Surface finishing Process control in electroplating and PCB manufacturing 02 Metrohm... • is the global market leader in titration • offers a complete portfolio for NIR and Raman analysis, in addition to all of the methods of • ion analysis – titration, voltammetry, and ion chromatography • is a Swiss company and manufactures almost exclusively in Switzerland • grants a 3-year instrument warranty and a 10-year warranty on chemical suppressors for anion chromatography • provides you with unparalleled application expertise • offers you over 2000 applications free of charge • supports you with dependable on-site service worldwide • is not listed on the stock exchange, but is owned by a foundation • takes a sustainable approach to corporate management, putting the interests of customers • and employees ahead of maximizing profit Metrohm – customized analysis for surface finishing An industry with high standards 03 The coating and finishing of surfaces using electroplating required precision − both in the laboratory and atline and techniques is a highly sophisticated process. Be it the online in the process environment. finishing of metal parts or the coating of printed circuit boards, the quality required in the intermediate and end Count on our support products is only achieved if the composition of the We offer you not only first-rate instrumentation, but process baths is right. At the same time, rising costs of rather complete solutions for the particular task at hand. raw materials and energy make it absolutely essential to Your Metrohm contacts are experienced specialists, who drive production as efficiently as possible. develop customized applications for you and support you in every aspect of the production process. As a leading manufacturer of instruments for chemical analysis we know about these challenges. That is why we Discover on the following pages what solution Metrohm offer you state-of-the-art instrumentation to control and offers you to ensure the quality of your products. optimize the quality of your coating processes with the Challenge us! Part I: Solutions for laboratory analysis pages 4−12 Part II: Processes and applications pages 13−27 Part III: Solutions for atline, online, and inline analysis pages 28−39 Part I: Solutions for laboratory analysis 04 Titration and pH/conductivity measurement Titration is an established analytical technique in quality The rugged, compact instruments are characterized by control of electroplating processes. Titration combines their ability to measure anywhere and by an exceptional utmost precision with a very easy procedure. In most ease of use that is thanks to their well-organized user cases it is possible to use undiluted sample solution to interface and offer various options for data managment, determine the compenents of reaction solutions. This like printout, storage to a PC or LIMS. enables even semiskilled users to carry out the analysis quickly and accurately. Because of the wide range of opportunities for automation, the amount of work required for analysis is generally limited to providing an aliquot of sample and pressing a key. Versatile and convenient Another benefit of titration is its versatility. Different analyses can be performed with one and the same basic instrument: e.g., monitoring the content of electroplating baths, analyzing acid mixtures in etching baths or checking the purity of rinsing solutions. Solutions for every budget and every requirement The 912 Conductometer, 913 pH Meter, and 914 pH/ Conductometer are “two-in-one” meters for laboratory and field use and therefore ideally suited for routine analyses in the lab and for applications in the field. 848 Titrino plus The 848 Titrino plus is the most economical solution for all routine potentiometric titrations, such as acid/base, redox, precipitation and surfactant titrations, and also complexometry. Its ease of use, the output of results on paper and the collection of results in the database software tiBase make documentation of results perfectly easy. Plate Titrando 05 The Plate Titrando offers a comprehensive package for the most common potentiometric analyses in the electroplating industry. It contains all the accessories for acid/ base and redox titration and for the determination of chloride. Its complete intelligence monitors all the important system components, such as buret or sensor. The patented Dosino technology provides for contact-free handling of reagents and burets. Robotic Transfer Analyzer Metrohm offers you comprehensive solutions for the complete automation of your titrimetric analyses. The benefit is evident: higher sample throughput, minimized risk for operating errors, more precise and consistent results and, of course, enormous savings on time and costs. All of this comes to your lab with the Robotic Transfer Analyzer. Just put your samples on the rack – everything else from sample preparation to analysis is taken care of by the automated system. OMNIS – The new, fully modular titration platform OMNIS combines all measurement results for a 06 offers titration performance on a whole new level sample Expand your system as you go If multiple parameters were measured in a sample, Start with a single OMNIS titrator and add titration and OMNIS links them all directly to the sample and shows dosing modules when needed for further applications or the results at a glance. samples to be analyzed. By including additional measuring interfaces and burets, you can have up to five differ-For a brass plating bath, the results for the determination ent applications ready for use – even in parallel. of the copper content, zinc content, free cyanide, and carbonate are all linked. If sample throughput is increasing, add an OMNIS Sample Robot for fully automated titration. Thanks to modular work stations, racks, and pumps, OMNIS is capable of analyzing four samples fully automatically in parallel. OMNIS Sample Robot M with 4 Work Stations for simultaneous, fully automated analysis of 4 samples. 