 1 74 The data obtained with the TestFl20 Filter procedure 67 NOVA Getting started The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 75 1E 6 oe WE TD Current A _ eet 1E 6 1 0 5 J ORs Potential applied Vv Figure 1 75 The expected result of the TestFl20 Filter procedure The test is successful if the measured data can be compared to the reference data 1 6 10 Test of FI20 Integrator The TestFl20 Integrator procedure can be used to test the correct functionality of the integrator circuit of the Fl20 Integrator module for the Autolab PGSTAT series except the PGSTAT101 for which a specific test is provided see Section 1 6 11 and the yAutolab II and Ill The Fl20 Integrator needs to be properly calibrated before the test Integrator calibration is performed in the Diagnostics application Please refer to Section 1 5 of the Getting Started manual or the FI20
167. ments will update the driver for all the instruments Clicking either one of the two buttons in the Driver Manager will update the driver for both instruments to NOVA only or GPES compatible depending on the selected driver In Figure 1 16 all the connected instruments have been updated to NOVA only driver 23 Page NOVA Getting started Select the driver used to control your Autolab instrument Nova only recommended setup Select this driver when you only use Nova 1 or higher on your PC Advantages Faster USB data exchange Connect a maximum of 16 Autolab instruments Supports 64 bit Windows Ready for future applications GPES compatible Select this driver when you want to use Nova 1 7 or higher together with Nova 1 6 or lower and or GPES on this PC Restrictions Slower USB data exchange Connect a maximum of 6 Autolab instruments Doesn t support 64 bit Windows No further developments are done with this driver Nova only instruments 2 GPES compatible instruments 0 Total number of instruments 2 Figure 1 16 Updating the driver for all the connected instruments When more than 8 instruments are connected to the same computer through the GPES compatible driver NOVA will initialize the first 8 instruments and will provide a connection error message in the user log for the remaining instruments see Figure 1 17 24 Page User log message All USE addresses are in use Try using lat
168. n and displays the measured data as WE 1 Current vs Potential applied in the measurement view Figure 3 4 shows a measurement on the dummy cell a with the Autolab Cyclic voltammetry potentiostatic procedure 127 Page NOVA Getting started 1 0 5 J OS Potential applied W Figure 3 4 The measured data obtained with the standard dummy cell a with the Cyclic voltammetry potentiostatic procedure 3 2 Cyclic voltammetry galvanostatic Hardware Tags None Profile Tags Basic Application Tags Energy The Cyclic voltammetry galvanostatic procedure is similar to the potentiostatic version It is a typical galvanostatic staircase cyclic voltammetry procedure The procedure has the following parameters e Preconditioning current 0 A e Duration 5 s e CV Staircase O O O O O Start current 0 A Upper vertex current 1 mA Lower vertex current 1 mA Stop current 0 V Number of stop crossings 2 Step current 2 44 pA Scan rate 100 uA s Figure 3 5 shows an overview of the Cyclic voltammetry galvanostatic procedure 128 Commands Cyclic voltammetry galvanostatic NOVA Getting started Parameters Remarks Cyclic voltammetry galvanostatic m End status Autolab axl Signal sampler Time WE 1 Current WE 1 Potential a Options No Options m Instrument AUT40008 Instrument description Autolab control aa Set current 0 000E 00 Set cell On Err Wait time s 5 E CV staircase galvanostatic 0 000E 00
169. nd Booster20A respectively Before these tests can be performed make sure that the hardware setup is defined properly and that the Booster is installed correctly Load the TestBooster10A or TestBooster20A procedure depending on the type of Booster Connect the PGSTAT and the Booster to the special booster test cell Press the start button to begin the measurement 62 NOVA Getting Started A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the working electrode is scanning between 1 V and 1 V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 67 estBooster 1A a Testbooster UA Measured dataj fem ives E Measured data a Testboosterl UA Reference cata a ivs E Reference data Figure 1 67 The data obtained with the TestBooster10A procedure The data for the TestBooster20A is displayed in a similar way The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 68 Small deviation can be observed between the measured data points
170. nstallation of Nova A progress bar will be displayed during the installation When the software setup is completed the Installation Complete window will appear see Figure 1 5 Click the button to finish the installation process 14 NOVA Getting started ff Nova 1 10 O Installation Complete Mowa 1 10 has been successfully installed Click Close to exit Flease use Windows Update to check for any critical updates to the NET Framework Cancel lt Back Close Figure 1 5 Installation finished A shortcut to Nova will be added to your desktop or on the Windows 8 menu 1 2 3 USB Drivers installation After Nova has been successfully installed connect the Autolab instrument to the computer using an available USB port Switch on the instrument Windows will attempt to find a suitable driver for the instrument Since the Autolab is not automatically recognized by Windows no drivers will be installed at this point Start the Autolab Driver manager application by using the shortcut provided in the Start menu All Programs Autolab Tools Driver manager 1 10 or by using the shortcut tile on the Windows 8 Menu see Figure 1 6 15 NOVA Getting started Driver Manager Upgrade files to Nova 1 10 Diagnostics 1 10 1 10 b Nova 1 10 Figure 1 6 Use the shortcut tile to start the Driver Manager application This will start the Driver Mana
171. o link it to the parameter I see Figure 2 33 119 Page NOVA Getting started El Calculate signal Oo Name log i C1Single value Unt Expression 10LOG ABS i Parameters Functions Signals Full CV staircase Potential applied Time WE 1 Current i Clear am E pe Figure 2 33 Creating the log i signal part 3 Linking the parameters of the expression to the available signals The linked parameter will be displayed between brackets next to the name of the signal The name of the signal will be displayed in red indicating that it is linked to a parameter see Figure 2 34 ey LY staircase Figure 2 34 A detailed view of the expression builder 120 Page NOVA Getting started Click the OK button to finish the calculation of the new signal The contents of the data grid will be updated indicating that the new signal has been added to the list of available signals see Figure 2 35 The expression used to calculate this signal is displayed in the calculation frame 7 Potential applied V WE 1 Potential v Time s WE 1 Current A Scan Index logi CoAT C a jomas somes O l1 3 lsa noors Joooeosess eyes zewo i fa amr C O O E a ooa fomes feme ames ms oos lesmas ases io y a ooms oors fess fisse h fe farus C a O E 0 0219727 0 0227722 6 89106 2 12971E 5 10 46 178
172. ode can be grounded using the green ground connector embedded in the CE WE cable of the PGSTAT302F A Warning Instrument performance can be substantially degraded when the PGSTAT302F is operated in floating mode The instrument specifications provided by Metrohm Autolab can only be achieved when the PGSTAT302F is used in non floating mode Special precautions must be taken with the cell connections when the PGSTAT302F is used in floating mode Only the working electrode can be connected to ground all other electrodes must be isolated from ground External equipments connected to the PGSTAT302F must be isolated when the instrument is used in floating mode Keep in mind that grounding of external equipment can occur through connections to a computer if applicable for example through a USB or RS232 cable 4 The compliance voltage of the PGSTAT302F is 10 V in floating mode The compliance voltage in grounded mode is 10 V with the default cell cables and 30 V with optional modified cell cables Please contact your Autolab distributor for more information 180 NOVA Getting started 4 4 1 Front panel and cell cable connection There are four connectors on the front panel of the PGSTAT The cable that connects to the WE and CE should be plugged into the WE CE socket while the cable with the differential amplifier leading to the RE S and optionally WE2 electrodes connects to the RE S socket A ground cable embedded in the
173. olab com www metrohm autolab com Description Instrument for electrochemical research and voltammetric analysis This instrument is designed and tested according to the standards Electromagnetic compatibility Emission EN 61326 1 1997 A1 1998 A2 2001 A3 2003 EN 61000 3 2 2006 EN 61000 3 3 1995 A1 2001 A2 2005 Electromagnetic compatibility Immunity EN 61326 1 1997 A1 1998 A2 2001 A3 2003 Safety specifications EN 61010 1 The instrument is in conformity with EU directives 89 336 EEC and 3 23 EEC and fulfils the following specifications EN 61326 Electrical equipment for measurement control and laboratory use EMC requirements EN 61010 1 Safety requirements for electrical equipment for measurement control and laboratory use Metrohm Autolab B V is holder of the TUV certificate of the quality system ISO 9001 2008 for quality assurance in development production sales and service of instruments and accessories for electrochemistry and biochemistry registration number 7528 2 2 Utrecht 1 October 2009 J J M Coenen A Idzerda QC Manager Head of Production Metrohm Autolab B V at Utrecht will not accept any liability for damages caused directly or indirectly by connecting this instrument to devices which do not meet relevant safety standards AUTOLAB was developed as a laboratory research instrument Metrohm Autolab B V cannot under any circumstance be held responsible for the
