Metrohm – customized analysis for surface finishing, Process control in electroplating and PCB manufacturing
Surface ﬁnishingProcess control in electroplating andPCB manufacturing
02 Metrohm... • is the global market leader in titration • is the only company to offer a complete range of ion analysis equipment – titration, voltammetry and ion chromatography • is a Swiss company and manufactures exclusively in Switzerland • grants a 3-year instrument warranty and a 10-year warranty on chemical suppressors for ion chromatography • provides you with unparalleled application expertise • offers you more than 1300 applications free of charge • supports you with expert service through local representatives and regional support centers • is not listed on the stock exchange, but is owned by a foundation • gives the interests of customers and employees priority over maximizing profit
Metrohm – customized analysis for surface ﬁnishingAn industry with high standardsThe coating and finishing of surfaces using electroplating required precision − both in the laboratory and atline and 03techniques is a highly sophisticated process. Be it the online in the process environment.finishing of metal parts or the coating of printed circuitboards, the quality required in the intermediate and end Count on our supportproducts is only achieved if the composition of the We offer you not only first-rate instrumentation, butprocess 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, whodrive 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 chemicalanalysis we know about these challenges. That is why we Discover on the following pages what solution Metrohmoffer 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 - 10Part II: Processes and applications pages 11 - 25Part III: Solutions for atline and online analysis pages 26 - 31
Part I: Solutions for laboratory analysis04 Titration and pH measurement Titration is an established analytical technique in quality Solutions for every budget and every requirement control of electroplating processes. Titration combines pH measurement – 826 pH mobile / 827 pH lab utmost precision with a very easy procedure. In most The 827 pH lab and its portable twin, the 826 pH mobile, cases it is possible to use undiluted sample solution to are robust, easy-to-use pH meters that make no compro- determine the compenents of reaction solutions. This mises when it comes to accuracy and reliability. Their enables even semiskilled users to carry out the analysis memory can store up to 200 GLP-compliant determina- quickly and accurately. Because of the wide range of tions with date, time and sample identification, which opportunities for automation, the amount of work can be documented either electronically or on paper. required for analysis is generally limited to providing an aliquot of sample and pressing a <Start> 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 electroplat- ing baths, analyzing acid mixtures in etching baths or checking the purity of rinsing solutions. TM Modern titration software such as tiamo reduce paper- work to a minimum. All the determinations are saved in the database and can at any time be classified according to whatever criteria one chooses by means of the search functions and, if necessary, printed out in freely selectable formats. 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 soft- ware tiBase make documentation of results perfectly easy.
905 Plate TitrandoThe Plate Titrando offers a comprehensive package for 05the most common potentiometric analyses in the electro-plating industry. It contains all the accessories for acid/base and redox titration and for the determination ofchloride. Its complete intelligence monitors all the impor-tant system components, such as buret or sensor. Thepatented Dosino technology provides for contact-freehandling of reagents and burets.Automation for Titration862 Compact TitrosamplerThe 862 Compact Titrosampler combines the functionsof the 848 Titrino plus with the possibility for automationfor up to 11 samples in one instrument – on a minimalfootprint. Due to the preprogrammed automated meth-ods, including rinsing procedures, operation of theequipment is amazingly simple.Robotic Transfer AnalyzerMetrohm offers you comprehensive solutions for thecomplete automation of your titrimetric analyses. Thebenefit is evident: higher sample throughput, minimizedrisk for operating errors, more precise and consistentresults and, of course, enormous savings on time andcosts. All of this comes to your lab with the RoboticTransfer Analyzer. Just put your samples on the rack –everything else from sample preparation to analysis istaken care of by the automated system.
Ion chromatography06 Multicomponent determination with a single analysis Metrohm Inline Sample Preparation Techniques 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 tech- niques, 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.
