RoHS analysis Determination of hazardous substances in electrical and electronic equipment 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 interest of customers and employees priority over maximizing profit Metrohm – customized RoHS analysis for the determination of hazardous substances in electrical and electronic equipment 03 The Restriction of the Use of certain Hazardous Substances You can count on our support in Electrical and Electronic Equipment (RoHS) Directive, As a leading manufacturer of precision instruments for which has been in effect since 2006, stipulates maximum chemical analysis, we are aware of these challenges. For limits for various hazardous substances in electrical and this reason, Metrohm offers you not only the most ad - electronic equipment. Its importance has almost made it vanced equipment, but rather complete solutions for the a world standard. In many countries, similar directives are particular tasks at hand. Your partners at Metrohm are being discussed, being implemented, or already in force experienced professionals who develop customized (China RoHS, Korea RoHS). applications for you and provide you with competent support concerning all RoHS-related matters. Meeting the RoHS Directive requires reliable equipment and methods. On the following pages, discover the solutions Metrohm offers to ensure the quality and safety of your products. The RoHS Directive Hazardous substances in electrical and electronic 04 The EU Directives RoHS (2002/95/EC) and WEEE equipment (2002/96/EC) As a result of increased production and continuously To counteract this development, two EU directives were decreasing lifetimes of electronic and electrical equip-adopted that aim to significantly reduce the amount of ment, the global volume of electronic waste is increasing electronic waste through recycling targets and to protect at three times the rate of any other type of household humans and the environment from toxic substances by waste. Worldwide, nearly 40 million tons of electronic establishing limit values: waste is now generated annually – and the rate is in - creas ing. Improper disposal prevents the recycling of • The Waste Electrical and Electronic Equipment (WEEE) valuable raw materials such as precious metals and the Directive has been in effect since May 2005 and stipu-rare elements indium or ruthenium. Furthermore, the lates the environmentally friendly disposal of electrical toxic heavy metals and persistent brominated flame and electronic devices at the end of their working life. retardants used in electronic equipment represent an • The RoHS Directive has been in effect since July 2006. environmental hazard. It supplements the WEEE Directive and limits the use of certain hazardous substances in electrical and electronic equipment. 05 Selecting the right analysis equipment and methods Maximum concentration in homogeneous materials Wet chemical analyses The RoHS Directive stipulates maximum concentration If an initial routine inspection of a material points to an levels for lead, cadmium, mercury, hexavalent chromium, elevated concentration of a RoHS-regulated substance, polybrominated biphenyls (PBB) and polybrominated conformity must be assessed via a more detailed (wet) diphenyl ethers (PBDE) for homogeneous materials in chemical elemental analysis. Metrohm offers you a com-electrical and electronic devices. The limit values are prehensive range of equipment and methods for the 100 mg/kg for cadmium and 1000 mg/kg for each of the rapid and precise detection of hazardous substances in remaining elements and compounds. By definition, a electrical and electronic devices. homogeneous material, such as a plastic housing or a metal frame, is of uniform composition throughout and cannot be further mechanically disjointed into different materials. Analyte Technique Page Lead and cadmium Voltammetry 8 Mercury Voltammetry 9 Voltammetry 10 Chromium(VI) Ion chromatography 12 Polybrominated biphenyls and diphenyl ethers Ion chromatography 14 Bromine and other halogens Combustion ion chromatography 15 06 Voltammetry The RoHS Directive limits the use of the heavy metals to its high precision and sensitivity, voltammetry has a lead, cadmium, mercury and hexavalent chromium