07 Make your laboratory safer with 3S adapter tech- Secure information transfer: The RFID chip in the bottle nology cap provides all relevant information on the content of We have made chemical handling easier and safer. The the bottle. result is our patented Liquid Adapter with 3S Technology. Smart connection: The reagent data is automatically 3S stands for: transmitted to the titration system. Safe chemical handling: Just connect the OMNIS Liquid Adapter to the bottle cap and avoid contact with the bottle contents. Ion chromatography 08 Multicomponent determination with a single Metrohm Inline Sample Preparation Techniques analysis in surface coating: Ion chromatography (IC) enables the determination of • Inline Ultrafiltration to remove particles from various numerous main and secondary components of electro-samples plating baths as well as traces of impurities in the form of • Inline Dialysis for ion analysis in emulsions and organic and inorganic ions or polar substances with soap-containing rinsing solutions utmost reliability and precision. A major benefit of ion • Inline Dilution to monitor acid baths and component chromatography is that chemically similar substances can analysis of electroplating bath solutions be determined in parallel in a single analysis. The analyte • Inline Matrix Elimination to analyze rinsing solutions concentrations may extend from the ng/L to % ranges. such as isopropanol • Inline Preconcentration for trace analysis in ultrapure Save time and costs with automated sample water preparation • Inline Neutralization and Inline Cation Removal for Ion chromatographic analyses can be automated easily analyzing impurities in electroplating baths and efficiently; interfering matrix effects can be avoided • Intelligent Partial-Loop Injection Technique by choosing the appropriate detection method or com-guarantees variability and simplicity in your analysis bining the sample delivery with one of our numerous Inline Sample Preparation Techniques. These inline techniques, some of them patented by Metrohm, make it possible to integrate the sample preparation into the analysis and to automate it completely. This increases reliability, saves manual work and guarantees traceability of the entire analysis. 940 Professional IC Vario – solution for demand- 09 ing tasks The 940 Professional IC Vario system can be used both to analyze acid baths and for trace analysis of impurities in ultrapure water, rinsing solutions, and adsorption solutions. Because of the system’s self-monitoring functions operating errors are virtually eliminated. Owing to the complete automation, including Metrohm Inline Sample Preparation (MISP), the system can be recommended both for routine analysis and for complex applications in research and development. 930 Compact IC Flex – predestined for routine analysis The 930 Compact IC Flex is the ideal solution for routine analysis, if the focus is on only one application. Like the 940 Professional IC Vario, the 930 Compact IC Flex is also equipped with intelligent hardware components. To - gether with the MagIC Net ion chromatography software the system enables intuitive operation. Just like the 940 Professional IC Vario, the 930 Compact IC Flex can be automated in various ways and complemented by Metrohm Inline Sample Preparation Techniques. Voltammetry 10 Voltammetry is an electrochemical analytical method 884 Professional VA that provides information on – among other substances The 884 Professional VA is a flexible measuring instru- – the type and amount of metals contained in a dissolved ment for accurate and sensitive voltammetric and polaro-sample on the basis of a current-voltage relationship. The graphic analyses. The analyses can be easily automated importance of voltammetry is based on its high degree of by adding Dosinos and a sample changer. The accompa-accuracy and sensitivity, the possibility of speciation nying viva software enables individual optimization of analysis and the good price-to-performance ratio. methods. Precise measurements even in the presence of Convenient data management high salt concentrations All the relevant measurement data and results obtained The particular challenge for analysis in the electroplating with the 884 Professional VA and viva can be transferred sector are the large quantities of salts typically contained very easily to your LIMS − as text data or in xml format. in electroplating samples. For such samples, many measuring techniques can at best provide unsatisfactory results; others cannot provide any results at all. Here, electrochemical analysis is able to demonstrate its strengths; the disadvantage for other methods is trans-formed into a big advantage: large amounts of salt equal good conductivity, which is a prerequisite for electrochemical analysis. Furthermore, the infrastructure required for a voltammetric measurement system requires hardly any expenditure. All it needs is electricity and a supply of nitrogen. Ven - tilation, flammable gases and associated safety requirements are no issues. 884 Professional VA CVS (Cyclic Voltammetric Stripping) Standard method in PCB manufacturing The main CVS applications in the electroplating 11 Cyclic Voltammetric Stripping (CVS) and Cyclic Pulse and semiconductor industries Voltammetric Stripping (CPVS) are widely used methods in the electroplating industry for the determination of Suppressor Brighteners Leveler organic additives. The CVS method is an essential com- Process DT – Dilution • LAT – RC – ponent of production control in many industrial coating Titration Linear Response processes, especially in the manufacture of printed circuit Titration Curve boards or semiconductors. Approximation Techique • MLAT – With CVS or CPVS it is possible to determine the concen-Modified tration of additives exactly. The effective concentration of Linear the particular additive in the bath sample is shown Approximation directly in mL additive per L bath. Precise subsequent Technique dosing to meet the target concentration then becomes possible. This ensures continuous, trouble-free operation of the plant. Complete voltammetry systems – the right system for each application Metrohm offers systems packages that are ready-to-use operation, systems with automatic addition of solutions and suit the needs of the electroplating and semiconduc-and fully automated systems for high sample through- tor industries. There are systems available for manual put. 884 Professional VA semiautomated for CVS MVA-23 – fully automatic determination of The 884 Professional VA semiautomated is the standard organic additives in sample series system for routine determination of organic additives in The MVA-23 is the high-end system for the determina-individual samples. Auto matic addition of auxiliary solution of additives in electroplating baths with the samples tions such as VMS, intercept or standard solutions is being added automatically by an 858 Professional carried out with Dosinos. For brightener determination Sample Processor. The suppressor content of up to 56 the sample only has to be added manually. In the case of samples can be determined. When determining brighten-suppressor determination, this is also done automatically. ers, up to 28 samples can be analyzed. Various methods can also be combined in a single measuring procedure. Potentiostats/Galvanostats by Metrohm Autolab 12 Systems for electrochemical analysis in research Autolab PGSTAT-potentiostats for all electro- and development chemical methods The electrochemical interface has been of particular inter-At the fundamental level, the Autolab PGSTAT provides est in fundamental and applied research for many decades. the scientist with all the electrochemical methods of inter-The understanding of the nature of the processes involved est for surface science. Potentiostatic and galvanostatic at the electrochemical interface, from mass transport to control allow the researchers to accurately control the reac-electron transfer kinetics, provides invaluable information tions taking place at the electrochemical interface as well which can be used to optimize existing surface prepara-as the rate of these reaction and the quantity of material tions processes and develop new methods. involved. Using these methods, the composition, rough- ness, structure, and growth mode of deposited materials For example, Electrochemical Atomic Layer Deposition can be controlled. (EALD) and Surface-Limited Redox Replacement (SLRR) are two particular examples of novel electrochemical methods which are now used in technologically relevant applications. Other novel electrochemical surface preparation techniques involve the use of the macromolecular assem-blies using dendrimers or nanoscale templating. 