850 Professional IC – solution for demandingtasks 07The 850 Professional IC System can be used both toanalyze acid baths and for trace analysis of impurities inultrapure water, rinsing solutions and adsorption solu-tions. Because of the system’s self-monitoring functionsoperating errors are virtually eliminated. Owing to thecomplete automation, including Metrohm Inline SamplePreparation (MISP), the system can be recommendedboth for routine analysis and for complex applications inresearch and development.881 Compact IC pro – predestined for routineanalysisThe 881 Compact IC pro is the ideal solution for routineanalysis, if the focus is on only one application. Like the850 Professional IC, the 881 Compact IC pro is alsoequipped with intelligent hardware components. To-gether with the MagIC NetTM ion chromatographysoftware the system enables intuitive operation. Just likethe 850 Professional IC, the 881 Compact IC pro canbe automated in various ways and complemented byMetrohm Inline Sample Preparation Techniques.
Voltammetry08 Voltammetry is an electrochemical analytical method that provides information on – among other substances 797 VA Computrace The 797 VA Computrace is a modern voltammetric meas- – the type and amount of metals contained in a dissolved uring stand that is connected to a PC via a USB port. The sample on the basis of a current-voltage relationship. The PC software provided controls the measurement, records importance of voltammetry is based on its high degree of the measuring data and evaluates them. Due to the well- accuracy and sensitivity, the possibility of speciation laid out program structure operation is amazingly easy. analysis and the good price-to-performance ratio. The integrated potentiostat guarantees the highest degree of sensitivity with a reduced amount of noise. The Precise measurements even in the presence of unique Multi-Mode Electrode (MME) and rotating disk high salt concentrations electrodes (RDE) made from various materials are availa- The particular challenge for analysis in the electroplating ble as working electrodes. sector are the large quantities of salts typically contained in electroplating samples. For such samples, many meas- Convenient data management uring techniques can at best provide unsatisfactory All the relevant measurement data and results obtained results; others cannot provide any results at all. Here, with the 797 VA Computrace can be transferred very electrochemical analysis is able to demonstrate its easily to your LIMS − as text data or in xml format. 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 electro- chemical analysis. Furthermore, the infrastructure required for a voltammet- ric measurement system requires hardly any expenditure. All it needs is electricity and a supply of nitrogen. Ven- tilation, flammable gases and associated safety require- ments are no issues.
CVS (Cyclic Voltammetric Stripping)Standard method in PCB manufacturingCyclic Voltammetric Stripping (CVS) and Cyclic Pulse The main CVS applications in the electroplating and semiconductor industries 09Voltammetric Stripping (CPVS) are widely used methodsin the electroplating industry for the determination of Suppressor Brighteners Levelerorganic additives. The CVS method is an essential com- Process DT – Dilution • LAT – RC –ponent of production control in many industrial coating Titration Linear Responseprocesses, especially in the manufacture of printed circuit Titration Curveboards or semiconductors. Approximation Techique • MLAT –With CVS or CPVS it is possible to determine the concen- Modifiedtration of additives exactly. The effective concentration of Linearthe particular additive in the bath sample is shown Approximationdirectly in mL additive per L bath. Precise subsequent Techniquedosing to meet the target concentration then becomespossible. This ensures continuous, trouble-free operationof the plant.Complete voltammetry systems – the right systemfor each applicationMetrohm’s MVA systems are ready-to-use packages, your requirements, there are extended MVA accessorywhich are customized to suit the needs of the electro- kits available for specific applications; use these to en-plating and semiconductor industries. Depending on hance the capabilities of the MVA basic system.MVA-12 – system for additive determination MVA-13 – fully automatic determination ofwith CVS organic additives in sample seriesThe MVA-12 is the standard system for routine determi- The MVA-13 is the high-end system for the determina-nation of organic additives in individual samples. Auto- tion of additives in electroplating baths with the samplesmatic addition of auxiliary solutions such as VMS, inter- being added automatically by an 838 Advanced VAcept or standard solutions is carried out with Dosinos. Sample Processor. The suppressor content of up to 56For brightener determination the sample only has to be samples can be determined. When determining brighten-added manually. In the case of suppressor determination, ers, up to 28 samples can be analyzed. Various methodsthis is also done automatically. can also be combined in a single measuring procedure.