in compact equipment and is associated with low investment electrical and electronic equipment. A versatile, sensitive and operating costs. and robust analysis method is required to minimize the instrument costs associated with monitoring the estab-Samples are prepared according to the recommenda- lished maximum concentration values. Voltammetry tions by the International Electrotechnical Commission in meets these requirements. It is used to quantify redox compliance with the IEC 62321 standard. Thereafter, active substances – which includes the heavy metals list-Voltammetry can be used to determine all four heavy ed above. Voltammetry is frequently employed to com - metals in polymers, metals and electronic components plement and validate spectroscopic methods. In addition within the required concentration ranges. 797 VA Computrace Detection limits in voltammetry 07 With the 797 VA Computrace, Metrohm offers you a Element Detection limit [ng/L] user-friendly, modern, all-round measuring stand. Beyond Antimony SbIII/SbV 200 covering the analytes required by the RoHS Directive, it Arsenic AsIII/AsV 100 permits the precise and sensitive trace analysis of metals Bismuth Bi 500 and nonmetals using voltammetric and polarographic Cadmium Cd 50 methods. Depending on the matrix, detection limits are Chromium CrIII/CrVI 25 in the ppt range (ng/L). Unlike spectroscopic methods, Cobalt Co 50 voltammetry distinguishes between the different oxida-Copper Cu 50 tion states as well as between free and bound metal ions Iron FeII/FeIII 50 (speciation). Lead Pb 50 Mercury Hg 100 Molybdenum MoIV/MoVI 50 Nickel Ni 50 Platinum Pt 0.1 Rhodium Rh 0.1 Selenium SeIV/SeVI 300 Thallium Tl 50 Tungsten W 200 Uranium U 25 Zinc Zn 50 Economical and compact – the modern, computer-controlled 797 VA Computrace 08 Lead and cadmium Lead and cadmium levels are determined using anodic Since the oxidation for the two metals takes place at stripping voltammetry (ASV). The two metals first un der-different potentials, lead and cadmium can be selectively go cathodic enrichment at the Multi-Mode Electrode and determined in parallel. Quantification is easy and reliable are then anodically stripped during the detection phase. with the standard addition method. Thus, matrix effects The current flowing during this process is proportional to do not influence the accuracy of the results. Concentrations the amount of material previously deposited and hence of 10 mg/kg lead and cadmium can be easily determined. to the metal concentration in the measured solution. Pb 600 400 I [nA] 200 Cd -0.80 -0.60 -0.40 -0.20 U [V] Simultaneous voltammetric determination of lead and cadmium in the range of the prescribed limit values (100 mg/kg Cd and 1000 mg/kg Pb) Mercury Mercury can also be determined using anodic stripping voltammetry. The determination process differs from that of lead and cadmium in that a gold rotating disk electrode is used for enrichment. The amount of deposited mercury and therefore the sensitivity of the determination can be controlled via the deposition time. In the subsequent determination, 1/10 of the required limit value can be easily detected. As the determination of lead and cadmium, mercury de termination can be accurately performed with the 797 VA Com put race. This merely requires exchanging the electrode set, which is quickly done since the electrodes are easily accessible. Voltammetric measuring cell with gold rotating disk electrode, reference electrode and glassy carbon auxiliary electrode 10 Chromium(VI) Determining chromium levels in the context of the RoHS methods, as specified by the IEC 62321 standard, are Directive is a special case since the concentration of the used in sample preparation. In order to comply with highly toxic hexavalent chromium – rather than the total the limit value, Cr(VI) concentrations in the extracts of concentration of the metal – must be identified. With polymers and electronic components have to be around voltammetry, Cr(VI) can be determined besides other 50 mg/L. In case of chromium coatings, 0.02 mg/L must chromium species without difficulty. be accurately detected. Voltammetry meets this difficult analytical challenge thanks to its high sensitivity and To rule out errors