174. omputer is 8 Data transfer is slower than with the NOVA only driver This driver is only compatible with 32 Bit versions of Windows Warning The GPES compatible driver is not available on a 64 Bit version of Windows Warning The GPES and FRA software only work using the GPES compatible driver To install one of the drivers click either one of the buttons in the Driver manager see Figure 1 8 17 NOVA Getting started Select the driver used to control your Autolab instrument Nova only recommended setup Select this driver when you only use Nova 1 7 or higher on your PC Advantages Faster USB data exchange Connect a maximum of 16 Autolab instruments Supports 64 bit Windows Ready for future applications GPES compatible Select this driver when you want to use Nova 1 7 or higher together with Nova 1 6 or lower and or GPES on this PC Restrictions Slower USB data exchange Connect a maximum of 6 Autolab instruments Doesn t support 64 bit Windows No further developments are done with this driver Nova only instruments 0 GPES compatible instruments 0 Total number of instruments 1 Figure 1 8 Click one of the two buttons of the Driver Manager to install the driver Note The NOVA only driver should be preferably installed A message will be displayed as shown in Figure 1 9 18 Page NOVA Getting started Windows Security Would you like to install t
175. or AC signals The earth connection between the cell and P E should always be broken If there is no possibility of doing this please contact Metrohm Autolab for a custom solution if available 4 5 12 Environmental conditions The PGSTAT101 may be used at temperatures of O to 40 degrees Celsius The instrument is calibrated at 25 degrees Celsius and will show minimum errors at that temperature The ventilation holes on the bottom plate and on the rear panel may never be obstructed nor should the instrument be placed in direct sunlight or near other sources of heat 4 5 13 Noise When measuring low level currents some precautions should be taken in order to minimize noise The personal computer must be placed as far away as possible from the electrochemical cell and the cell cables The cell cables should not cross other electrical cables Other equipment with power supplies can also cause noise For instance the interface for mercury electrodes IME should also be placed with some care If possible place the computer between the PGSTAT101 and other equipments Avoid using unshielded extension cables to the electrodes The use of a Faraday cage is also advised If the cell system has a ground connector it can be connected to the analog ground connector provided with the cell cable of the PGSTAT101 If a Faraday cage Is used it should be connected to this ground connector Some experiments concerning optimization of the signal to no
176. orresponds to the estimated errors on the different circuit elements in 76 Page NOVA Getting started bed Equivalent Circuit Editor _ OC Circuit Edit Generate CDC from Circuit Generate Circuit from CDC Properties Run Fit and Simulation F5 Resume Fit and Simulation F9 Generate Report N Circuit Report Element Parameter Value Estimated Error E Figure 1 87 The Equivalent Circuit Editor window can be used to display the details of the calculation The errors on the estimated parameters from the fitting algorithm must be smaller than 0 2 77 Page NOVA Getting started 1 6 13 Test of MUX The TestMUX procedure can be used to test the correct functionality of the MUX module This procedure can be used to test any type of MUX configuration Load the TestMUX procedure connect Channel 1 to dummy cell a and Channel 2 to dummy cell c as shown in Figure 1 88 DUMMY CELL2 g DUMMY CELL2 Figure 1 88 Overview of the connections to the dummy cell required for the TestMUX procedure left MULTI4 right SCNR16 Press the start button A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs two single potential scans The first scan is performed on Channel 1 and the second scan is performed on Channel 2 During each scan the potential of the working electrode is scanning between 1
177. otection circuitry and becomes active after crossing the 10 V limit This is implemented to avoid electrometer damage Please note that the Vov indicator will not light up for this type of voltage overload The measured voltage will be cutoff at an absolute value of 10 00 V Depending on the cell properties galvanostatic control of the cell could lead to a potential difference between the RE and the WE larger than 10 V This situation 222 Page NOVA Getting started will trigger the cutoff of the measured voltage to prevent overloading the differential amplifier 4 7 9 Active cells Some electrochemical cells such as batteries and fuel cells are capable of delivering power to the pAutolab This is allowed only to a maximum cell power Pmax of 0 5 W This means that cells which show an absolute voltage Vceil of less than 5 V between WE and CE are intrinsically safe They may drive the PGSTAT output stage into current limit but will not overload the amplifier On the other hand cells that have an absolute voltage higher than 5 V between WE and CE may only deliver a maximum current Imax given by i _ PMAX MAR Wyaxl 4 7 10 Grounded cells The measurement circuitry of the pAutolab is internally connected to protective earth P E This can be an obstacle when measurement is desired of a cell that is itself in contact with P E In such a case undefined currents will flow through the loop that is formed when the el
178. pear see Figure 1 99 86 NOVA Getting started Determine EQCM zero frequency Latest value Averages Minimum EQCM 1 AFrequency 0 230 Hz 0 086 Hz EQCM 1 Driving force 0 708 V 0 711 V 0 710 V EQCM 1 Temperature 23 0 C 20 0 C Time to average 10 Driving force 0 5 10 15 20 25 Time 5 Clear plot Abort OK Figure 1 99 The determine EQCM zero frequency window can be used to adjust the driving force Using the provided adjustment tool rotate the trimmer on the EQCM oscillator in order to minimize the driving force refer to the EQCM user manual for more information When the driving force has been properly minimized the LED on the EQCM oscillator must be green Click the 7 button in the Determine EQCM zero frequency window to zero the value of the EQCM 1 AFrequency signal After minimizing the AFrequency signal click the OK button to proceed with the measurement The procedure records the three signals provided by the EQCM module during ten seconds The EQCM 1 AFrequency and EQCM 1 Temperature Signals are shown on plot 1 and the EQCM 1 Driving force signal is shown on plot 2 see Figure 1 100 87 NOVA Getting started i 0 925 02 23 565 0 15 EP 0 924 T T 0 1 23 555 o 092 gt D O ha TE 2 0 05 nn D Z 0 922 D 545 U Q Di L 4 23 54 a 0 934 0 09 gt O 23 535 6 O E 5 O Pr LU 0 1 Eg L Ww UY 0 15 23 529 09418 Q 5 10 15 20 5 10
179. peration and installation Not following these instructions when using AUTOLAB may cause unsafe operation General The following safety practices are intended to ensure safe operation of the equipment Not following these instructions when using Autolab may cause unsafe operation Metrohm Autolab is not liable for any damage caused by not complying with the following instructions Electrical Hazards 1 There are no user serviceable parts inside servicing should only be done by qualified personnel 2 Removal of panels exposes to potentially dangerous voltages Always disconnect the instrument from all power sources before removing protective panels 3 Replace blown fuses only with size and rating stipulated on or near the fuse panel holder and in the manual 4 Replace or repair faulty or frayed insulation on power cords and control cables 5 Replace control cables only with original spare parts 6 When replacing power cord use only approved type and conform local regulations 7 Be sure power cords are plugged into the correct voltage source and always use a wall outlet with protective earth 8 Check all connected equipment for proper grounding Do not move the instrument with power cords connected General Precautions 1 Do not place the instrument on an unstable surface 2 Do not expose the instrument to damp or wet conditions 227 NOVA Getting started 3 To prevent overheating care should be taken not to cove