Potentiostats/Galvanostats by Metrohm Autolab10 Systems for electrochemical analysis in research and development Autolab PGSTAT-potentiostats for all electro- 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 The Autolab EQCM module (Electrochemical Quartz which are now used in technologically relevant applica- Crystal Microbalance) further extends the versatility of the tions. Other novel electrochemical surface preparation Autolab PGSTAT. It provides the means to measure mass 2 techniques involve the use of the macromolecular assem- changes in the ng/cm range. This allows the users to blies using dendrimers or nanoscale templating. detect the formation of the very first atomic layers on the surface of a piezo-electric quartz sensor. With this technol- ogy, the formation of metallic deposits during electrolytic or electroless processes can be monitored in situ.
11Part II: Processes and application solutionsQuality control of basic chemicals and raw materialsQuality assurance in production begins when the basic chemicals used are checked. Analytical instruments fromMetrohm make it possible to establish the concentrations of acids or bases reliably, quickly and easily, determine themetal content of various raw materials or detect any impurities in trace quantities.Titrimetric applications Sample Titrant Metrohm ElectrodeSulfuric acid, hydrochloric acid, sodium hydroxide, H2SO4 c(NaOH) = 0.1 mol/L 6.0255.100 Profitrodeammonia and hydrogen peroxide are some of the most HCl c(NaOH) = 0.1 mol/L 6.0255.100 Profitrodefrequently used basic chemicals in the electroplating NaOH c(HCl) = 0.1 mol/L 6.0255.100 Profitrodeindustry. Normally their content is checked by means of NH4OH c(HCl) = 0.1 mol/L 6.0255.100 Profitrodepotentiometric titration when incoming goods are exam- H2O2 c(KMnO4) = 0.1 mol/L 6.0431.100 Pt Titrodeined, to ensure the particular mixture is in the right pro-portions for subsequent use or dilution.
12 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 Precon- 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 a quirements here area are not only work that is free of big role here. For this, an IC system is equipped with blank readings and of any carryover, but also exact meas- Inline Matrix Elimination. This rules out any matrix effect urement of the preconcentration volume. All this is made and makes reliable analysis possible. 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 stand- ard solution. chloride; 49.2 µg/L 1.16 1.14 1.12 1.10 Conductivity [µS/cm] fluoride; 24.5 µg/L 1.08 1.06 nitrate; 24.8 µg/L sulfate; 16.4 µg/L 1.04 phosphate; 6.6 µg/L nitrite; 14.4 µg/L bromide; 9.1 µg/L 1.02 1.00 0.98 0.96 0.94 0.92 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Time [min] Determination of 30% hydrogen peroxide spiked respectively with 10 μg/L F¯, Cl–, NO2–, Br–, NO3–, PO43– and SO42–; column: Metrosep A Supp 5 - 150/4.0; preconcentration column Metrosep A PCC 1 HC/4.0; eluent: 3.2 mmol/L Na2CO3 + 1.0 mmol/L NaHCO3, 0.8 mL/min; column temperature: 25 °C; sample volume: 20 μL
Voltammetric applications Analytes Raw materialTraces of heavy metals in basic chemicals Zinc, cadmium, lead, nickel, cobalt Sodium hydroxideHeavy metal ions present in the basic chemicals can Zinc, cadmium, lead, nickel, cobalt Hydrochloric acidcause interference during the production process. For Iron Phosphoric acidthis reason, a purity check is carried out when goods are Iron, nickel, cobalt Sulfuric acidreceived. Zink, lead, iron Copper sulfateOn the other hand, in the electroplating industry largequantities of basic chemicals are used and as a result size-able quantities of heavy metals are introduced into theproduction process. This contamination needs to be pre-vented as far as possible right at the start of the produc-tion chain, to avoid the need to remove it at great costlater. Such checks are a classic application of voltammetry.Nickel in sodium hydroxide by means ofadsorptive stripping voltammetry (AdSV)To analyze the concentration of nickel in a solution ofsodium hydroxide, the solution is first acidified to bringthe nickel into its ionic form. The pH is then adjusted to9.6 with an ammonium chloride buffer. Dimethylglyoxime(DMG) is added to produce a Ni-DMG complex, whichcan be preconcentrated on the mercury dropping elec-trode. Quantification is by means of standard addition.