that derive from conversions between great flexibility. trivalent and hexavalent chromium, only extraction -350 CrVI -300 -250 -200 I [nA] -150 -100 -50.0 -1.00 -1.20 -1.40 U [V] Determination of hexavalent chromium in a chromium coating in the range of the permissible limit value (0.02 mg/L) 11 Ion chromatography 12 Ion chromatography (IC) permits the efficient separation chro mi um(VI). After separation on a polyalcohol anion-and determination of inorganic and low-molecular-weight exchange column and subsequent post-column derivati-organic anions and cations. It can determine chemically zation with 1,5-diphenylcarbazide, chromium(VI) is similar substances within a very short time in a single detected with high sensitivity as a violet chromium-analysis. Different separation mechanisms and detection diphenylcarbazone complex at 540 nm. When using a types as well as the possibility of automation and sample 1000 μL sample loop, the chromate detection limit deter-preparation render IC a versatile analytical technique. mined in accordance with DIN 32645 is less than 10 ng/L. Chromium(VI) For polymers and chromium coatings, the RoHS Directive In addition to voltammetric measuring methods, ion requires the analysis of chromium(VI) in different concen-chro matography is often used in the determination of tration ranges. 60 20 55 18 50 45 16 40 U] U] 14 35 12 30 20 mg/L spike 10 25 10 mg/L spike 20 8 0.5 mg/L spike Absorption [mA Absorption [mA 15 unspiked polymer sample 6 10 4 20 µg/L spike 5 2 chromium-coated metal sample 0 0 1 2 3 4 5 6 7 8 9 10 11 12 0 1 2 3 4 5 6 7 8 9 10 11 12 Time [min] Time [min] Chromium(VI) analysis in a chromium-coated metal sample, Chromatograms of a polymer sample (black) and with the unmodifi ed (black) and with the addition of 20 μg/L of chro-addition of 0.5 mg/L (red), 10 mg/L (blue) and 20 mg/L (green) mi um(VI) (red). The recovery rate is 100%. Column: Metrosep chromium(VI): The analysis is linear over the entire determination A Supp 5 - 150/4.0; eluent: 10 mmol/L Na CO , 1 mmol/L 2 3 range. Extension is possible through varying the sample amount NaHCO , 0.7 mL/min; sample volume: 200 μL; post-column 3 as well as the dilution and injection volume. Column: Metrosep derivatization with 1,5-diphenylcarbazide. A Supp 5 - 150/4.0; eluent: 10 mmol/L Na CO , 1 mmol/L 2 3 NaHCO , 0.7 mL/min; sample volume: 20 μL; sample amount: 3 5 g fi nely ground polymer in 1000 mL Na CO /NaOH solution; 2 3 post-column derivatization with 1,5-diphenylcarbazide. 844 UV/VIS Compact IC 13 The 844 UV/VIS Compact IC can be used for the accurate and sensitive determination of chromium(VI) in chromium-coated metal and polymer samples. The instrument also allows to determine the organobromine compounds as required by the RoHS Directive (see page 14). For the fully automated determination of chromium(VI), an 844 UV/VIS Compact IC is used in combination with an 863 Compact IC Autosampler. The analysis method provides excellent precision: 1.49% relative standard deviation for a 10 μg/L chromium(VI) standard (n = 6). 14 Polybrominated organic compounds Determining flame retardants, such as polybrominated Using GC-MS, monobrominated to decabrominated biphenyls (PBB) and polybrominated diphenyl ethers bi phenyls and monobrominated to decabrominated (PBDE), in polymers is also part of RoHS Directive diphenyl ethers can be quantified after Soxhlet extrac-2002/95/EC. Their concentration in electrical and election. Two alternative analysis methods are presented tronic equipment is limited to 1000 mg/kg. below: Determining PBBs and PBDEs using liquid chromatography The polybrominated substances in the plastic are concen-sed-phase C18 column, their absorption is recorded at trated in a suitable solvent using Soxhlet extraction. The diffe rent wavelengths in a UV detector. Both polybromi-extract is then filtered and injected. After chromatographic nated compounds and chromium(VI) can be determined separation of the polybrominated compounds on a re ver-using the 844 UV/VIS Compact IC (see page 13). 