13 Part II: Processes and application solutions Quality control of basic chemicals and raw materials Quality assurance in production begins when the used basic chemicals are checked. Analytical instruments from Metrohm make it possible to establish the concentrations of acids or bases reliably, quickly and easily, determine the metal content of various raw materials or detect any impurities in trace quantities. Titrimetric applications Sample Titrant Metrohm Electrode Sulfuric acid, hydrochloric acid, sodium hydroxide, H SO c(NaOH) = 0.1 mol/L 6.0255.100 Profitrode 2 4 ammonia, and hydrogen peroxide are some of the most HCl c(NaOH) = 0.1 mol/L 6.0255.100 Profitrode frequently used basic chemicals in the electroplating NaOH c(HCl) = 0.1 mol/L 6.0255.100 Profitrode industry. Normally their content is checked by means of NH OH c(HCl) = 0.1 mol/L 6.0255.100 Profitrode 4 potentiometric titration when incoming goods are exam- H O c(KMnO ) = 0.1 mol/L 6.0431.100 Pt Titrode 2 2 4 ined, to ensure the particular mixture is in the right pro-portions for subsequent use or dilution. 14 Ion chromatographic applications Impurities in hydrogen peroxide, isopropanol, etc. Determination of ultratraces Ion chromatographic applications are used to monitor When ultratraces need to be determined, Inline Pre con-etching, extracting and rinsing solutions. Analyses of im - centration is added to Inline Matrix Elimination. The re - purities, e.g., in hydrogen peroxide or isopropanol, play quirements here area are not only work that is free of a big role here. For this, an IC system is equipped with blank readings and of any carryover, but also exact Inline Matrix Elimination. This rules out any matrix effect measurement of the preconcentration volume. All this is and makes reliable analysis possible. made possible by the patented 800 Dosino. This state-of-the-art liquid handling system provides complete flexibility in the choice of injection volume and can be adapted at any time to the required degree of sensitivity. At the same time the method can be calibrated with just one standard solution. Determination of 30% hydrogen peroxide spiked respectively with 10 μg/L Fˉ, Cl–, NO –, Br–, NO –, PO 3– and SO 2–; column: Metrosep A 2 3 4 4 Supp 5 - 150/4.0; preconcentration column Metrosep A PCC 2 HC/4.0; eluent: 3.2 mmol/L Na CO + 1.0 mmol/L NaHCO , 0.8 mL/min; 2 3 3 column temperature: 25 °C; sample volume: 20 μL 15 Voltammetric applications Analytes Raw material Traces of heavy metals in basic chemicals Zinc, cadmium, lead, nickel, cobalt Sodium hydroxide Heavy metal ions present in the basic chemicals can Zinc, cadmium, lead, nickel, cobalt Hydrochloric acid cause interference during the production process. For Iron Phosphoric acid this reason, a purity check is carried out when goods are Iron, nickel, cobalt Sulfuric acid received. On the other hand, in the electroplating industry large quantities of basic chemicals are used and as a result size-able quantities of heavy metals are introduced into the production process. This contamination needs to be prevented as far as possible right at the start of the production chain, to avoid the need to remove it at great cost later. Such checks are a classic application of voltammetry. Nickel in sodium hydroxide by means of adsorptive stripping voltammetry (AdSV) To analyze the concentration of nickel in a solution of sodium hydroxide, the solution is first acidified to bring the nickel into its ionic form. The pH is then adjusted to 9.6 with an ammonium chloride buffer. Dimethylglyoxime (DMG) is added to produce a Ni-DMG complex, which can be preconcentrated on the mercury dropping elec- trode. Quantification is by means of standard addition. 16 Metal production by means of electrodeposition In metal production by means of electrodeposition, the high purity of the metals used is crucial for the quality of the resulting surfaces. Metrohm offers you reliable methods to detect any impurities with highest precision. Zinc electrolysis Analyte Sample In the production of zinc the metal is deposited electro-Cadmium Zinc electrolyte lytically on a cathode. The zinc electrolyte used contains Lead Zinc electrolyte impurities due to heavy metals. Using voltammetry it is Copper Zinc electrolyte possible to determine traces of heavy metals in the Thallium Zinc electrolyte electrolyte reliably and, as a result, to monitor metal Nickel Zinc electrolyte deposition in the electroplating process with the required Cobalt Zinc electrolyte precision. Iron Zinc electrolyte Antimony(III) Zinc electrolyte Germanium Zinc electrolyte Selenium Zinc electrolyte Metals as main components of electroplating baths The concentration of metals in electroplating baths can vary considerably depending on intended purpose. The required 17 thickness of the coating, the nature of the material and market prices for the expensive noble metals are the key parameters. The appropriate analytical technique is selected according to the concentration of the metal to be determined. Metrohm offers suitable systems for carrying it out. Titrimetric applications Ion chromatography applications Copper and nickel in acidic metal baths Silver and ammonium in etching baths containing Multilayer systems are widespread in corrosion protec- hydrofluoric acid tion. For example, corrosion-inhibiting nickel is applied Ion chromatography is often used to determine medium on top of an intermediate layer of copper. In the deposi-to low concentrations of metals in etching solutions and tion processes the concentration of the metal being electroplating baths. Because such solutions and baths deposited is an important parameter for the electric cur-often contain high ionic matrices, Metrohm Inline rent to be applied. If the concentrations are too low, a Dilution is used here. An example of a typical ion chro-stronger current has to be applied, which can drive up matography application is the determination of silver in the production costs significantly. the mg/L range along with ammonium in the g/L range in etching baths containing hydrofluoric acid. The copper content in acidic copper baths is determined by redox titration with c(Na S O ) = 0.1 mol/L, following 2 2 3 prior reduction of Cu(II) to Cu(I) by means of potassium iodide. The nickel content is determined by way of com-plexometric titration with c(Na EDTA) = 0.1 mol/L. 2 18 Voltammetric applications Metal determination and speciation analyses in