14 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 Arsenic Zinc electrolyte deposition in the electroplating process with the required Nickel Zinc electrolyte precision. Cobalt Zinc electrolyte Iron Zinc electrolyte Antimony(III) Zinc electrolyte Germanium Zinc electrolyte Selenium Zinc electrolyte
Metals as main components of electroplating bathsThe concentration of metals in electroplating baths can vary considerably depending on intended purpose. The required 15thickness of the coating, the nature of the material and market prices for the expensive noble metals are the keyparameters. The appropriate analytical technique is selected according to the concentration of the metal to be deter-mined. Metrohm offers suitable systems for carrying it out.Titrimetric applications Ion chromatography applicationsCopper and nickel in acidic metal baths Silver and ammonium in etching baths containingMultilayer systems are widespread in corrosion protec- hydrofluoric acidtion. For example, corrosion-inhibiting nickel is applied Ion chromatography is often used to determine mediumon top of an intermediate layer of copper. In the deposi- to low concentrations of metals in etching solutions andtion processes the concentration of the metal being electroplating baths. Because such solutions and bathsdeposited is an important parameter for the electric cur- often contain high ionic matrices, Metrohm Inline Dilutionrent to be applied. If the concentrations are too low, a is used here. An example of a typical ion chromatographystronger current has to be applied, which can drive up application is the determination of silver in the mg/Lthe production costs significantly. range along with ammonium in the g/L range in etching baths containing hydrofluoric acid.The copper content in acidic copper baths is determinedby redox titration with c(Na2S2O3) = 0.1 mol/L, followingprior reduction of Cu(II) to Cu(I) by means of potassiumiodide. The nickel content is determined by way of com-plexometric titration with c(Na2EDTA) = 0.1 mol/L.
16 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 between various oxidation states of metal ions or bet- ween 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 ofelectroplating bathsOrganic and/or inorganic additives are included in electroplating baths to control the physical properties (ductility, 17hardness, tear strength, brazeability, etc.) of the deposited metal layer. In the case of decorative electroplating, thevisual appearance of the surface is optimized with additives. Complexing agents are also added to baths to keep largequantities of metal in solution.Essentially, acids, bases and ions in low concentrationscan be used to influence the nature of the surfaces ofprinted circuit boards, contacts, metal components etc.These bath additives must be analyzed at regular inter-vals, so the production process is most efficient and aconsistent end product quality ensured.
18 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 determined 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. hydroxide solution. The determination is carried out directly in the plating bath sample; nickel and other metal ions do not interfere.
