CVS – Cyclic Voltammetric Stripping with Metrohm CVS in the Laboratory CVS Atline Systems CVS Online Systems CVS – Cyclic Voltammetric Stripping 02 Cyclic Voltammetric Stripping (CVS) and Cyclic Pulse Vol - printed out directly in mL additive per L bath liquid. This tam metric Stripping (CPVS) are widely used methods in means that topping up to the preset bath concentration the electroplating industry for the determination of or ga-can be carried out with highest accuracy. This guarantees nic additives in electroplating baths. A simple, robust and continuous and interference-free operation of the proc-affordable rotating disk electrode made of platinum is ess. The method has become generally accepted in the used in these analyses. For many technical coatings, par-electroplating industry, in particular thanks to the accu-ticularly in the manufacture of PCBs and semiconductor racy of the analytical results it supplies. components, this method is an essential part of production control. The most important fields of application The most important fields of application are acidic cop- per baths and tin-lead baths. Quantitative determination Suppressors of the additive is carried out via its influence on the DT – Dilution Titration deposition of the main component of the electroplating bath. As the measurement is based on an electrode reac-Brighteners tion that corresponds to the production process, the LAT – Linear Approximation Technique activity of the additive and thus its effectiveness in the MLAT – Modified Linear Approximation Technique electroplating process can be measured directly. The concentration of the additive can be determined exactly Leveler with CVS or CPVS. The effective concentration of the RC – Response Curve particular additive in the bath sample is shown and Applications Suppressor determination 03 Irrespective of whether hourly, daily or even weekly de - Each measurement is traceable and can be saved to the ter mination of suppressor components is necessary, dilu-hard disk together with the calibration if required. tion titration allows the suppressor concentration to be reliably determined. Determination The software automatically takes over the measurement Calibration curve parameters and the calibration data from the previously To calibrate the method, a standard solution is added to recorded calibration, inserts these into the measurement a base solution (VMS = Virgin Make-up Solution) in very method and is therefore ready for measurement in just a small steps and a calibration curve is recorded. This cali-few steps. Simple matching of the addition volume to bration curve is valid over a long period, but can be the sample, even saving VMS is possible. checked or renewed at any time. A new file is created for each measurement to avoid overwriting of previous calibration data. Determination of suppressor in acid copper with calibration curve Suppressor c = 12.774 +/- 0.111 mL/L (0.87%) DT determination of suppressor Z = 16.224 +/- 0.131 uL/L 1.00 15.0m Suppressor 800m 10.0m 600m )A )0 I ( Q( Q/ 0.13 5.00m 0.16 400m 0 200m -5.00m 0 0 0.50 1.00 1.50 0 5.00e-2 1.00e-1 1.50e-1 2.00e-1 Measuring curve for a suppressor determination – dilution titration 04 Brightener determination MLAT (Modified Linear Approximation Technique) or LAT tion of the additive is carried out via its influence on the (Linear Approximation Technique) allows fast, simple and deposition of the main component of the electroplating precise quantification of the amount of added brighten-bath. As the measurement is based on an electrode reac-er. Within just a few minutes time the result can be read tion corresponding to the production process, the activ-off the screen, exported to a LIMS or used for the auto-ity of the additive and thus its effectiveness in the elec-matic generation of a report. The quantitative determina-troplating process can be measured directly. MLAT CVS for brightener MLAT CVS for brig r htener brightener c = 15.158 mL/L +/- 1.196 mL/L (7.89%) 1.20m 00m 0 1.0 brigghten t er 1.00m 00u 0 50 800u ) ) (AA t (C I rcepte 'In 600u - Q 0 Q 400u - 00u 0 50 200u -3.7 0 -4.00e0 -2.00e0 0 2.00e0 4.00e0 0 0.50 1.00 1.50 Measuring curve for a brightener determination – MLAT 05 Leveler determination Besides the additives previously mentioned (brightener bration curve is also valid over a long period, but can be and suppressor), modern electroplating baths have a checked or renewed at any time. Each individual calibra-third substance added (leveler). This bath additive can tion is traceable and is saved to the hard disk. Calibration also easily be analyzed with the 797 VA Computrace. The can be carried out at any time during, between or after method for determining levelers, which is also performed a sample series. in two steps (calibration and determination), completes the comprehensive monitoring of the components Determination used. The software automatically takes over the measurement parameters and the calibration data from the previously Response Curve recorded response curve, inserts this data into the In this measurement mode, which is similar to suppressor method and is therefore ready for measurement in just a determination with DT, a calibration or response curve is few steps. The bath sample can be added directly to recorded in the first step. An electrolyte made up of VMS the prepared electrolyte solution or solutions can be and additives is used as the base solution here. This cali-ex changed. leveler determination leveler with RC c = 3.276 mL/L Sample with RC +/- 0.053 mL/L (1.60%) 1.00 6.00m leveler 800m 1.6 4.00m 600m 2.00m )A 0) I ( Q(Q/ 400m 0 -2.00m 200m -4.00m 0 0 0.50 1.00 1.50 0 1.00e0 