180. perometry fast procedure uses the Chrono methods command instead of the Record signals command The Chrono methods command can be used for fast electrochemical measurements The interval time can be lower than 1 ms Because this command works with higher sampling rates compared to the Record signals command the data cannot be plotted real time The measured data Is displayed at the end of the measurement The procedure has the following parameters e Preconditioning potential O V e Duration 5s e Potential step 1 0 V e Potential step 2 0 3 V e Potential step 3 0 3 V e Potential step 4 O V 33 Down to 100 us 145 NOVA Getting started The response of the cell is measured with an interval time of 100 us At the end of the measurement switch to the analysis view to see the measured data points Figure 3 19 shows an overview of the Chrono amperometry fast procedure Commands Parameters Links Chrono amperometry fast as a ie The levels used in this procedure are shown in Figure 3 20 Remarks End status Autolab Signal sampler Options Instrument Instrument description Autolab control Set potential Set cell Wait time s Chrono methods Number of repeats Total duration s Estimated number of points Signal sampler Corrected time Level Time WE 1 Current Index ivst Set cell ae Figure 3 19 The Chrono amperometry fast procedure 146 Page Chrono amperometry fast Time WE
181. potentiostatic e FRA impedance galvanostatic e FRA potential scan The actual number of procedures listed in the Autolab group of procedures in the Setup view depends on the active profile Please refer to the User manual for more information on the use of profiles in Nova For example if the Hardware based profile is active only the procedures that are compatible with the connected Autolab are shown Profiles can be selected from the Profile menu see Figure 3 2 3 Requires the FI20 module or the on board integrator uAutolab II III and PGSTAT101 4 Requires the SCANGEN or the SCAN250 module 2 Requires the ADC750 or the ADC10M 2e This procedure is intended to be used in combination with the Autolab RDE using the Remote control option on the Autolab motor controller 27 The IME663 or the IME303 module must be declared in the Hardware setup 8 Not available on the yAutolab I III and PGSTAT10 2 Requires the FRA2 or FRA32M module 124 NOVA Getting started File View Profile Run Tools Help be tee eee Harchvare based Basic X Intermediate Advanced Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors Reset user profile Import user profile Export user profile Hicle Ctrl H Unhicle Ctl Shift H Show all Figure 3 2 The profile menu can be used to set one or more profiles active This section provides information on the Autolab procedures Som
182. provides 141 NOVA Getting started an example of a sampled DC polarography measurement in NOVA During this procedure a new Hg drop Is created at the end of each potential step This procedure requires the optional IME663 or IME303 module to be selected in the Hardware setup More information about the use of these Autolab accessories is provided in the Voltammetric analysis tutorial available from the Help menu in NOVA 3 13 Chrono amperometry At gt 1 ms Hardware Tags None Profile Tags Basic Application Tags Corrosion Education Electroanalysis Energy Interfacial electrochemistry Semiconductors The Chrono amperometry At gt 1 ms procedure has three consecutive potential Steps After each potential step the current response is recorded during five seconds with an interval time of 10 ms The Record signals gt 1 ms command is used to measure the electrochemical signals This command samples the signals with a smallest possible interval time of 1 30 ms The procedure has the following parameters e Preconditioning potential O V e Duration 5s e Potential step 1 0 V e Potential step 2 0 5 V e Potential step 3 0 5 V Figure 3 15 shows an overview of the Chrono amperometry At gt 1 ms procedure Remarks Chrono amperometry At gt 1 ms m End status Autolab m Signal sampler Time WE 1 Potential WE 1 Current a Options 1 Options m Instrument AUT40008 Instrument description Autolab control
183. r any of the instrument ventilation holes and not to place the instrument close to a heating source 4 Full EMC compliance can only be achieved when the electrochemical cell is placed inside a Faraday cage 5 2 General specifications Power Supply V Power Line frequency Power consumption VA max Fuse A slow slow Fuse A fast Operating Environment Storage Environment 228 Booster20A pAutolab type Ill uAutolab type II FRA2 PGSTAT101 PGSTAT204 BSTR10A IME303 IME663 PGSTAT302N PGSTAT302F PGSTAT128N PGSTAT100N Multi Autolab 47 63 Hz UAutolab type III uAutolab type III FRA2 PGSTAT101 PGSTAT204 Multi Autolab 12 M101 PGSTAT302N PGSTAT302F PGSTAT128N PGSTAT100N Booster20A BSTR10A IME303 IME663 UAutolab type III 1 6 uAutolab type III FRA2 1 6 PGSTAT101 2 PGSTAT204 3 5 Booster20A 8 100V PGSTAT302N PGSTAT302F 315 PGSTAT128N l PGSTAT100N 3 15 BSTR10A IME303 IME663 630 m Multi Autolab refer to backplane 50r8 100 240V 10 auto select 100 240V 10 selectable in 2 ranges 100 92 132V 240 198 264V 100 240V 10 selectable in 4 ranges 100 90 121V 120 104 139V 220 198 242V 240 207 264V 100 240V 10 selectable in 4 ranges 100 90 121V 120 104 139V 230 198 242V 240 207 264V 100 240V 10 auto select 144 40 200 300 180 247 950 650 50 120V 220V 230V 240V 3 15 1 6 1 6 3 15 1 25 1 25 4 4 630 m 315 m 315 m
184. re 4 43 The procedure validation step always checks the applied current values for the allowed linearity Note In potentiostatic mode this check is not performed It is possible to measure a current value in a fixed current range even if the current value exceeds the linearity limit of the active current range This triggers a current overload warning When this happens during a measurement a message will be shown in the user log suggesting a modification of the current range see Figure 4 44 Time Date Command 5109 PM 1179 2010 11 9 2010 CY staircase Lserlog message WU Autolab USB connected AUT40009 4 Overload occurred in 100 nA current range try using a higher current range 2 52 04 PR Figure 4 44 When a current overload is detected a suggestion is shown in the user log 213 Page NOVA Getting started 4 6 8 Maximum reference electrode voltage The differential electrometer input contains an input protection circuitry that becomes active after crossing the 10 V limit This is implemented to avoid electrometer damage The red status LED indicator on the front panel will not light up for this type of voltage overload The measured voltage will be cutoff at an absolute value of 10 00 V Depending on the cell properties galvanostatic control of the cell could lead to a potential difference between the RE and the S WE larger than 10 V This situation will trigger the cutoff of the measured voltage to p
185. re Tags None Profile Tags Basic Application Tags Energy The Chrono charge discharge procedure uses the Repeat n times command to repeat a combination of Set potential and Record signals gt 1 ms sequence The response of the cell is recorded during 2 5 s with an interval time of 10 ms The Chrono charge discharge procedure has the following parameters e Preconditioning potential O V e Duration 5s e Repeat 10 times o Potential step 1 1 2 V duration 2 5 s o Potential step 2 O V duration 2 5 s Figure 3 25 shows an overview of the Chrono charge discharge procedure 152 NOVA Getting started Commands Parameters Links Remarks Chrono charge discharge End status Autolab nail Signal sampler Time WE 1 Potential WE 1 Current a Options 1 Options sal Instrument AUT40008 Instrument description Autolab control ina it Set potential 0 000 Set cell On Wait time s 10 E Repeat n times 10 Number of repetitions 10 Set potential 1 200 Record signals 1 ms 2 5 0 01 Set potential 0 000 Record signals gt 1 ms 2 5 0 01 E lt gt Set cell Off z gt Figure 3 25 The Autolab Chrono charge discharge procedure The signals sampled during this procedure are e Corrected time e Time e WE 1 Potential e WE 1 Current e Index Figure 3 26 shows a measurement on the dummy cell a with the Autolab Chrono charge discharge procedure 153 Page NOVA Getting started 1E 6 SE DE 4E 7
186. red curve and the data after baseline correction see Figure 1 46 NOVA Getting started 1E 6 4E 9 SE 7 2E 9 6E 7 Eg at T 16 9 Gg CP 3 1E 9 Y 3E 9 6E 7 4E 9 8E 7 5E 9 1E 6 BE 9 0 5 0 0 5 1 0 5 0 0 5 1 Potential applied Potential applied W Figure 1 46 The data points recorded during the TestCV measurement left and the data points after linear baseline correction right The difference between the maxima observed in the residual current plot should be lt 40 nA The second group located under TestCV Reference data contains data from a reference measurement This data can be used for comparison with the data points obtained during the test Two reference curves are provided the i vs E plot and the Residual plot after baseline correction The third group located under Limits contains the absolute maximum and minimum limit allowed for the residual current calculated from the measured data points Figure 1 47 shows an overlay of the residual current calculated from the measured data the residual current plot provided as reference data and the absolute limits allowed for the residual current 48 Page NOVA Getting started 20 000 n 13 000 n 10 000 n 2 0000 n 0 0000 3 O000 n Residual current 4 70 000 N 15 000 n 20 000 n 1 0 5 J 0 5 Potential applied W Figure 1 47 An overlay of the residual current obtained from the measured data blue curve