Ion-chromatographic analysesConcentrated acids in etching solutions 19One of the uses of ion chromatography is to check the (0.25 μL) makes possible, for example, fully automaticcontent of an electroplating bath. For this, the anion analysis of concentrated acid mixtures such as an etchingconcentrations of the acids and acid mixtures used are solution containing 10% HF, 30% HNO3, 30% H2SO4 anddetermined. The unique combination of Metrohm Inline 13% H3PO4.Dilution Technique and a minimum injection volume fluoride; 13.9% 80 70 nitrate; 29.3% 60 sulfate; 30.9% Conductivity [µS/cm] 50 phosphate; 15.2% 40 sulfite; 8.1% 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Time [min]Etching solution diluted inline 1:100, column: Metrosep A Supp 5 - 150/4.0; eluent: 3.2 mmol/L Na2CO3+ 1.0 mmol/L NaHCO3,0.7 mL/min; sample volume: 0.25 μL (internal loop)
20 Nitrate in nickel baths Starter substances, catalysts or contamination from pre- Organic acids in electroplating baths Organic ionic and polar substances can also be deter- vious steps in the μg/L to mg/L range can be determined mined using ion chromatography. Typical applications are by way of ion chromatography for the purpose of proc- determinations of organic acids in electroplating baths. ess 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 iden- tify 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). nitrate; 23.4 µg/L 1.10 1.08 1.06 Conductivity [µS/cm] 1.04 chloride; 2.0 µg/L sulfate; 0.4 µg/L 1.02 nitrite; 1.4 µg/L 1.00 0.98 0.96 0.94 0.92 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Time [min] Rinsing solution after bath cleaning; column: Metrosep A Supp 5 - 150/4.0; eluent: 3.2 mmol/L Na2CO3+ 1.0 mmol/L NaHCO3, 0.8 mL/min; column temperature: 25 °C; sample volume: 200 μL
Voltammetric applications Analyte Type of bathLead in nickel baths Lead, antimony, bismuth Nickel bathLead is added to nickel baths chemically as a stabilizer. In Cobalt, sulfite Gold bathaddition, it has a large effect on nickel deposition itself. Cobalt, cadmium, thallium Cyanide bathThe quantity of lead must be maintained in the low mg/L Chromium(III) / chromium(VI) Chromium bathrange, in order to be able to guarantee uniform deposi- Saccharin Acidic copper bathtion of nickel. Using voltammetry, it is possible to monitor Thiourea Acidic copper bathlimits reliably, quickly and easily.Antimony/bismuth in nickel bathsIncreasingly, nickel baths are being treated with antimo-ny and/or bismuth as an alternative to lead. Here too, theuse of voltammetry can be recommended.
22 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 Determination of suppressor in acid copper with calibration curve boards and semiconductors. DT determination of suppressor Suppressor 15 10 I [mA] 5 0 -5 0 0.5 1.0 1.5 U [V] Measuring curve for a suppressor determination – dilution titration
Monitoring of wastewater and process waterIn electroplating installations wastewater is produced at various points in the manufacturing process. Depending on 23the step in the process (degreasing, electroplating, passivating, pickling, etc.), this wastewater might be highly toxicand therefore require elaborate treatment, in order to eliminate any risks to humans and the environment. Strictlimits apply to the substances concerned and these need to be monitored throughout. Metrohm offers you numeroussolutions for analyzing process water and wastewater; with them you can optimize the productivity of your proc-esses and ensure optimized compliance with environmental legislation.pH and conductivity measurement in wastewaterWhether directly within the process or in the laboratory,the pH value can always be determined quickly andreliably with the 826 pH mobile or the 827 pH lab andthe Unitrode. With the 856 Conductivity Module and the867 pH Module it is possible to determine not only thepH value, but also the conductivity – if necessary, also aspart of a measurement in the same vessel.