2.00e0 3.00e0 Measuring curve for leveler determination – Response Curve 06 797 VA Computrace – the laboratory solution The lab measuring system allows fast, flexible and, of course, also precise performance of additive determination. CVS measurements can be realized in every laboratory, even in a very limited space. Manual or automated operation Even without additional accessories, the 797 VA Computrace is a fully functional analysis system meeting highest standards of accuracy and sensitivity. We offer you enhanced convenience with various upgrade options. MVA systems for the CVS technique Our recommendation for additive determination with CVS 07 The semi-automated 797 VA Computrace system for easy determination of additives with CVS. MVA-12 is the standard system for routine determination of organic additives in individual samples. Without a sample changer, it allows convenient determinations with a minimum of operator interventions. Automatic addition of auxiliary solutions such as VMS, intercept or standard solutions is carried out with model 800 Dosino dosing systems. For brightener determination the sample has to be added manually. For suppressor determination, sample addition is also automatic. With the aid of an optional pump, the measuring vessel can be automatically rinsed after each analysis. Fully automatic determination of organic additives in sample series. Fully automatic system with sample changer for CVS When determining brighteners, up to 28 samples can be analysis in the routine laboratory. analyzed. The possibility of recalibrating determinations during a series of samples guarantees outstanding accu-MVA-13 is our high-end system for the determination of racy. It is also possible to combine different methods in additives in electroplating baths with the samples being a single measuring procedure. The 843 Pump Station is added automatically by the 838 Advanced VA Sample used to automatically empty and rinse the measuring Processor. The suppressor content of up to 56 samples vessel after each sample. can be determined. 08 The 10 most important benefi ts The 797 VA Computrace opens up new possibilities: • Determination of additives in electroplating and voltammetric trace analysis with a single instrument • Outstanding precision thanks to the combination of proven Metrohm solid and reference electrodes with a highly sensitive potentiostat • Perfect Liquid Handling with proven Dosino technology • Automation with the 838 Advanced VA Sample Processor, 875 ProcessLab or an Applikon ADI 2045 VA online system • Important analysis methods from leading bath manufacturers are supplied • Results output in many different formats • Built-in quality assurance with GLP mode, individual rights of access for each user and automatic electrode test • Simple operation thanks to the user interface oriented on Windows operating procedures • Connection to the USB port of the PC • Thermostated operation (optional) Quality assurance made easy with the 797 VA Computrace Acces rights Electrode test 09 Acces rights to every program part can be freely defined The electrodes used are automatically checked before for each user. This allows convenient user management. each determination. If problems occur then the faulty electrode is identified and the fault shown on the screen. Validation with the GLP Wizard This test can, of course, also be triggered manually to The software automatically checks the validation inter-check the system. vals of the analysis system and informs the user when the next validation is due. Each report shows whether the Curve evaluation validation is still valid. The GLP Wizard guides the user The software of the 797 VA Computrace automatically step by step through the various validation tests and evaluates the measured curves and calculates the final automatically determines whether the test has been result. passed or not. Certified quality Diagnosis The development and manufacture of the instrument The built-in diagnosis program allows the individual com-and the software have been carried out in accordance ponents of the instrument to be checked. This diagnosis with the most stringent quality assurance criteria, which is a part of the GLP Wizard, but it can also be carried out we guarantee by issuing a quality certificate. The refer-independently. ence electrode and the electrolyte and standard solutions contained in the accessories can be identified by their serial number and are supplied together with individual certificates. ProcessLab Atline Systems – process-oriented, fully automatic determination of organic additives 10 11 Atline versus online analysis systems In an atline system the sample is taken manually and All components are accommodated in a rugged splash-trans ferred to the system. In this way various samples protected housing (IP 54) for use in rough production from different process stages or units can be easily ana-environments. An operating unit with touch-sensitive lyzed. In contrast to this, in an online system the sample surface allows easy and convenient operation. is automatically transferred to the analyzer via a bypass. The system is controlled by ProcessLab software with a Fully or semi-automated system with or without simplified user interface. Defined analysis sequences can sample changer for atline CVS process analysis be started at the press of a button thus ensuring error-Voltammetry (VA), which is already well established in free operation. The system is configured according to the the laboratory, and Cyclic Voltammetric Stripping (CVS) process requirements and is therefore optimally matched are also available for on-site operational routine analysis. to