187. responds to the DAC164 output It is controlled by software and is meant to be used to control external devices like the rotating speed of a Rotating Disc Electrode RDE The output level varies between 10 V and the output impedance is very low lt 1 Q The output amplifier is capable of providing 5 mA at full scale so load impedance should be gt 2 kQ Vin This input corresponds to the ADC164 input This input can be used for measuring a second signal The input range is 10 V and the input impedance is 50 Q 4 7 4 High stability and High speed The pAutolab is equipped with two different bandwidth settings High stability HSTAB and High speed The bandwidth can be defined using the Autolab control command see Figure 4 48 hers Autolab control 0 J pAutolab Ill lt Basic aie cel ort Integrator Summary Mode Potentiostatic v a Current range 1 mA we Bandwidth High stability wi High stability High speed wJ Advanced Figure 4 48 The Autolab control window can be used to set the bandwidth of the pAutolab The purpose of these different modes of operation is to provide a maximum bandwidth maintaining stability in the PSTAT or GSTAT control loop The normal mode of operation is High stability This gives the Control Amplifier a bandwidth of 12 5 kHz The High speed mode is automatically selected during impedance measurements at frequencies gt 10 kHz while the High stability
188. revent overloading the differential amplifier 4 6 9 Active cells Some electrochemical cells such as batteries and fuel cells are capable of delivering power to the PGSTAT204 This is allowed only to a maximum cell power Pmax of 8 W This means that cells showing an absolute voltage Vel of less than 10 V between WE and CE are intrinsically safe They may drive the PGSTAT204 output Stage into current limit but will not overload the amplifier On the other hand cells that have an absolute voltage higher than 10 V between WE and CE may only deliver a maximum current imax given by i _ Puax MAX Vmax 4 6 10 Grounded cells The measurement circuitry of the Autolab is internally connected to protective earth P E This can be an obstacle when measurement is desired of a cell that is itself in contact with P E In such a case undefined currents will flow through the loop that is formed when the electrode connections from the PGSTAT204 are linked to the cell and measurements will not be possible Please note that not only a short circuit or a resistance can make a connection to earth but also a capacitance is capable of providing a conductive path for AC signals The earth connection between the cell and P E should always be broken If there is no possibility of doing this please contact Metrohm Autolab for a custom solution if available 4 6 11 Environmental conditions The PGSTAT204 may be used at temperat
189. ring this measurement an integration time constant of 0 01 s is used At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 81 TestFleU IntegratorPias TATU 5 TestFl2ntegratar PGSTATIO Measured data Al ivs E Measured data S TestFl20Integrato PGSTATION Reference data i H iws E Reterence data Figure 1 81 The data obtained with the TestFl20 Integrator PGSTAT101 procedure The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 82 72 NOVA Getting started 1 2E 6 1E 6 BE 7 T 6E7 D 4E 7 i a 267 m z T 2E 7 5 R AET D go _6E 7 GE 1E 6 1 2E 6 E 0 5 0 0 5 Potential applied tv Figure 1 82 The expected result of the TestFl20 Integrator PGSTAT101 procedure The test is successful if the measured data can be compared to the reference data The current recorded during current integration cyclic voltammetry strongly depends on the value of the capacitance included in the circuit of dummy cell a This capacitance has a tolerance of 5 The measured data points should therefore be qualit
190. rovided in Section 4 8 4 5 Autolab PGSTAT101 and M101 information This section provides specific information for the Autolab PGSTAT101 and the M101 potentiostat galvanostat module for the Multi Autolab 4 5 1 Front panel and cell cable connection PGSTAT101 There are two connectors on the front panel of the PGSTAT101 The cell cable should be plugged into the CELL socket on the front panel of the instrument The I O socket on the front panel can be used to connect the optional I O cable see Figure 4 29 POTENTIOSTAT GALVANOSTAT Status LED PGSTAT101 I O cable socket Cell cable socket Figure 4 29 Overview of the Autolab PGSTAT101 front 195 NOVA Getting started The cell cable is labelled as follows e Working or indicator electrode WE red e Sense electrode S red e Reference electrode RE blue e Auxiliary or counter electrode CE black An additional ground connection for shielding purposes e g a Faraday cage is also provided with the cell cable In a four electrode setup each of the cell cable connectors is used independently In a three electrode set up the working electrode and sense lead are both connected to the working electrode In a two electrode set up the counter and reference electrode lead are both connected to the same electrode see Figure 4 30 RE CE WE S RE CE WE S RE S CE WE Figure 4 30 Overview of the possible cell connections with
191. s Five chapters are included in this document e Chapter 1 provides installation instructions for Nova and the Autolab e Chapter 2 describes a quick cyclic voltammetry measurement e Chapter 3 describes the Autolab standard procedures e Chapter 4 provides information about the Autolab hardware e Chapter 5 provides information regarding Warranty and Conformity f Warning Please read the Warranty and Conformity carefully before operating the Autolab equipment 7 NOVA Getting started The philosophy of Nova Nova differs from most software packages for electrochemistry The classic approach used in existing electrochemical applications is to code a number of so called Use cases or Electrochemical methods in the software The advantage of this approach is that it provides a specific solution for well defined experimental conditions The disadvantage is that it is not possible to deviate from the methods provided in the software Moreover it is not possible to integrate all the possible electrochemical methods since new experimental protocols are developed on a daily basis This means that this type of software will require periodical updates and will necessitate significant maintenance efforts Figure 1 shows a typical overview of a classic method based application for electrochemistry Method 3 CV linear Method 2 CV staircase with pH Method 1 Method 4 Method n LSV staircase CV staircase scan Frequen
192. sctah d TestADC SCAN Measured data gem j ys E Measured data a TestADGSCAN Reference data H j vs E Reterence dataj Figure 1 96 The data obtained with the TestADC SCAN procedure The first group located under TestADC SCAN Measured data contains the measured current plotted versus the measured potential The second group contains data from a reference measurement This data can be used for comparison with the data points obtained during the test 84 NOVA Getting started The measured data should be similar to the reference data provided for comparison as shown in Figure 1 97 1 Current Ay WEI i Us 0 0 5 WEL 1 Potential Y Figure 1 97 The expected result of the TestADC SCAN procedure The test is successful if the measured data can be compared to the reference data The current recorded during a measurement during the TestADC SCAN procedure strongly depends on the value of the capacitance included in the circuit of dummy cell a This capacitance has a tolerance of 5 The measured data points should therefore be qualitatively compared to the reference data provided with the test 35 NOVA Getting started 1 6 17 Test of the EQCM The TestEQCM procedure can be used to test the correct functionality of the filter circuit of the EQCM f Warning This procedure cannot be performed on the dummy cell and it requires about 2 ml of water Load the TestEQCM procedure and inser
193. se button 106 PGSTAT description 164 195 206 PGSTAT100 164 PGSTAT100N 164 PGSTAT101 195 PGSTAT12 164 PGSTAT128N 164 PGSTAT204 206 PGSTAT30 164 PGSTAT302 164 PGSTAT302F 52 180 PGSTAT302N 164 Plotting data 110 Polarization resistance 124 Polarography 124 Positive feedback 124 155 Potential 169 184 199 208 Potential offset 159 Potential range 159 Potential scan 156 Potential step 163 Power up settings 167 182 198 208 Print diagnostics report 40 Procedure 99 Procedure browser 100 Procedure editor frame 100 Procedure progress 108 Procedure validation 105 Pulse methods 145 RE 166 181 196 198 207 216 Real time display 106 108 Record signals gt 1 ms 142 152 Record signals galvanostatic gt 1 ms 144 Reference electrode 166 181 196 198 207 216 224 Repeat for each value 138 Repeat loop 139 Repeat n times 152 Resolution 159 163 Rotating disc electrode 124 Rotation rate 138 S 166 173 181 187 196 198 202 207 211 Safety information 227 Sampled DC voltammetry 124 Sampling rate 161 Save data 122 Save diagnostics report 40 Save procedure 104 Scan rate 163 SCAN250 124 131 158 SCANGEN 124 131 158 Sense 166 173 181 187 196 198 202 207 211 Set reference potential 136 Setup view 29 99 Shielding 181 224 Short interval time 145 Signals 111 Sinewave 158 Software installation
194. shortcut key as shown in Figure 2 11 106 Page NOVA Getting started File Profile Run Tools Help gt b 9 Advanced procedure view EME E Be eee va e Ca ge Setup View Mult Autolab View Measurement View Analysis View User log p Autolab display F10 FRA manual conta MDE manual cont Show hide Autolab display MUX manual control External manual control File View Profile Run Tools Help Di BE m a ahal aE N E E KD Ca a Show hide Autolab display Figure 2 11 Select the Autolab display option in the View menu or use the dedicated button in the toolbar to show or hide the Autolab display window Figure 2 12 shows the Autolab display during the measurement Autolab display Ed Autolab manual control AUT40008 T ovl I owl GSTAT 10 pA V ovl iR C 1 yA 100 nA 10 mA 10 nA 1 mA current range 0 000 c Figure 2 12 The Autolab display 107 Page NOVA Getting started The Autolab display provides real time information about the sampled signals and the hardware settings and provides additional controls like the ese button which can be used to reverse the scan direction The procedure used in this quick start guide performs a single scan on the dummy cell When the scan is finished the stop button becomes a start button again indicating that Nova Is ready to perform a new measurement At the end of the measuremen