24 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. regulations, effectiveness of cleaning steps or quality requirements can be answered during production. Fur- thermore, ion chromatography makes it possible to detect impurities, carryover or discharges right down to the ng/L range. lithium; 254 ng/L 1.1 1.0 monoethylamine (MEA); 502 ng/L ammonium; 332 ng/L 0.9 Conductivity [µS/cm] 0.8 diethylamine (DEA); 478 ng/L triethylamine (TEA); 465 ng/L sodium; 260 ng/L 0.7 potassium; 226 ng/L 0.6 0.5 0.4 0.3 0.2 0.1 0 1 2 3 4 5 6 7 8 9 10 11 12 Time [min] 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 HNO3, 1.0 mL/min; column temperature: 45 °C; sample volume: 10.0 mL
25Voltammetric applications Analyte SampleHeavy metal analysis in wastewater and process Tin Wastewater, process waterwater Iron Wastewater, process waterThe strict regulations for environmentally compatible and Zinc, cadmium, lead, copper Wastewater, process waterefficient use of metals have always had a great impact on Nickel, cobalt Wastewater, process waterthe operation of electroplating installations. With the Chromium(total) Wastewater, process water797 VA Computrace you are fully able to satisfy the re- Mercury Wastewaterquirements for heavy metal analysis in wastewater. Arsenic Wastewater NTA, EDTA WastewaterNot only wastewater, but also the process waters used Thallium Process waterneed to meet strict criteria, depending on the particular Selenium Process wateruse. Whether you are determining the concentration ofiron in boiler feed water or monitoring traces of metal in(rinsing) waters due to carryover – with voltammetricsystem solutions from Metrohm you are on the safe side.
Part III: Solutions for atline and online analysis26 Atline process analysis with ProcessLab Process monitoring in electroplating ProcessLab – robust, flexible and easy to use 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 IP 54 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 or drop below the defined consists of a touch-screen 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 range and are combined specifically for each customer It is a great advantage if samples do not first have to be 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 operating personnel and held ready. Analysis on the to be operated at maximum efficiency. ProcessLab is started by a single touch of the touch- screen 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 meas- urement data are shown on the ProcessLab with the appropriate action and warning limits. Especially when samples have to be taken at different measuring points in the process and implementation of an online solution is ruled out for reasons of cost, ProcessLab provides an ideal solution for fast and reliable process control.
27Combination of analytical methods Incorporation of instruments from other manu-ProcessLab combines various analytical methods on a facturersminimal footprint: titration, direct potentiometry, voltam- Many process baths are mixtures of several substancesmetry, photometry and spectroscopy. The same principle that cannot be determined using the usual wet chemicalapplies throughout: fully automatic processing of samples analysis methods. ProcessLab provides a number of inter-with robust and proven modules and thus process con- faces for incorporating instruments from other manufac-trol with minimized errors. turers to determine density, surface tension or refractive index. These samples also are delivered by ProcessLabConsequently, entire process chains can be monitored and the analyzers are cleaned, checked and calibratedwith a single system – from pretreatment to finishing fully automatically. The results are transferred togetherbaths and on to wastewater monitoring. The perform- with the other parameters to the database and transmit-ance of the individual subprocesses can be increased by ted to the process control system by way of the Process-the individual frequency of samples; Thus, the baths can Lab interfaces.be operated within the optimum parameters and, as aresult, the required product quality can be guaranteed.
Application examples28 Monitoring electroless nickel baths: nickel sulfate, hypophosphite and pH value Monitoring alkaline zinc baths: zinc, sodium hydroxide and carbonate Electroless nickel baths are used for various applications. To protect iron and steel components from corrosion, The advantages of chemical nickel deposition are even zinc continues to be the main material used as a protec- distribution of the coating as well as the possibility to use tive coating. The plating baths deposit zinc on the com- it with rack and barrel facilities. ponents electrolytically, thereby ensuring that the materi- als have a long life. The finishing baths are alkaline; over In electroless deposition processes the electrons required time the concentration of carbonates in them increases, to reduce the metal ions are generated by a chemical impairing the deposition properties and cost efficiency of process in the solution. The reagents used have to be the process. The zinc that has been deposited has to be topped up to achieve even deposition. Increasing salt replaced, so the parts being galvanized are coated evenly. concentrations of the unincorporated ions in the solution The entire process chain, from cleaning of the compo- can impair the coating properties or the rate of deposi- nents in degreasing baths and galvanizing through to tion. These increases in salt concentration must be moni- passivating of the zinc coating on the finished item can tored in order to prolong the bath-life through regene- be monitored with ProcessLab. rative measures. ProcessLab ensures economic and envi- ronmentally aware production throughout the process chain. 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