254 nm 210 nm 65 60 55 50 45 A) A) 40 T A) omobisphenyl A (TBBP 35 (OC (DEC abr omodiphenyl ether omodiphenyl ether 30 tetr 25 octabr decabr Absorption [mAU] 2 mg/L spike 20 15 unspiked polymer sample 10 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Time [min] Determination of various polybrominated compounds in a The detector signal is linear over a large concentration range. polymer sample using UV detection at 254 and 210 nm. In the For OCTA, a correlation coeffi cient of 0.99999 and a relative original sample (black), neither PBBs nor PBDEs can be detected. standard derivation of only 0.53% (n = 3) were found. With the addition of merely 2 mg/L TBBPA, OCTA and DECA (red), the bromine-containing organic substances can be easily determined. This concentration is one order of magnitude below the limit value. Column: Nucleosil EC 100-7-C18; eluent: 97% methanol with 3% phosphate buffer (17.5 mmol/L Na HPO and 2 4 11.0 mmol/L KH PO ) at pH 7 (H PO ), 1 mL/min; sample volume: 2 4 3 4 20 μL; sample amount: 2 g fi nely ground polymer in 100 mL n-propanol. Combustion IC for the simultaneous quantification The principle 15 of halogens in polymers After inline pyrolysis of the polymer matrix, the gaseous Combustion IC is a modern and powerful analysis meth-combustion products are led into an oxidizing absorption od for the simultaneous determination of halogens and solution that is then fed into an ion chromatograph for sulfur in all solid and liquid combustible samples. Elec- analysis. Combustion IC can differentiate the halogen tro nic components, colors, pharmaceutical products, soil content of combustible samples and is thus ideally suited samples as well as fossil and biogenic fuels can be exam-for determining if a material can be labeled «halogen-free» ined in addition to plastics. In contrast to the times of the in accordance with the requirements of IEC 61249-2-21. oxygen bomb, no lengthy sample preparation is required. The completely automated Combustion IC features high sample throughput, low detection limits as well as excellent precision and accuracy. Halogen and sulfur determination in three PVC-containing power cable insulation materials using combustion IC. In addi-1.16 d) tion to a high chloride content of up to 25%, low amounts of 1.14 fl uoride (< 30 mg/L) and sulfate (< 75 mg/L) were determined. 1.12 Bromide, which elutes at approx. 9 min, was not detected. 1.10 Column: Metrosep A Supp 4 - 250/4.0; eluent: 1.7 mmol/L 1.08 Na CO , 1.8 mmol/L NaHCO , 1 mL/min; sample volume: 2 3 3 1.06 fluoride chloride sulfate phosphate (internal standar 10 μL; sample amount: 10 mg fi nely cut polymer material; 1.04 internal standard: 10 mg/L phosphate. Conductivity [µS/cm] Determ. 1 1.02 1.00 Determ. 2 Determ. 3 0.98 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Time [min] 16 Metrohm Quality Service® Reliable results – for the lifetime of your analyzer Metrohm analysis equipment is highly suitable for RoHS cation (IQ/OQ), you can significantly reduce costs and analysis. In combination with the comprehensive services save time, since the analysis system is configured accord-of the Metrohm Quality Service®, our equipment ensures ing to your needs. As a result your system can be put into that laboratory managers can depend 100% on the mea-ope ra tion quickly and professionally. User orientation surement results – for the entire lifetime of the equipment. and training then ensure safety and operator accuracy. Metrohm Compliance Service® includes complete docu-Metrohm Compliance Service® mentation and guarantees conformity with common Benefit from Metrohm Compliance Service®, for instance requirements of quality management systems such as for the professional initial qualification of your analysis GLP/GMP and ISO. equipment. With Initial Qualification/Operational Quali fi- Metrohm Quality Service® 17 The Metrohm Quality Service® is available worldwide. bet ween different types of service contracts. With a full Preventive maintenance carried out on a regular basis ser vice contract, for example, you can rely on the opti-extends your instrument’s lifetime while providing mum performance of your Metrohm instruments at any trouble-free operation. All maintenance work done time, whilst giving you complete control of costs and pro-under the label Metrohm Quality Service® is carried out viding fully compliant verification documentation. by our own certified service experts. You can choose