195. splay the data in real time during a measurement 99 NOVA Getting started the Analysis view used to perform data analysis and the Multi Autolab view used to control the Multi Autolab or more than one instrument at the same time The Setup view contains several areas also called frames Figure 2 1 shows an overview of the Setup view x Toolbar disti Quick access toolbar EA File 5 tun Tools Help BD Me Bs Sm a ph EE E E E ayy Commands Procedures Commands Links 5 Autolab Cyclic voltammetry potentiostatic Edit options EES Cyclic voltammetry potentiostatic Remarks Cyclic voltammetry pote i Cyclic voltammetry galvanostatic End sinies Anini a hee g 3 Signal sampler Time WE 1 Potential WE 1 Current y i Cyclic voltammetry current integration i pol i Options 1 Options a b Cyclic voltammetry linear scan EE Instrument AUT40008 i Cyclic voltammetry linear scan high speed _ i f jz 3 Instrument description Linear sweep voltammetry potentiostatic E i ae i Autolab control z i Linear sweep voltammetry galvanostatic gt ae Sa Set potential 0 000 i Linear polarization l aya Set cell On ssa i Hydrodynamic linear sweep ae i in Wait time s 5 Differential pulse voltammetry sias Pig quare wave voltammetry Optimize current range S EE CV staircase 0 000 1 000 1 000 0 000 2 0 1000000 Sampled DC polarography
196. ssage will be shown in the procedure validation screen see Figure 4 51 221 NOVA Getting started Validation results 0 The following problems were encountered during validation Message Command USAUT 0530 O The specified value 5 mA is too high for the selected currentrange 1mA Set curent The specified value 5 mA is too high for the selected current range 1 mA The current range must be 10 mA or higher OK Cancel Figure 4 51 The procedure validation step always checks the applied current values for the allowed linearity Note In potentiostatic mode this check is not performed It is possible to measure a current value in a fixed current range even if the current value exceeds the linearity limit of the active current range This triggers a current overload warning When this happens during a measurement a message will be shown in the user log suggesting a modification of the current range see Figure 4 52 User log message Time Date Command 4 Autolab USB connected u3AUT 70530 1 09 36 PM 1 15 2013 amp Overload occurred in 1 pA current range use a higher currentrange 23842 PM 1 15 2013 CV staircase Figure 4 52 When a current overload is detected a suggestion is shown in the user log The maximum measurable current with the pAutolab II and III is 80 mA 4 7 8 Maximum reference electrode voltage The electrometer RE input contains an input pr
197. strument or perform individual tests to verify the correct operation of the instrument Depending on the instrument type the following items are required e wAutolab type II wAutolab type Ill and pAutolab type III FRA2 the Standard Autolab dummy cell For the diagnostics test the circuit a is used e PGSTAT101 and M101 module the internal dummy cell is used during the test no additional items are required e PGSTAT204 the standard Autolab dummy cell For the diagnostics test the circuit a is used e Other PGSTATs the standard Autolab dummy cell and a 50 cm BNC cable For the diagnostics test the circuit a is used The BNC cable must be connected between the ADC164 channel 2 and the DAC164 channel 2 on the front panel of the instrument The PGSTAT302F must be tested in normal mode In the case of a PGSTAT with serial number not starting with AUT7 or AUT8 connect the BNC cable between DAC channel 4 and ADC channel 4 35 NOVA Getting started The Diagnostics application supports multiple Autolab instruments When the application starts it detects all available instruments connected to the computer see Figure 1 30 GE Diagnostics Diagnostics is searching for instruments Figure 1 30 The Diagnostics application automatically scans for all the connected instruments If more than one instrument is detected a selection menu is displayed before the Diagnostics starts see Figure 1 31
198. sult of the TestMUX procedure Channel 1 left and Channel 2 right The test is successful if the measured data can be compared to the reference data 79 NOVA Getting started 1 6 14 Test of pX and pX1000 The TestpX and TestpX1000 procedures can be used to test the correct functionality of the pX and pX1000 modules respectively Both tests are performed on the dummy cell Load the TestpX or the TestpX1000 procedure depending on the module to test from the Standards database Connect the pX pX1000 cable to the module on the front panel of the instrument Connect the V lead from the pX pX1000 cable red lead to dummy cell a and the V lead from the pX pX1000 cable black lead to the CE connector on the dummy cell Connect the PGSTAT cables to dummy cell a see Figure 1 91 To pX1000 module To pX1000 module C4 R6 C WE S d 1p 5kQ DUMMY CELL2 Figure 1 91 Overview of the connections to the dummy cell required for the TestpX and the TestpX1000 i Warning During the TestpX procedure designed to verify the functionality of the pX module make sure that the 50 Ohm resistor BNC shunt is NOT connected to the G BNC input on the front panel of the pX module Press the start button to start the measurement A message will be displayed when the measurement starts The test uses the cyclic voltammetry staircase method and performs a single potential scan During this scan the potential of the workin
199. t the User log can be updated depending on the events that occurred during the measurement For example if a current overload occurred during the experiment a message will be shown in the log see Figure 2 13 User log message Time Date Command 4 Autolab USB connected AUT40008 10 20 35 AM 1 15 2013 amp Overload occurred in 1 pA current range use a higher current range 10 2318 AM 1 15 2013 CV staircase Figure 2 13 The User log is automatically updated at the end of the experiment Although the measurement view displays the measured data during and after the experiment it is not meant for data analysis Data analysis is performed in the dedicated analysis view Switching to the analysis view can be done by clicking the corresponding button amp on the toolbar see Figure 2 14 File View Profile Run Tools Help ERETTE eR a a eR SS ee ee Ll Ge E Analysis View Figure 2 14 Switching from the measurement view to the analysis view 2 2 3 Analyzing the measured data The analysis view is used to manage experimental data and perform data analysis Figure 2 15 shows the default layout 21 Please refer to the Cyclic voltammetry tutorial available from the Help Tutorials menu for more information 108 NOVA Getting started NOVA 0 ea Toolbar File z un Tools Help ne TEN N e a EEE E OEE Procedure name Time stamp Remarks Instrument Instrument description Database frame
200. t a 6 MHz EQCM crystal in the EQCM cell Fill the cell with ca 2 ml of water and check for leakage Connect the cell to the EQCM oscillator and the oscillator to the Autolab PGSTAT using the provided cable Leave the cell connectors from the PGSTAT disconnected Please refer to the EQCM user manual for more information Press the start button to start the measurement Two messages will be displayed when the measurement starts see Figure 1 98 TestEQCM TestEQCM This procedure is designed to test the basic A Verify thatthe LED on the EQCM oscillator is ON Wait A functionality ofthe EQCM module Connect the EQCM approx 15 minutes for the EQCM to warm up Click OK oscillator to the Autolab Insert a 6 MHz crystal into the to continue A new window will be displayed Using EQCM cell Fillwith approx 2 ml of water Connectthe the provided trimmer adjust the driving force of the cellto the EQCM oscillator after checking for leakage EQCM as described in the user manual When the Leave the cell cables from the Autolab disconnected driving force is minimized press the Zero Af button to Press OK to continue a zero the frequency me w N Figure 1 98 Two messages are displayed at the beginning of the measurement When the second message appears verify that the LED on the EQCM oscillator box is ON red or green A Warning Wait 15 minutes for the EQCM to warm up Click OK to continue The Determine EQCM zero frequency window will ap