29Monitoring acidic copper baths in semiconductor Monitoring a phosphatizing processproduction In the various cleaning, degreasing and rinsing baths andThe most important processing bath in the production of also in the phosphatizing bath itself the various parame-printed circuit boards (PCBs) is the acidic copper bath. ters involved must be adhered to exactly. Those deter-The components that are contained therein and need to mined in the degreasing and rinsing baths are pH value,be monitored are copper, sulfuric acid, chloride and also conductivity, free alkalinity and total alkalinity, while theorganic bath additives such as suppressors and brighten- phosphatizing bath is analyzed for free and total acids,ers. While the concentrations of copper, sulfuric acid and accelerator, zinc and fluoride.chloride are determined titrimetrically, Cyclic VoltammetricStripping (CVS) and Cyclic Pulse Voltammetric Stripping ProcessLab monitors, records and documents all the(CPVS) are used to analyze the organic bath additives. important analytical parameters of the phosphatizing process. The combining of the analytical methods withinProcessLab records all components centrally, thereby one system as well as the intuitive handling via the well-allowing the entire production facility to be monitored arranged user interface ensure easy and reliable monitor-quickly and efficiently. ing of the entire process.
Online process analysis30 Customized process control Online analyzers from Applikon Analytical are designed Robust design Applikon analyzers are designed for the rigorous demands for continuous operation and enable fully automatic of the production environment. The housings meet the monitoring of process baths in electroplating and PCB specifications of NEMA 4 and protection class IP66. manufacturing – round the clock, seven days a week. There are no limits: whether your requirement is for one sample stream or several sample streams, for a single parameter or multiple parameters, Applikon Analytical will configure the right system for you. Of course, your wastewater treatment can also be controlled or moni- tored with online analyzers from Applikon Analytical. Proven wet chemistry methods Applikon Analytical online analyzers are based on wet chemistry methods such as titration, photometry and measurements with ion-selective electrodes. For these methods, sampling and sample preparation are at least as important as the analysis itself. Applikon Analytical has great expertise in this field and configures the sampling system to exactly fit your application including, e.g., fil- tration, sample taking from pressurized containers or degassing. All Applikon Analytical online analyzers come with digital and analog data outputs. Thus, results can be transmit- ted using the usual process signals and alarms triggered by digital outputs. Or digital inputs can be employed for remote start/stop commands. ADI 2040 explosion-proof with reagent cabinet
31Application examplesThe majority of laboratory methods can be adapted to Acidic components of etching bathsthe requirements in an online system as they are. Some Online analyzers from Applikon Analytical can also betypical applications in the electroplating industry and PCB used to monitor the composition of acidic etching baths.manufacturing are described below: By integrating different measuring methods within a single analytical system and developing analytical meth-Heavy metals in wastewater ods for each individual process bath it is usually possibleWastewater from the electroplating and electronics to monitor the entire facility with just one ADI 2040industries is normally polluted with metals, including heavy system.metals, e.g., copper, nickel and cobalt. The ADI 2045 Vol-tammetric Analyzer from Applikon Analytical is an online Composition of electroplating bathssystem that ensures continuous monitoring of the concen- The ADI 2040 system can be recommended for fullytration of these and other metals. In addition, non-metal automatic monitoring of nickel electroplating baths.components, such as hydrazine, can also be monitored. Apart from quantifying the nickel content, it also allows measurement of hypophosphite.
32 Service you can rely on – Metrohm Quality Service® 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 analytical instruments. Initial Qualification/Operational control. Systems that are installed and commissioned by Qualification carried out by our experts saves you time professionals and maintained on a regular basis ensure a and money, as your analytical system is configured maximum degree of reliability. according 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 trainings ensure error-free lation of your instruments to regular maintenance care operation 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 rely 100 documentation and guarantees compliance with the percent on results produced during the entire lifetime of standards of quality management systems such as GLP/ your Metrohm instruments. GMP and ISO.