electroplating baths Of course, the concentration of the metal used as the main bath component can also be determined by means of voltammetry. In addition, it is possible to differentiate bet ween various oxidation states of metal ions or between free and bound metal ions. Typical applications are: Analyte Type of bath Gold (I) Cyanidic gold bath Palladium Activator Chromium(III), chromium(VI) Chromium bath Nickel Nickel bath Cobalt Cobalt bath Inorganic and organic secondary components of electroplating baths Organic and/or inorganic additives are included in electroplating baths to control the physical properties (ductility, 19 hardness, tear strength, brazeability, etc.) of the deposited metal layer. In the case of decorative electroplating, the visual appearance of the surface is optimized with additives. Complexing agents are also added to baths to keep large quantities of metal in solution. Essentially, acids, bases and ions in low concentrations can be used to influence the nature of the surfaces of printed circuit boards, contacts, metal components etc. These bath additives must be analyzed at regular inter-vals, so the production process is most efficient and a consistent end product quality ensured. 20 Titrimetric analyses Boric acid and tetrafluoroboric acid in nickel baths Surfactant determination in electroplating baths Apart from chloride and sulfate, nickel plating baths also To improve surface properties, surfactants are added to contain boric acid, which is used as a buffer to maintain electroplating baths, because they improve surface wet-a certain pH value. Using potentiometric titration it is ting and emulsify brighteners. Standard anionic surfac-possible to determine both the free boric acid and the tants (like, for example, in nickel baths) are determi ned by free tetrafluoroboric acid. After addition of mannitol, the means of potentiometric titration with TEGO®trant A100 formed mannitol complexes are titrated with sodium and an «Ionic Surfactant» electrode. hyd roxide solution. The determination is carried out directly in the plating bath sample; nickel and other metal ions do not interfere. Ion-chromatographic analyses 21 Concentrated acids in etching solutions One of the uses of ion chromatography is to check the (0.25 μL) makes possible, for example, fully automatic content of an electroplating bath. For this, the anion analysis of concentrated acid mixtures such as an etching concentrations of the acids and acid mixtures used are solution containing 10% HF, 30% HNO , 30% H SO and 3 2 4 determined. The unique combination of Metrohm Inline 13% H PO . 3 4 Dilution Technique and a minimum injection volume Etching solution diluted inline 1:100, column: Metrosep A Supp 5 - 150/4.0; eluent: 3.2 mmol/L Na CO , 1.0 mmol/L NaHCO , 2 3 3 0.7 mL/min; sample volume: 0.25 μL (internal loop) 22 Nitrate in nickel baths Organic acids in electroplating baths Starter substances, catalysts or contamination from Organic ionic and polar substances can also be deter-previous steps in the μg/L to mg/L range can be deter- mined using ion chromatography. Typical applications are mined by way of ion chromatography for the purpose of determinations of organic acids in electroplating baths. process control. For example, citric acid, formic acid and lactic acid in the g/L range are monitored by means of ion-exclusion One example here is the determination of nitrate in chromatography. nickel baths to check the rinsing procedure and to identify unwanted contamination in a newly prepared nickel By contrast, ion-exchange chromatography is used to electroplating bath. By using the intelligent Partial Loop determine organic acids together with inorganic compo-Injection Technique it is possible to cover a concentration nents in electroplating baths or starter substances (e.g., range of 1:10‘000 with a single calibration. The sample tartaric acid and citric acid together with hypophosphite volume varies within the range 2 − 200 μL. and tungstate). Rinsing solution after bath cleaning; column: Metrosep A Supp 5 - 150/4.0; eluent: 3.2 mmol/L Na CO , 1.0 mmol/L NaHCO , 2 3 3 0.8 mL/min; column temperature: 25 °C; sample volume: 200 μL 23 Voltammetric applications Analyte Type of bath Lead in nickel baths Lead, antimony, bismuth Nickel bath Lead is added to nickel baths chemically as a stabilizer. In Cobalt, sulfite Gold bath addition, it has a large effect on nickel deposition itself. Cobalt, cadmium, thallium Cyanide bath The quantity of lead must be maintained in the low mg/L Chromium(III) / chromium(VI) Chromium bath range, in order to be able to guarantee uniform deposi-Saccharin Acidic copper bath tion of nickel. Using voltammetry, it is possible to monitor Thiourea Acidic copper bath limits reliably, quickly and easily. Antimony/bismuth in nickel baths Increasingly, nickel baths are being treated with antimony and/or bismuth as an alternative to lead. Here too, the use of voltammetry can be recommended. 24 CVS and CPVS to determine organic additives Analyte Type of bath Cyclic Voltammetric Stripping (CVS) and Cyclic Pulse Suppressor Acidic copper bath, Voltammetric Stripping (CPVS) are widely used methods tin bath, tin-lead bath in the electroplating industry for the determination of Brightener Acidic copper bath organic additives. The CVS method is an essential com- Leveler Acidic copper bath ponent of production control in many industrial coating processes, especially in the manufacture of printed circuit boards and semiconductors. Measuring curve for a suppressor determination – dilution titration Monitoring of wastewater and process water In electroplating installations wastewater is produced at various points in the manufacturing process. Depending on 25 the step in the process (degreasing, electroplating, passivating, pickling, etc.), this wastewater might be highly toxic and therefore require elaborate treatment, in order to eliminate any risks to humans and the environment. Strict limits apply to the substances concerned and these need to be monitored throughout. Metrohm offers you numerous solutions for analyzing process water and wastewater; with them you can optimize the productivity of your processes and ensure optimized compliance with environmental legislation. pH and conductivity measurement in wastewater Whether directly in the process or in the laboratory, the pH and conductivity value can always be determined quickly, reliably and GLP conform with the 912/913/914 meters. The 912 Conductometer is ideal for determining conductivity as a single parameter. The pH value can be determined with the 913 pH meter. With the 914 pH/ Conductometer it is possible to determine both parame- ters even in the same measuring vessel. 