201. t description The database consists of one single folder However if required a specific entry of the database can be exported as a single file 22 Please refer to the User Manual for more information 109 Page NOVA Getting started The analysis view features a dedicated toolbar see Figure 2 17 File View Profile Run Tools Help i Sh a I TS coe eG i Figure 2 17 The analysis view toolbar highlighted To view and analyze the data from a measurement the corresponding entry of the database has to be loaded in the Data explorer frame Double click the Quick start Cyclic voltammetry entry of your database to load it in the data explorer frame The database entry will appear in this frame as shown in Figure 2 18 File View Profile Run Tools Help eee We ee eee Ce ee Me Procedure name Time stamp Remarks Instrument Instrument description Quick start cyclic voltammetry 6 13 2011 5 29 51 PM N Cyclic voltammetry potenti PSAUT 70462 Quick start cyclic voltammetry C staircase H ivs E Figure 2 18 Loading the measured data in the data explorer Once the data from the database has been loaded into the data explorer frame it is available for data analysis To view the data click the blue i vs E item in the data explorer The measured data will be displayed using the default settings i e plotting the Potential applied on the X axis and the measured current WE 1 Current on the Y axis
202. t menu to restart the instrument detection see Figure 1 38 The list of available devices will be displayed after the detection process is finished see Figure 1 30 and Figure 1 31 41 Page NOVA Getting started Diagnostics AUT83071 0 Select All Tests Results Deselect Optional Tests E PT i Windows Information i WP Embedded Processor Test cH WY License information H WF EEProm Test H a Timer Test H A Autolab Test Hardware setup 2e instrument r E Autolab Test AD Converter Test DA Converter Test Potentiostat Test Noise Test Galvanostat Test cH Pal AD Converter Test cH WF DA Converter Test cH PT al Potentiostat Test iH A Noise Test H Galvanostat Test Progress Figure 1 38 It is possible to restart the instrument detection at the end of the test to diagnose another device When a Fl20 Integrator is specified in the Hardware setup for instruments with a FI20 module or an on board integrator a message will be displayed at the end of the Integrator test see Figure 1 39 Integrator calibration Integrator calibration Calibration factor currently 1 Calibration factor currently 1 02 Calibration factor measured 1 02 Calibration factor measured 1 02 Save measured factor OK Cancel OK X N Wi Figure 1 39 The value of the measured Integrator calibration factor is displayed at the end of the integrator test left calibration factor different from stored value
203. tarts see Figure 1 50 50 Page NOVA Getting started TestCV PGSTAT101 This testis designed to verify the basic functionality of the Autolab PGSTAT101 The internal dummy cell will be used for this test Connect CE to RE and 3 to WE Make sure thatthe cell cable is not connected to an external cell Click OK to continue Data evaluation should be carried out in the Analysis view Figure 1 50 A message is displayed at the beginning of the measurement The test uses the cyclic voltammetry staircase method and performs a single potential scan starting from O V between 1 V and 1V At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 51 E Teste PasTAT 01 S Tese PGSTAT1O1 Measured data H ive E Measured data El S Testy PGSTAT101 Reference data ivs E Reference data Figure 1 51 The data obtained with the TestCV PGSTAT101 procedure The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 52 51 NOVA Getting started 1E 6 8E 7 6E 7 AE 7 2E 7 roa WEET Current 4 4E 7 6E 7 8E 7 1E 6 1 0 8 06 04 0 2 J 02 U4 0 6 Uo Potent
204. tat mode this large impedance between CE and RE will usually not lead to stability problems because of the current feedback regulation 4 6 6 Galvanostat potentiostat and iR compensation bandwidth For galvanostatic measurements on low current ranges the bandwidth limiting factor becomes the current to voltage circuit rather than the control amplifier For stability reasons it is not recommended to use the High speed mode for current ranges lt 10 pA The Ultra high speed mode is also not recommended for current ranges lt 1 MA As the current measurement circuit plays an important role in the iR compensation technique its use is also subject to bandwidth limitations A general indication of the maximum available bandwidth for GSTAT and for iR compensation can be found in Table 4 8 Mode GSTAT iR C PSTAT 100 mA 100 uA gt 1 MHz gt 1 MHz 10 pA 10 kHz 50 kHz 1 pA 10 kHz 50 kHz 100 nA 500 Hz 500 Hz 10 nA 500 Hz 500 Hz Table 4 8 Bandwidth overview for the PGSTAT204 At the same time the iR compensation bandwidth limits indicate up to which frequency current measurements can be made in potentiostatic mode either with or without iR compensation 4 6 7 Galvanostatic operation and current range linearity For galvanostatic experiments automatic current ranging is not possible The measurements are performed in a fixed current range Each current range on the e3 Empirical value 211 NOVA Getting started
205. te value of 10 00 V Depending on the cell properties galvanostatic control of the cell could lead to a potential difference between the RE and the S WE larger than 10 V This situation will trigger the cutoff of the measured voltage to prevent overloading the differential amplifier 4 5 10 Active cells Some electrochemical cells such as batteries and fuel cells are capable of delivering power to the PGSTAT101 This is allowed only to a maximum cell power Pmax of 8 W This means that cells showing an absolute voltage Veal of less than 10 V between WE and CE are intrinsically safe They may drive the PGSTAT101 output Stage into current limit but will not overload the amplifier On the other hand cells that have an absolute voltage higher than 10 V between WE and CE may only deliver a maximum current imax given by i _ Puax MAX 77 Vmax 204 NOVA Getting started 4 5 11 Grounded cells The measurement circuitry of the Autolab is internally connected to protective earth P E This can be an obstacle when measurement is desired of a cell that is itself in contact with P E In such a case undefined currents will flow through the loop that is formed when the electrode connections from the PGSTAT101 are linked to the cell and measurements will not be possible Please note that not only a short circuit or a resistance can make a connection to earth but also a capacitance is capable of providing a conductive path f
206. the Autolab PGSTAT101 from top to bottom two electrode three electrode and four electrode setup 4 5 2 Front panel and cell cable connection M101 The M101 potentiostat galvanostat module can be installed in the Multi Autolab frame up to a maximum of 12 modules in a single frame The M101 is identical in 196 NOVA Getting started specification to the PGSTAT101 All information provided in the rest of section 4 5 applies to both the PGSTAT101 and the M101 gt installed in the Multi Autolab There are three connectors on the front panel of each M101 module installed in the Multi Autolab see Figure 4 31 DIO cable socket I O cable socket Status LED Cell cable socket Figure 4 31 Overview of the M101 front in Multi Autolab frame Each M101 module is identified by a module label on the front panel indicating the location and the purpose of each connector see Figure 4 32 Cell status LED Figure 4 32 Detailed view of the M101 module label gt gt In the rest of this section the M101 and PGSTAT101 will be referred to as PGSTAT101 197 Page NOVA Getting started The cell cable should be plugged into the lowest socket labelled by the symbol on the front panel of the module The I O socket on the front panel can be used to connect the optional I O cable The DIO cable used to connect to the optional IME663 or IME303 or for TTL triggering can be connected to the DIO connector on the front panel
207. the Autolab RDE is set using the Contro Autolab RDE command linked to the values of a repeat for each value command This procedure is intended to be used with the Remote switch of the Autolab motor controller enabled on the back plane of the controller and with a BNC cable connected between the DAC164 lt 1 connector Vou for the pAutolab Il Ill the PGSTAT101 PGSTAT204 and the Multi Autolab and the Remote input plug on the back plane of the Autolab RDE motor controller see Figure 3 13 32 Remote control of the Autolab RDE requires a BNC cable between the Autolab and the Autolab motor controller 138 NOVA Getting started Figure 3 13 The Hydrodynamic linear sweep Voltammetry is intended to be used with the Autolab RDE and motor controller Please refer to the Autolab RDE User Manual for more information The Hydrodynamic linear sweep voltammetry has the following parameters Preconditioning potential 1 V Set RDE rotation rate to 0 RPM Duration 15 s Repeat for each value o Set RDE rotation rate o Wait 15s o LSV Staircase e Start potential 1 V e Stop potential O V e Step potential 2 44 mV e Scan rate 100 mV s Figure 3 14 shows an overview of the Hydrodynamic linear sweep voltammetry procedure 139 Page NOVA Getting started Commands Hydrodynamic linear sweep Hydrodynamic linear sweep requires an RDE connected Remarks End status Autolab Signal sampler Options Instrument Instrument