the process. ProcessLab is optimally designed for additive determination in electroplating baths, whereby the samples are A database with the option of graphical presentation of transferred to the system either one by one or automati-the results in an SPC chart (Statistical Process Control cally by a sample changer. chart) provides information on the status of the production line under control at any time. CVS online process analysis Applikon ADI 2045 – Online – fully automated 12 determination of organic additives with CVS The Applikon 2045VA is an online instrument for per-the PLC controls all the external units and the additional forming voltammetric analyses. This measuring technique pumps, the PC controls the VA Computrace and the has been used for decades in routine laboratory opera-Dosino dosing systems connected. The touch screen user tion; Applikon has now also successfully implemented it interface allows easy and intuitive operation. An addi-for online analysis. Quality control of electroplating baths tional USB keyboard or mouse can be connected to the with CVS can now take place directly in an operational system, as required. The operating section of the soft-environment. ware contains a large number of options, whereas in the status section the current system status can be checked The system is controlled by a combination of industrial at any time. PC and programmable logic controller (PLC). Whereas 13 Technical specifi cations 14 Laboratory system 797 VA Computrace Voltammetric measuring stand with built-in potentiostat and galvanostat potentiostat / galvanostat Voltage range ±5 V Output voltage ±12 V Current range ±80 mA Current measurement 7 ranges (10 nA to 10 mA) Sweep rate (CV) <1 mV/s...3 V/s (at 1 mV resolution) <1 mV/s...35 V/s (at 10 mV resolution) Power supply Voltage 100...240 V; frequency 50...60 Hz Power consumption 120 VA Temperatures Nominal working range 0...45 °C at 20…80% relative humidity ProcessLab – atline-process analysis Sample Sampling frequency 1...20 / day Analysis time typically <15 min Sample types >10 Sample volumes 0.2 mL...250 mL Sample temperature 5 °C...45 °C Connections Digital inputs 24 V DC, e.g. emergency off, liquid level sensors, ... Digital outputs 24 V DC, stirrer, peristaltic pumps, ... Analog inputs 4...20 mA, number variable Analog outputs 4...20 mA, number variable Relay outputs 1 A at 120/230 V Operation TFT screen with fully functional membrane keyboard and touch pad Touch screen optional Temperature Nominal working range 0..+40 °C at 20…80% relative humidity ADI 2045VA – online process analysis Samples and sample flow Sampling frequency programmable Analysis time typically approx. 30 min Sample currents maximum 4 Sample volume 0.2 mL...50 mL Sample temperature 5 °C...45 °C Sample pressure 0...0.5 bar, i.e. 0...7.2 psi (without preparation) Connections Results output (analog) 4...20 mA, max 16 channels Digital remote control 24 VDC, Start, Stop, Continue, Samples 1,2,3,4 Digital input detector 24 V DC, max 12 channels (leak sensor, reagent monitoring, etc.) Digital output relay 2 A, Power On, Sequence Running, Warning, Error, Result alarm, 1,2,3,4, Service General Touch screen operation Ordering Information 797 VA Computrace – for laboratory use 15 2.797.0030 797 VA Computrace for CVS (Cyclic Voltammetric Stripping) for analyzing organic additives in electroplating baths. Measuring stand with integrated potentiostat and galvanostat. Three-electrode system with rotating platinum disc electrode (Pt RDE), Ag/AgCI reference electrode and platinum auxiliary electrode. Can be equipped with Metrohm Multi-Mode Electrode (MME). Includes PC program 6.6053.010 and comprehensive accessories for setting up the measuring station. MVA-12 Semi-automatic 797 VA Computrace system for convenient determination of organic additives. 1 x 2.797.0030 797 VA Computrace 3 x 2.800.0010 800 Dosino 1 x 6.3032.250 807 Dosing Unit 50 mL (glass) 2 x 6.3032.120 807 Dosing Unit 2 mL (glass) 1 x 2.843.0040 843 Pump Station (optional) 1 x 2.846.0010 Dosing Interface (optional to connect 4 additional 800 Dosinos) MVA-13 Fully automatic 797 VA Computrace system for unattended determination of organic additives. 1 x 2.797.0030 797 VA Computrace 1 x 2.838.0310 838 Advanced VA Sample Processor 1 x 2.843.0040 843 Pump Station 3 x 2.800.0010 800 Dosino 1 x 6.3032.250 807 Dosing Unit 50 mL (glass) 3 x 6.3032.120 807 Dosing Unit 2 mL (glass) 1 x 2.846.0010 Dosing Interface (optional to connect 4 additional 800 Dosinos) ProcessLab – atline process analysis A wide range of additional modules and components are available. Here is just a small selection: - ProcessLab measuring amplifier for connecting various sensors - ProcessLab digital input and output 24 V DC - ProcessLab analog input and output 4...20 mA - ProcessLab relay output - ProcessLab sensor connection - ProcessLab measuring vessel with stirrer and various measuring vessels - ProcessLab peristaltic pump with 40 mL/min, 120 mL/min or 320 mL/min - ProcessLab sampling system with associated sample loops - ProcessLab overflow pipettes in various sizes - ProcessLab solenoid valve module to control liquid currents - Containers in various sizes, with liquid level sensor Please contact your local representatives for precise ProcessLab contact address dimensions and design of your ProcessLab system. www.metrohm-processlab.com Thanks to its modularity, the instrument can be optimally Online process analysis contact address adapted on-site to meet specific requirements. www.applikon-analyzers.com www.metrohm.com G, Herisau ohm A witzerland by Metr , printed in S SW Subject to change Layout Ecknauer+Schoch A 8.797.5001EN – 2009-08