26 Ion chromatographic applications Trace analysis to monitor wastewater and rinsing water The advantages of ion chromatography are most appar- An example of this is ultratrace analysis of anions and ent in the monitoring of wastewater, rinsing water and cations in ultrapure water. Reliable results, unaffected by process water. Because of its versatility a wide range of interferences, are possible if Metrohm Inline Preconcen-questions concerning compliance with environmental tration is used in combination with Inline Calibration. re gulations, effectiveness of cleaning steps or quality requirements can be answered during production. Furthe rmore, ion chromatography makes it possible to detect impurities, carryover or discharges right down to the ng/L range. Fully automatic and precise analysis of cation traces of ion exchange eluates: column: Metrosep C 3 - 150/4.0; preconcentration column: Metrosep C PCC 1 HC/4.0; eluent: 2.5 mmol/L HNO , 1.0 mL/min; column temperature: 45 °C; sample volume: 10.0 mL 3 27 Voltammetric applications Analyte Sample Heavy metal analysis in wastewater and process Tin Wastewater, process water water Iron Wastewater, process water The strict regulations for environmentally compatible and Zinc, cadmium, lead, copper Wastewater, process water efficient use of metals have always had a great impact on Nickel, cobalt Wastewater, process water the operation of electroplating installations. With the Chromium Wastewater, process water (total) 884 Professional VA you are fully able to satisfy the re - Mercury Wastewater quire ments for heavy metal analysis in wastewater. Arsenic Wastewater Thallium Process water Not only wastewater, but also the process waters used Selenium Process water need to meet strict criteria, depending on the particular use. Whether you are determining the concentration of iron in boiler feed water or monitoring traces of metal in (rinsing) waters due to carryover – with voltammetric system solutions from Metrohm you are on the safe side. Part III: Solutions for atline, online, and inline analysis Deviations from target values must be controlled Processes that rely on any analytical measurement to 28 Many processes are control ed within tightly defined maintain the process near to an operating target and limits for many basic parameters such as temperature within an operating window will be accurate dependent or pH. Other more unique parameters include acid con-on: centration in etching solutions and organic additives in • The analytical instrument employed copper plating processes. • Error of sampling from the process and sample Often control of these parameters is critical to maintain preparation product and process specifications to achieve optimal • Frequency of analysis product quality and consistency. Deviation of these pa- • Process variation error rameters from target values can negatively impact product quality and lead to excessive operating costs via: Limitations of offline analysis Offline laboratory analysis can have a negative impact • Excess chemical consumption on process accuracy by introducing sampling error • Reduced throughput/fluctuations in plating rate and limiting analysis frequency due to manual limitations • Higher energy usage and differences between analysts. • Out of specification product / rejects / reworks • Lower yields 2035 Process Analyzer configured for potentiometric titrations 29 Improve accuracy, reduce sampling error Increase your competitive advantage Introducing inline, atline, or online process analyzers Moving from manual laboratory sampling to a process reduces the sampling error and increases the sampling analyzer al ows you to run production much closer to frequency as well as improving the prediction error for your operating target, resulting in increased yield, im-the analysis. proved final product quality and consistency. All this leads to increased profit margins and less out of spec-Improving all these steps leads to significant improve-ification product. ments in process accuracy narrowing the normal operating window to ensure the process is operating at its Also, the reduction in process variation can mean prod-most efficient. uct specifications may be further tightened, increasing the efficiency competitiveness of the manufacturing process. Atline process analysis with ProcessLab Process monitoring in electroplating ProcessLab – robust, flexible, and easy to use 30 In the electroplating process, material is continuously ProcessLab is a robust and easy-to-use analysis system being deposited on the workpieces. To ensure that the that is operated directly at the process line. With an IP54 quality of the treated surfaces is consistent, the concen-protection classification the system is able to withstand tration of the relevant bath ingredients and the reaction even the harshest process conditions. The analysis system products must not exceed nor drop below the defined consists of a touchscreen TFT control unit, a customized tolerance limits. This demands close process monitoring, analysis module and a sample delivery station. All mod-which is normally carried out using wet chemical analyses. ules are based on proven components from the Metrohm portfolio and are combined specifically for each cus- It is a great advantage if samples do not first have to be tomer according to applications. taken to a laboratory, but can be analyzed directly on the production floor by shift personnel. This allows the yield Samples are taken from the process manually by the of the raw materials used to be optimized and the plant oper ating personnel and held ready. Analysis on the to be operated at maximum efficiency while saving time ProcessLab is started by a single press on the touchscreen and money over cumbersome laboratory techniques. and then proceeds fully automatically. Process integration comes with the usual process signals. After analysis, the measurement data are passed on directly to the plant’s process control system. The measurement data are shown on the ProcessLab with the appropriate action and warning limits. 31 Combination of analytical methods ProcessLab combines various analytical methods on a minimal footprint: titration, direct potentiometry, and photometry. The same principle applies throughout: ful y automatic processing of samples with robust and proven modules and thus process control with minimized errors. Consequently, entire process chains can be monitored with a single system – from pretreatment to finishing baths and on to wastewater monitoring. The perfor- mance of the individual subprocesses can be increased by the individual frequency of samples. Thus, the baths can be operated within the optimum parameters and, as a result, the required product quality can be guaranteed. Atline application examples 32 Monitoring electroless nickel baths: Monitoring alkaline zinc baths: nickel sulfate, hypophosphite and pH value zinc, sodium hydroxide and carbonate Electroless nickel baths are used for many applications. To shield iron and steel components from corrosion, zinc The advantages of chemical nickel deposition are an continues to be the main material used as a protective even distribution of the coating as well as the possibility coating. The plating baths deposit zinc on the compo-to use it with rack and barrel facilities. nents electrolytically, thereby ensuring that the materials have a long life. The finishing