33 ®Metrohm Quality ServiceMetrohm’s worldwide Quality Service®, especially sched- A full service contract, for example, offers you optimumuled and preventive maintenance, extends the lifetime of certainty for work without any worries, while giving youyour analysis systems. Qualified service technicians with complete control of costs and providing fully compliantproof of training carry out the maintenance work. You documentation.can choose between different types of service contracts.Metrohm Quality Service® at a glance ®Metrohm Quality Service Customer benefitsApplication support by means of Application Bulletins,Application Notes, monographs, validation brochures, Fast and professional resolution of all application issuestechnical posters and scientific/technical articles and complex analytical challengesPersonal consultation by our specialists via e-mail ortelephoneTraining Competent users contribute to the reliability of results Accurate measurement results Documentary evidenceCertified calibrations, e.g. of dosing and exchange units to comply with regulations and for efficient auditsRemote maintenance Fast resolution of software issuesBackup support High data securityt Short response time and thus rapid resolution ofEmergency services, e.g. express repairs on-site problems and minimization of downtimeSpare parts, made in Switzerland by Metrohm and Sustainable repair success, short delivery times,available worldwide, with guarantee spare parts minimization of downtimesavailability ten years after instrument discontinuationRegional repair workshops available worldwide and a Instruments soon available for use againcentral workshop at the manufacturer’s premisesMetrohm Quality Service® ensures reliable measure-ment results − throughout the life of an analyzer
Ordering information34 Instruments for titration 2.827.021X 827 pH lab with Unitrode 2.826.0010 826 pH mobile 2.848.0010 848 Titrino plus 2.801.0040 801 Magnetic stirrer with support 2.862.0010 862 Compact Titrosampler 2.800.0010 800 Dosino 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 tiamoTM 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 6.2104.020 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 / 862 Compact Titrosampler 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 chromatography2.850.2030 850 Professional IC Anion – MCS 352.850.1010 850 Professional IC Cation2.850.3030 850 Professional IC AnCat – MCS2.881.0030 881 Compact IC pro Anion2.881.0010 881 Compact IC pro Cation2.858.0030 858 Professional Sample Processor with peristaltic pump and valve2.863.0010 863 Compact IC AutosamplerProfIC 4 Fully automatic Professional IC System for inline dilutionProfIC 5 Fully automatic Professional IC System for inline preconcentrationProfIC 9 Fully automatic Professional IC System for inline matrix elimination6.1006.520 Metrosep A Supp 5 - 150/4.06.1006.500 Metrosep A Supp 415 Guard/4.06.1010.450 Metrosep C 3 Guard - 150/4.06.1006.310 Metrosep A PCC 1 HC/4.06.1010.310 Metrosep C PCC 1 HC/4.0Instruments for voltammetry2.797.0010 797 VA Computrace for voltammetric trace analysis. With Multi-Mode Electrode (MME), Ag/AgCl reference electrode and platinum auxiliary electrode.MVA-02 Analysis system for voltammetric trace analysis and training. With two 800 Dosinos for automatic addition of auxiliary and standard solutions.MVA-03 Fully automatic analysis system for voltammetric trace analysis and training. With 863 Compact VA Autosampler and two 800 Dosinos for fully automatic analysis of small series of samples.2.797.0030 797 VA Computrace for CVS (Cyclic Voltammetric Stripping) for the analysis of additives in electroplating baths. With rotating platinum disk electrode (Pt-RDE), Ag/AgCl reference electrode and platinum auxiliary electrode.MVA-12 Semi-automatic 797 VA Computrace system for the determination of organic additives by way of CVS. With three 800 Dosinos for automatic addition of auxiliary solutions and sample.MVA-13 Fully automatic 797 VA Computrace System for the determination of organic additives by way of CVS. With an 838 Advanced VA Sample Processor, three 800 Dosinos and rinsing kit. For sample series of up to 56 samples.
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