An overview of Metrohm Quality Service® Our Services Benefit for the Customer Application support by means of our vast selection of Application Bulletins, Applications Notes, monographs, Quick and professional solution to all arising application validation brochures, technical posters and articles questions and complex analytical challenges Personal consultation by our specialists per telephone or e-mail Competent users contribute substantially to Training courses reliable results Accurate results Certified calibrations, for example of dosing and Verification documentation for compliance with exchange units regulations and for efficient audits Remote maintenance Expeditious resolution of software questions Back-up support High data security Short response times and thus rapid problem resolution Emergency service, for example express on-site repairs Minimization of downtimes Original spare parts, made in Switzerland and available Lasting, successful repair; short delivery times world wide Minimization of downtime Guaranteed spare parts available for at least 10 years Protection of your investment through long-term beyond instrument discontinuation date availability of spare parts and accessories Regional repair workshops available worldwide and Quality repairs done quickly, so your instruments a central workshop in Switzerland are ready for use again Thanks to Metrohm Quality Service®, you can rely on your results for the lifetime of the analytical instrument. Ordering information 18 Voltammetry 2.797.0010 797 VA Computrace for manual operation MVA-2 VA Computrace system with automatic standard addition consisting of 797 VA Computrace with two 800 Dosinos for automatic addition of auxiliary solutions MVA-3 Fully automated VA Computrace system consisting of 797 VA Computrace with 863 Compact VA Autosampler and two 800 Dosinos for automatic addition of auxiliary solutions. Allows the automatic processing of up to 18 samples. This system is the optimum solution for automatic analysis of small sample series. MVA-Hg Complete equipment for mercury determination at the gold rotating disk electrode Ion chromatography Chromium (VI) determination 2.844.0020 844 UV/VIS Compact IC with post-column reactor 2.863.0010 863 Compact IC Autosampler 6.1006.520 Metrosep A Supp 5 - 150/4.0 Determination of polybrominated organic compounds – LC 2.844.0010 844 UV/VIS Compact IC Nucleosil EC 100-7-C18 Determination of polybrominated organic compounds – Combustion IC 2.881.0030 881 Compact IC pro Anion – MCS 6.6059.211 MagiC NetTM 2.1 Compact CD: 1 license 6.2148.010 Remote Box MSB 6.2141.370 Cable for connecting Metrohm IC – PAC Combustion System 6.2141.140 Cable for connecting Metrohm IC – Mitsubishi Combustion System 6.1006.520 Metrosep A Supp 5 - 150/4.0 6.1006.500 Metrosep A Supp 4/5 Guard/4.0 Equipment for combustion can be purchased from PAC, L.P. and Mitsubishi Chemical Corporation. The described determinations are based on the following Application Notes, which can be downloaded from http://products.metrohm.com AN-V-185 Cadmium and lead in electronic components as part of electrotechnical products AN-V-186 Chromium(VI) in electronic components as part of electrotechnical products AN-V-187 Mercury in electronic components as part of electrotechnical products AN-V-188 Cadmium and lead in polymer materials as part of electrotechnical products AN-V-189 Chromium(VI) in polymer materials as part of electrotechnical products AN-V-190 Mercury in polymer materials as part of electrotechnical products AN-V-191 Cadmium and lead in metallic materials as part of electrotechnical products AN-V-192 Chromium(VI) in chromate coating on metallic materials as part of electrotechnical products AN-V-193 Mercury in metallic materials as part of electrotechnical products AN-U-039 Polybrominated diphenyl ethers in polymers by UV detection, as per IEC 62321 method for RoHS testing AN-U-040 Chromium(VI) in colorless and colored chromate coating on metallic samples as per IEC 62321 method for RoHS testing AN-U-041 Chromium(VI) in polymers as per IEC 62321 method for RoHS testing 19 rohs.metrohm.com ohm AB, CH-9101 Herisau ; print: Metr SW eserve the right to make changes. e rW Design: Eckhauer + Schoch A 8.000.5022EN - 2010-07