baths are alkaline; over Control of this process is critical for consistent plating time the concentration of carbonates in solution increas-rates and bath stability. Nickel consumption is not replen-es, impairing the deposition properties and reducing cost ished by a dissolving anode as in electroplating process-efficiency of the process. The deposited zinc must be es. Therefore, frequent analysis and chemical addition re placed so the parts being galvanized are coated evenly. are required to control the bath within tolerated limits. The entire process chain, from cleaning of the compo-Also increasing salt concentrations of the unincorporated nents in degreasing baths and galvanizing to passivation ions in the solution can impair the coating properties or of the zinc coating on the finished item can be moni-the rate of deposition. These increases must be mo ni- tored with ProcessLab. tored to prolong the bath life through re gen e rative measures. ProcessLab ensures economic and environ- mentally aware production throughout the process chain. Process Application Note • Online analysis of Ni and hypophosphite content. AN-PAN-1012 Schematic diagram of the various process stages in electrogalvanization. The various baths are: 1: Acid degreasing bath 2 + 3: Rinsing baths 4: Acid pickling bath 5 + 6: Rinsing baths 7: Alkaline zinc bath 8 + 9: Rinsing baths 10: Passivating bath 11 + 12: Rinsing and cleaning baths 33 Monitoring a phosphatizing process ProcessLab monitors, records and documents all the In cleaning, degreasing, and rinsing baths, and also in im portant analytical parameters of the phosphatizing the phosphatizing bath itself, the various parameters process. The combination of the analytical methods involved must be adhered to exactly. Those determined within one system as well as the intuitive handling via the in the degreasing and rinsing baths are pH value, con-well-arranged user interface ensure easy and reliable ductivity, free alkalinity, and total alkalinity, while the monitoring of the entire process. phosphatizing bath is analyzed for free and total acids, accelerator, zinc, and fluoride. Online process analysis 34 Customized process control Robust design Online analyzers from Metrohm Process Analytics are Our process analyzers are designed for the rigorous designed for continuous operation and enable fully auto-demands of the production environment. The housings matic monitoring of process baths in electroplating and meet the specifications of NEMA 4 and protection class PCB manufacturing – around the clock, seven days a IP66. week. There are no limits: whether your requirement is for one or several sample streams, for a single component or multiple parameters, we will configure the right system for you. Of course, your wastewater treatments can also be controlled or monitored with online analyzers from Metrohm Process Analytics. Proven wet chemistry methods Metrohm Process Analytics online analyzers are based on proven wet chemistry methods such as titration, ion chromatography, photometry, and mea surements with ion-selective electrodes. For these methods, sampling and sample preparation are at least as important as the analysis itself. Metrohm Process Analytics has great expertise in this field and configures the sampling system to exactly fit your application including, e.g., filtration, sample taking from pressurized containers, or de gassing. All Metrohm Process Analytics online analyzers come with digital and analog data outputs. Thus, results can be transmitted using the usual process signals and alarms triggered by digital outputs. Or digital inputs can be employed for remote start/stop commands. ADI 2045TI with reagent cabinet Safety benefits of online process analysis Eliminate exposure to hazardous chemicals High temperatures 33 35 Many hazardous substances are utilized to process dif- Hot alkaline solutions for etching and degreasing pro- ferent raw materials in the sector of metal surface fin-cesses are universal, and dangerous incidents can oc- ishing. When carrying out any risk assessment, the last cur in the vicinity of such substances. Process analysis resort is the use of personal protective equipment (PPE), removes the operator from direct involvement during and any potential exposure risks should ideal y be engi-sampling and measurement, limiting any unsafe contact. neered out of any process. Sensitivity to metals The use of an online analyzer completely eliminates risk Sensitivity to some metals is also another common in-of exposure to the hazards associated with the chemi- dustrial y-induced il ness. This can be triggered by expo-cals used in a process. There is no requirement for man-sure to many metal compounds such as platinum group ual sampling from an acidic bath, for instance, as the metals, nickel, and more. Once an operator is sensitized, analyzer can automatical y carry this out making the pro-he or she can no longer work in the vicinity of such sub-cess safer. There is also potential for automated dosing, stances due to serious al ergic responses. further reducing handling of hazardous chemicals. Carcinogens Corrosive and lethal substances Carcinogenic nickel, chromium, and other toxic metals Hydrofluoric acid (HF) is one of the most corrosive chem-although not instant threats, can over a period of ex- icals used in this industry, and it has serious acute and posure lead to adverse health effects such as cancer, chronic health effects, if one has been exposed. Even leading to death. Removal of the operator from process exposures to dilute solutions of HF have led to amputa-areas which utilize these metals reduces the probabilition and even death, especial y in cases where response ty of serious health issues by limiting exposure. There-time was slow. Potential y lethal cyanide (CN-) is com-fore atline or online process analysis is recommended in mon in many plating baths. Handling of such solutions these situations. incorrectly could lead to generation of the highly toxic hydrogen cyanide gas. ADI 2045TI with reagent cabinet 32 36 Online application examples The majority of laboratory methods can be adapted to Monitoring acidic copper baths in semiconductor the requirements in an online system as they are. Some production typical applications in the electroplating industry and PCB The most important processing bath in the production of manufacturing are described on the following pages. printed circuit boards (PCBs) is the acidic copper bath. The components which are contained therein and need Heavy metals in wastewater constant monitoring are copper, sulfuric acid, chloride, Wastewater from the electroplating and electronics and also organic bath additives such as suppressors and industries is normally polluted with metals, including heavy brighteners. While the concentrations of copper, sulfuric metals, e.g., copper, nickel, and cobalt. acid, and chloride are determined titrimetrically, Cyclic Voltammetric Stripping (CVS) and Cyclic Pulse The ADI 2045 Vol tam metric Analyzer (2045VA) from Voltammetric Stripping (CPVS) are