208. the User log after initialization see Figure 1 20 ser log message Time Late Command J Created hardware setup for u3AUT 70530 441 PM Bedelli J Autolab USB connected u34UT 70530 14rd Pea Sfedfe2011 Figure 1 20 Nova creates the hardware setup automatically for instruments connected the first time 26 Page NOVA Getting started Not all the modules and instruments can be detected automatically It is always recommended to check the hardware setup after initialization to verify configuration see Section 1 3 3 If the computer is connected to the internet NOVA will automatically check if a new version is available for download on the Metrohm Autolab website 1 3 1 Connection and identification of individual instruments Individual instruments connected to the computer are identified by a unique serial number after the initialization process Depending on the type of instrument and the configuration several identification strategies can be encountered Instruments with serial number beginning with AUTY or with uU2AUT7 connected through an external USB interface are identified by the serial number of the interface USB7XXXX Instruments with an internal USB interface or instruments with serial number beginning with AUT7 connected through an external USB interface are identified by their own serial number Table 1 1 shows an overview of different situations that can be encountered during the initialization of an
209. the cell cable or to ground connector GND at rear of the Autolab instrument 4 8 4 Grounding of the instrument Not proper grounding of the Autolab and PC will decrease the signal to noise ratio Always use a grounded power point and grounded power cables Be sure to connect the Autolab and PC to the same power ground This means they should be connected to the same outlet 4 8 5 Magnetic stirrer In some cases a magnetic stirrer can cause noise problems Try the measurements with the stirrer on and off and monitor the current If the stirrer causes a lot of noise please try to find another way of stirring 4 8 6 Position of the cell Autolab and accessories The signal to noise ratio can often be improved by changing the positions of the cell computer and ancillary equipment relative to the Autolab In general the electrochemical cell should be placed as far as possible from the computer and 224 NOVA Getting started other devices without extending the cell cables with unshielded cables If the noise level remains too high a Faraday cage may be necessary 4 8 7 Measurements in a glove box When the cell needs to be place into a glove box it is highly recommended to use feed through that allows the Autolab cell cables to be connected to the cell inside the glove box If necessary the cell cables of the Autolab can be fitted with BNC connectors rather than 4 mm banana connectors This allows using BNC feedthroughs
210. the connections required for the test see Figure 1 34 NOVA Getting started Please connect the Dummy cell as shown Please connect a BNC cable between the DAC164 channel and the ADC164 channel as shown below e k 00000000000 l t L__j Figure 1 34 A visual reminder is shown at the beginning of the Diagnostics test During the test the progress will be displayed and a successful test will be indicated by a green symbol see Figure 1 35 39 Page NOVA Getting started ce Diagnostics AUT83071 a File Edit Tools Tests Results Windows Information eset al Windows Information Embedded Processor Test H A Embedded Processor Test License information H A License information EEProm Test H a EEFrom Test Timer Test H A Timer Test Autolab Test H a Autolab Test AD Converter Test H A AD Converter Test DA Converter Test H A DA Converter Test Potentiostat Test H A Potentiostat Test Noise Test H A Noise Test Galvanostat Test H A Galvanostat Test Progress lt lt at Figure 1 35 The diagnostics report after all the tests have been performed successfully If one or more of the tests fails a red symbol will be used to indicate which test failed and what the problem is Figure 1 36 shows the output of the diagnostics tool for a failed PSTAT and GSTAT test Diagnostics AUT83071 _ O ES File Edit Tools Tests Results Windows Information E A Windows Informat
211. this setting particularly highly capacitive cells in PSTAT mode Increasing the bandwidth also increases the noise levels for the i and E signals It is possible to switch from High stability to High speed by clicking the HSTAB label in the Autolab display In High speed mode this label will be unlit on the Autolab display Clicking the HSTAB label again switches the bandwidth back to High stability For applications requiring very high bandwidth the Ultra high speed mode can be selected In this mode the control amplifier bandwidth is extended to 1 MHz There is a significant oscillation risk using this setting and the noise levels will generally show an increase relative to the High speed or High stability mode i Warning The higher the bandwidth the more important it is to pay attention to adequate shielding of the cell and the electrode connectors The use of a Faraday cage Is recommended in this case 201 NOVA Getting started 4 5 6 RE input impedance and stability The electrometer RE input contains a small capacitive load If the capacitive part of the impedance between CE and RE is comparatively large phase shifts will occur which can lead to instability problems when working in potentiostatic mode If the impedance between the CE and the RE cannot be changed and oscillations are observed it is recommended to select the High stability mode to increase the system stability In general the use of High stability leads to
212. thout iR compensation gt Empirical value 202 NOVA Getting started 4 5 8 Galvanostatic operation and current range linearity For galvanostatic experiments automatic current ranging is not possible The measurements are performed in a fixed current range Each current range on the instrument is characterized by a specific linearity limit and this specification determines the maximum current that can be applied in galvanostatic mode The linearity limitation also applies on measurements performed in potentiostatic mode in a fixed current range Table 4 7 provides an overview of the current range linearity for the PGSTAT101 Current range Linearity 10 mA 10 1mA 7 10 1 mA 7 100 1 pA 7 100 10nA 7 Table 4 7 Linearity limit for the PGSTAT101 For example in the 1 mA current range the maximum current that can be applied galvanostatically using the PGSTAT101 is 7 mA The maximum current that can be measured in the 1 mA current range is 10 mA although currents exceeding 7 mA will be measured outside of the linearity limit of this current range In galvanostatic operation the applied current values are checked during the procedure validation step When the applied current exceeds the linearity limit for the specified current range an error message will be shown in the procedure validation screen see Figure 4 36 Validation results 0 aa The following problems were encountered during validation
213. ting values are set to 0 Open the hardware setup Tools Hardware setup select instrument type in the Main module frame in the hardware setup window and adjust the value of C1 and C2 to 0 as shown in Figure 1 103 90 NOVA Getting started Hardware setup AUT84530 File Tools Main Module Additional Modules PGSTAT302N FRAIZM W FRAZ _JADC10M _JADC750 JADC 5Or4 SCAN250 SCANGEN m IBA BIPFOT ARRAY JEcD Fl20 Filter Fl20 Integrator Booster204 Booster tA JEQCM Jpx1000 px JECN 4 External External cable pAutolab IME303 IME663 MUS 0 00E 00 0 00E 00 Power Supply Frequency CI 50 Hz Y Import FRAG Calibration FRA offset DAC range 5V w OK Auto Cancel C Program Data Metrohm Autolab 11 0 HarcdwareSetup 4AUT84530 xml Figure 1 103 The value of C1 and C2 must be set to 0 before starting the measurements The determination of C1 and C2 requires the following items e Autolab Dummy cell e Faraday cage 1 6 18 1 Determination of C1 Follow the steps described in this section to determine the value of the C1 parameter 1 Start the Nova software Load the procedure PGSTAT C7 calibration from the Module test database 3 Connect the Autolab Dummy cell as shown in Figure 1 104 Connect the ground lead from the PGSTAT to the Faraday cage Do not connect the ground lead from the PGSTAT to the Dummy cell Place the dummy c
214. tutorial for more information Load the TestFl20 Integrator procedure connect dummy cell a and press the Start button 68 NOVA Getting started A message will be displayed when the measurement starts The test uses the cyclic voltammetry current integration staircase method and performs a single potential scan During this scan the potential of the working electrode is scanning between 1 V and 1 V During this measurement an integration time constant of 0 01 s is used At the end of the measurement switch to the Analysis view and load the data for evaluation The data set includes two groups of data points see Figure 1 76 a TestFl 0 Inteqgrator a a TestFle0Inteqrator Measured dataj Gem ivs E Measured data a S TestFl 0 Inteqrator Reterence cata Ge ws E Reference data Figure 1 76 The data obtained with the TestFl20 Integrator procedure The first group contains the measured data points The other group contains data points from a reference measurement This data can be used for comparison with the data points obtained during the test The measured data should be similar to the reference data provided for comparison as shown in Figure 1 77 1E 6 z oE integratori 1 Integrated Current 4 _ 1E 6 1 0 5 J es Potential applied V4 Figure 1 77 The expected result of the TestFl20 Integrator procedure The test is successful if the measured data can be compared to the referenc