used to analyze the Metrohm Process Analytics is an online system that organic bath additives. ensures continuous monitoring of the concentration of these and other metals. In addition, non-metal compo- The 2045VA records, all components centrally, thereby nents, such as hydrazine, can also be monitored. allowing the entire production facility to be monitored quickly and efficiently. Acidic components of etching baths Composition of electroplating baths 37 Online analyzers from Metrohm Process Analytics can The ADI 2045 Process Analyzer can be recommended for also be used to monitor the composition of acidic etch-fully automatic monitoring of nickel electroplating baths. ing baths. By integrating different measuring methods Apart from quantifying the nickel content, it also allows within a single analytical system and developing analyti-measurement of hypophosphite. cal methods for each individual process bath it is usually possible to monitor the entire facility with just one ADI 2045 system. Inline analysis with near infrared spectroscopy (NIRS) 38 Real-time analysis inline For the analysis of acids, baths, and finishing processes, inline NIR spectroscopic analysis is also an option. NIR analysis operates via taking a light source to the sample with fiber optics and analyzing the returning light to identify any changes in absorbance in the NIR region. The analyzer then can interpret the signal and convert this into concentrations of bath components. The light is interfaced with the process using low-dis-persion fiber optic cables. In this way, real-time data is col ected quickly and without the need for chemical analysis. Metrohm Process Analytics offers two spectroscopic in- NIRS Analyzer PRO: with built-in diagnostics and factory standardization struments for process analysis: the NIRS Analyzer PRO and the NIRS XDS Process Analyzer. Dual lamp systems guarantee high uptimes, as there is always a pre-cali- brated light source ready for action. Multicomponent analysis in a single scan One of the major benefits of NIR process analyzers is that they are capable of analyzing multiple components at once. Many parameters can therefore be quantified in one simple scan. Scan times are general y < 1 minute and the methodology is as close to real time as you can get with continuous high resolution data obtained. Save on chemical costs – go reagent-free! Because the methodology is based on the near-infrared light spectrum, there are no reagent requirements reducing costs and complications related to reagent handling. Expansion capabilities: 1 to 9 channels The NIRS XDS process analyzer can expand from one to nine sampling points with an integrated multiplexer. This capability opens up expansion possibilities for measurements, such as monitoring a production line of process baths. NIRS XDS Process Analyzer 32 39 Inline application examples Reagent-free near infrared spectroscopic process analyz-Analysis of mixed acid baths ers enable comparison of real-time spectral data from Titanium is normal y pickled in hydrofluoric acid and the process to a primary method (such as titration) to nitric acid, so-cal ed «mixed acid». As the titanium ion create a simple, yet indispensable model for your pro-concentration increases, HF is consumed by formation cess needs. NIRS is economical and fast, enabling quali-of titanium-fluoride complexes. The formation of these tative and quantitative analyses that are noninvasive and complexes has therefore a direct impact on the pickling nondestructive. Gain more control over your production rate and strongly affects the economics of the process. and increase the safety of your operations by integrating It is important to be able to monitor how the pickling inline spectroscopic techniques into the process. process proceeds to be able to control the addition of fresh acid. This is also important during the very common batch processing to know when each bath is at the end of life and should be discarded. Maintaining the correct bath composition during pickling is critical for optimum etch conditions and quality processing. NIRS process analysis utilizing flow cel s means accurate inline monitoring of HF and HNO can be accomplished 3 safely and reliably at all times. 40 Metrohm Quality Service – Service you can rely on Reliable results for the lifetime of your analytical Metrohm Compliance Service instruments Benefit from the Metrohm Compliance Service when it Whether your field is electroplating or PCB manufactur-comes to the professional initial qualification of your ing – you must always be able to rely on your process ana lytical instruments. Installation Qualification/ control. Systems that are installed and commissioned by Operational Qualification carried out by our experts professionals and maintained on a regular basis ensure a saves you time and money, as your analytical system is maximum degree of reliability and uptime. configured ac cord ing to your needs and put into operation fast and reliably. Relying on the Metrohm Quality Service gives you peace of mind from the very start. From the professional instal-Initial instructions and user training ensure error-free lation of your instruments to regular maintenance care ope ration of your new instruments by your staff. The and – should a failure ever occur – instant quality repairs, Metrohm Compliance Service includes comprehensive we do everything to make sure that you can do cumentation and guarantees compliance rely 100 per cent on results produced with the stand ards of quality manage- during the entire lifetime of your ment systems such as GLP/GMP Metrohm instruments. and ISO. Metrohm Quality Service 41 Metrohm Quality Service is available worldwide. Pre ven-With a full service contract, for example, you can rely on tive maintenance carried out on a regular basis extends the optimum performance of your Metrohm instruments, your instrument’s lifetime while providing for trouble-incur no additional costs and benefit from complete and free operation. All maintenance work done under the compliant verification documents. Thanks to our service label Metrohm Quality Service is carried out by our own you are perfectly prepared for audits. certified service engineers. You can choose the service contract that suits you best. Metrohm Quality Service Customer benefits • Minimizes downtime through preventive maintenance • Cost control and savings through free or discounted replacement materials Metrohm Care Contracts and consumables • Guaranteed reaction times and rapid on-site repair • Documented instrument certification as an ideal preparation for audits • High data security and maximum system performance through regular, Metrohm Software Care professional software maintenance • Customized services and documentation for analytical instrument qualification (AIQ) Metrohm Compliance Service • Professional start-up (IQ/OQ or Certified Installation) and requalification or recertification by specifically trained employees Metrohm Remote Support • Quick resolution of software and application issues directly at the workplace • Calibration of burets (e.g., dosing and exchange units) with certification Metrohm Buret Calibration • Accurate measurement results • Verification documentation for compliance with regulations and efficient audits • Rapid availability of repaired instruments thanks to decentralized repair workshops around the world and a central workshop at the manufacturer site Metrohm Repair Service • Highly qualified service technicians ensure sustainable repair success • Rapid resolution of problems and minimized downtimes through on-site emergency services and express repairs • Original spare parts, made in Switzerland and available worldwide • Short delivery times through warehousing from local distributers Metrohm Spare Parts • Investment security through ten-year spare parts guarantee after discontinuation • Free access to the Metrohm Application Finder (www.metrohm.com/en/ applications/) with more than 2000 applications (Application Bulletins, Application Notes, monographs, technical posters, and technical articles) Metrohm Application Support • Rapid and professional resolution of any application issues through personal consultations with our specialists by e-mail, telephone, or remote support • Support for the solution of complex analytical problems, as well as method optimization on-site or at our application laboratory • Basic and advanced training with local representatives, at the Metrohm Academy or directly on-site Metrohm Training Programs • Efficient and proper use of all analytical methods, as well as results reliability through competently trained users • Training documentation and certificates for trouble-free audits Ordering information 42 Instruments for titration 2.912.0210 Conductometer Lab with stand plate 2.913.0210 pH Meter Lab with stand plate 2.914.0220 pH/Conductometer Lab with stand plate 2.912.0110 Conductometer with conductivity sensor in case with various accessories 2.913.0110 pH Meter with Primatrode in case with various accessories 2.914.0120 pH/Conductometer with Primatrode, conductivity sensor in case with various accessories OMNIS Titrator Please contact your local Metrohm distributor to customize the titration system to your current or future titration needs 2.905.2020 Plate Titrando The Plate Titrando offers you a complete package for the most common analyses of plating baths. Apart from the titration software tiamo light and determination methods described in detail, you will also receive comprehensive accessories for your titrations. 2.856.0010 Conductivity Module – conductivity measuring module for upgrading Titrando systems or use as stand-alone unit in combination with a 900 Touch Control. Electrodes and buffer solutions 6.0255.100 Profitrode – comb. pH electrode with DJ reference system for titration 6.0258.010 Unitrode with Pt1000 temperature sensor (fixed cable) for measuring pH 6.0430.100 Ag Titrode for precipitation titrations with AgNO3 6.0431.100 Pt Titrode for redox titrations 6.0507.120 «Ionic Surfactant» electrode for titration of anionic and cationic surfactants 6.0750.100 LL ISE Reference 6.0915.130 Five-ring conductivity measuring cell, c = 1.0 cm–1 6.0917.080 Sturdy conductivity measuring cell, c = 0.5 cm-1 with Pt1000 for 912/914 meter 6.0918.040 Conductivity measuring cell of stainless steel, c = 0.1 cm-1, with Pt1000 temperature sensor for the 912/914 meters 6.0919.140 Conductivity measuring cell c = 1.6 cm-1 with Pt1000 for the 912 and 914 Conductometers 6.2104.020 Electrode cable 1 m 6.2106.020 Electrode cable for LL ISE Reference 6.2307.230 Buffer solutions pH 4/7/9 (3 x 10 x 30 mL) Intelligent Exchange Units for the 848 Titrino plus 6.3026.110 Exchange Unit 1 mL 6.3026.150 Exchange Unit 5 mL 6.3026.210 Exchange Unit 10 mL 6.3026.220 Exchange Unit 20 mL 6.3026.250 Exchange Unit 50 mL Intelligent Dosing Units for the Titrando 6.3032.120 Dosing Unit 2 mL 6.3032.150 Dosing Unit 5 mL 6.3032.210 Dosing Unit 10 mL 6.3032.220 Dosing Unit 20 mL 6.3032.250 Dosing Unit 50 mL Instruments for ion chromatography 43 2.940.2500 940 Professional Vario TWO/SeS/PP 2.930.2560 930 Compact IC Flex Oven/SeS/PP/Deg 2.850.9010 IC Conductivity Detector 2.858.0020 858 Professional Sample Processor with peristaltic pump and valve 2.919.0020 919 IC Autosampler plus ProfIC Vario 4 Fully automatic Professional IC Vario System for inline dilution ProfIC Vario 5 Fully automatic Professional IC Vario System for inline preconcentration ProfIC Vario 9 Fully automatic Professional IC System Vario for inline preconcentration and inline matrix elimination 6.1006.520 Metrosep A Supp 5 - 150/4.0 6.1010.420 Metrosep C 3 - 150/4.0 6.1006.340 Metrosep A PCC 2 HC/4.0 6.1010.310 Metrosep C PCC 1 HC/4.0 6.2832.000 MSM Rotor A 6.2842.000 MSM-HC Rotor A 6.2844.000 MSM-LC Rotor A 6.2842.200 MSM-HC Rotor C Instruments for voltammetry 2.884.1110 884 Professional VA semiautomated with 2 Dosinos for automatic addition of solutions 2.884.1210 884 Professional VA semiautomated for CVS with 2 Dosinos for automatic addition of solutions. Optional additional Dosinos for further solutions can be connected. MVA-22 Automated analysis system for trace determinations with voltammetry and polarography. Comprising 884 Professional VA for MME, 919 IC Autosampler plus for VA, two 800 Dosinos, 843 Pump Station. For sample series of up to 28 samples. MVA-23 Automated analysis system for the determination of organic additives in electroplating baths using CVS (“Cyclic Voltammetric Stripping”), CPVS (“Cyclic Pulse Voltammetric Stripping”). Comprising 884 Professional VA for CVS, 858 Professional Sample Processor, four 800 Dosinos, 843 Pump Station. For sample series of up to 56 samples. Instruments for process analysis We offer online, inline, and atline process analyzers that meet any requirement for industrial processes: from single-parameter to the most advanced multiparameter analyzers. Every analyzer can be custom-tailored to the specific task at hand. 2045PL ProcessLab system for atline determination of various parameters using titration, colorimetry, and ISE 2045 Series Multifunctional process analyzers, available for titration, ISE, photometry, and voltammetry 2035 Series Modular process analyzers designed for either photometry, potentiometric titration, or thermometric titration 202X Series Single method process analyzers, available for titration, pH, ISE or photometry ICON Analyzer Entry-level process analyzer for single parameter photometric analysis NIRS XDS Inline analyzers based on nondestructive near-infrared (NIR) analysis, with a scan range of 800–2200 nm and capable to expand from 1 to 9 measuring channels NIRS PRO Inline analyzers based on high-resolution diode array technology, the entire wavelength range (1100–1650 nm) is measured instantaneously for real-time analysis Process Ion Based on Metrohm ion chromatography, this process analyzer can monitor several ionic compounds in Chromatograph aqueous media from ng/L to % surface.metrohm.com G, CH-9101 Herisau ohm A , printed by Metr SW Subject to change Layout by Ecknauer+Schoch A 8.000.5249EN – 2018-04