215. ueceececueceececueceececueaueceeueneeaeenes 73 1 6 13 Test of MUX 2 0 ccecceccecccccceccececceececeeeeececaeeuececaeeeeseeaeeeesecateereeeaneaes 78 1 6 14 Test of pX and A O00 os raccnsssestendcsdicncnmyendantentusarancenhncnesdsstwendsndadiasss 80 1 6 15 Test of the SCANGEN or the SCAN250 aaaaaaenennnnnnrnrerrerernrnrnn 82 1 6 16 Test of the SCANGEN or the SCAN250 in combination with the ACD750 or the ADC10M uu cece ccc ceccecceececceeceececueeueeaeeaeeaeeaeeneeneeeeeeeeeeneeees 83 1 6 17 Test of the EQCM 2 0 0 cece cccccecccececcececcececcececeececueceseeseeetseeecerecaes 86 1 6 18 Determination of the C1 and C2 factors of the Autolab 89 1 6 18 1 Determination of C1 oo cccceceeccecccceccecceceeceececeeenececaueeesecaeeeeneeaneees 91 1 6 18 2 Determination of C2 oo cicccecceccecccceccecceceeceececeeeuececueeeesecaeeeeeeeaneees 95 2 A typical Nova measurement xxi cases consshshncnnsussonncsionaasndgiads anncteuaaaaccegeeanonetsdaniees 99 2 1 Starting up the software installation required see Chapter 1 99 2 2 Running cyclic voltammetry on the dummy cell ceeeeeeeeeeeeeee eee 101 NOVA Getting started 2 2 1 Setting up the experiment cccccseececcesseecceeseesceuseessaeseeseeseeess 102 2 2 2 Viewing the measured data i oj cedesvanisSeoansivvacxsesdudarsahcnduetadaoarsesicedstes 106 2 2 3 Analyzing the measured data
216. ures of O to 40 degrees Celsius The instrument is calibrated at 25 degrees Celsius and will show minimum errors at that temperature The ventilation holes on the bottom plate and on the rear panel may never be obstructed nor should the instrument be placed in direct sunlight or near other sources of heat 214 NOVA Getting started 4 6 12 Noise When measuring low level currents some precautions should be taken in order to minimize noise The personal computer must be placed as far away as possible from the electrochemical cell and the cell cables The cell cables should not cross other electrical cables Other equipment with power supplies can also cause noise For instance the interface for mercury electrodes IME should also be placed with some care If possible place the computer between the PGSTAT204 and other equipments Avoid using unshielded extension cables to the electrodes The use of a Faraday cage is also advised If the cell system has a ground connector it can be connected to the analog ground connector provided with the cell cable of the PGSTAT204 If a Faraday cage Is used it should be connected to this ground connector Some experiments concerning optimization of the signal to noise ratio can readily indicate whether or not a configuration is satisfactory More information on noise is provided in Section 4 8 4 6 13 Temperature overload The PGSTAT204 is fitted with a temperature overload protection circuit Wh
217. utolab When the FRA32M or FRA2 module is used in combination with the Autolab the C1 and C2 factors need to be determined These factors can be determined with the following procedures included in the Module test database e PGSTAT C1 calibration e PGSTAT C2 calibration These procedures can be used in combination with the Autolab dummy cell The C1 and C2 are predetermined when FRA32M or FRA2 module is preinstalled The C1 and C2 factors must be determined experimentally when a FRA32M or FRA2 module is installed into an existing instrument This determination must only be carried out upon installation of the module The C1 and C2 determination in not required for the M101 and the PGSTAT204 192 When the FRA32M or FRA2 is installed in a PGSTAT302F make sure that the PGSTAT302F is set to Normal mode 89 NOVA Getting started The typical values of C1 and C2 are listed in Table 1 3 for the different Autolab instruments Instrument type PGSTAT302N PGSTAT302F PGSTAT128N PGSTAT128N PGSTAT100N C1 1 6E 11 1 6E 11 2 6E 11 1 6E 11 1 6E 11 C2 3 0E 13 1 0E 12 1 0E 12 1 0E 12 5 OE 13 For instruments with serial number gt AUT84179 Table 1 3 Typical values for C1 and C2 The determination of the C1 and C2 values is not required for the M101 module used in combination with the FRA32M module in the Multi Autolab instrument Before starting the determination of C1 and C2 verify that the star
218. volved in other Windows activity accurate timing of events cannot be guaranteed and the effective interval time between two consecutive host commands will depend entirely on the amount of activity on the host PC Depending on the command sequence the time gap can be as short as 2 s transition between host command to measurement command or several seconds transition between measurement command and host command Transfer of large amounts measured data points is particularly time consuming 42 The on board memory of the fast sampling ADC module ADC10M or ADC750 can store up to one million data points Allow for gap times of several seconds when large data sets are transferred from the Autolab to the host computer 161 NOVA Getting started Figure 4 3 Shows the Autolab Linear polarization procedure in which measurement and host commands are identified using the green timing guide on left hand side Commands Parameters Links Linear polarization E E E E EE m Remarks End status Autolab Signal sampler Options Instrument Instrument description Autolab control OCP determination Set reference potential Set potential Set cell Wait time s Optimize current range LSV staircase start potential V stop potential V step potential Vv Scan rate V s Estimated number of points Interval time s Signal sampler Options Potential applied Time WE 1 Current WE 1 Potential Index Logi
219. will be unlit on the Autolab display Clicking the HSTAB label again switches the bandwidth back to High stability For applications requiring very high bandwidth the Ultra high speed mode can be selected In this mode the control amplifier bandwidth is extended to 1 MHZ There is a significant oscillation risk using this setting and the noise levels will generally show an increase relative to the High speed or High stability mode i Warning The higher the bandwidth the more important it is to pay attention to adequate shielding of the cell and the electrode connectors The use of a Faraday cage Is recommended in this case 210 NOVA Getting started 4 6 5 RE input impedance and stability The electrometer RE input contains a small capacitive load If the capacitive part of the impedance between CE and RE is comparatively large phase shifts will occur which can lead to instability problems when working in potentiostatic mode If the impedance between the CE and the RE cannot be changed and oscillations are observed it is recommended to select the High stability mode to increase the system stability In general the use of High stability leads to a more stable control loop compared to High speed or Ultra high speed and a significantly lower bandwidth To make use of the full potentiostat bandwidth Ultra high speed mode the impedance between CE and RE has to be lower than 35 kQ This value is derived by testing In galvanos
220. x lt aray gt h Evst z Set cell Off m T Figure 3 22 The Chrono potentiometry fast procedure 34 Down to 100 us 149 Page NOVA Getting started The levels used in this procedure are shown in Figure 3 23 pa Chrono methods editor 0 Step lt Basic step Text Step Step Current 0 A Step Duration 0 01 S sample Yes hl Interval time 0 0001 5 Estimated number of points 100 w Advanced aav Figure 3 23 Overview of the levels used in the Chrono potentiometry fast procedure The signals sampled during this procedure are e Corrected time e Level e Time e WE 1 Potential e Index The automatic current ranging option is not available during the galvanostatic chrono methods measurement This procedure uses the Autolab control command to set the instrument to galvanostatic mode high speed and in the 1 mA current range before the measurement starts Figure 3 24 shows a measurement on the dummy cell c with the Autolab Chrono potentiometry fast procedure 150 a J T NOVA Getting started WWE 1 Potential W J 0 005 0 01 wao 0 02 0 025 0 03 0 035 QO Corrected time 5 Figure 3 24 The measured data obtained with the standard dummy cell c with the Chrono potentiometry fast procedure 3 17 Chrono coulometry fast Hardware Tags FI20 or on board integrator Profile Tags Basic Application Tags Interfacial electrochemistry This procedure requires the optional FI
221. ynamic linear sweep e Diferential pulse voltammetry square wave voltammetry sampled DC polarography Chrono amperometry At gt 1 ms Chrono potentiometry At gt 1 ms Chrono amperometry fast Chrono potentiometry tast fe Chrono coulometry tast Chrono amperometry high speed fe Chrono potentiometry high speed Chrono charge discharge Hnterrupt Hnterrupt high speed Positive feedback FRA impedance potentiastatic FRA impedance galvanastatic 2 PRA potential scan Standards i My procedures Figure 3 1 The Autolab procedures group in the Procedure browser frame 123 NOVA Getting started The available procedures are e Cyclic voltammetry potentiostatic e Cyclic voltammetry galvanostatic e Cyclic voltammetry current integration e Cyclic voltammetry linear scan e Cyclic voltammetry linear scan high speed 2 e Linear sweep voltammetry potentiostatic e Linear sweep voltammetry galvanostatic e Linear polarization e Hydrodynamic linear sweep e Differential pulse voltammetry e Square wave voltammetry e Sampled DC polarography e Chrono amperometry At gt 1 ms e Chrono potentiometry At gt 1 ms e Chrono amperometry fast e Chrono potentiometry fast e Chrono coulometry fast e Chrono amperometry high speed e Chrono potentiometry high speed e Chrono charge discharge e i Interrupt e j Interrupt high speed e Positive feedback e FRA impedance

Nova 1.10 Getting Started

Contents

Download Pdf Manuals

Related Search

Related Contents