RoHS / ELV. Complying with European Chemical Substance Regulations

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Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment / End-of Life Vehicles RoHS / ELV Complying with European Chemical Substance Regulations

RoHS/ELV EU Regulations for Hazardous Substances Overview of Revised RoHS/ELV Directives The Environmental Problems of the European Union (EU) and Trends in Test Methods Upon implementation of the European Union s ELV Directive (End-of-Life Vehicle Directive), in effect since July 2003, automobiles, automotive parts or materials subject to the directive cannot be exported to the EU unless they contain no cadmium (Cd), lead (Pb), mercury (Hg) or Hexavalent chromium (Cr 6+ ). Similarly, the RoHS Directive (Restriction of Hazardous Substances in Electrical and Electronic Equipment), in effect since July 1, 2006, restricts the use of electric and electronic equipment containing any of six specified hazardous substances: two kinds of brominated flame retardants - polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE), Cd, Pb, Hg, and Cr 6+. Later, categories 8 (medical devices) and 9 (monitoring and control instruments) were added to the scope of RoHS Directive, with no additions or changes made with respect to the restricted substances or thresholds. The addition of phthalate esters (Bis(2-ethylhexyl) phthalate (DEHP), Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), and Diisobutyl phthalate (DIBP)) was finalized in 2015. IEC:62321, the international standard test method in this field, has been revised with corresponding modifications and additions. Since, in particular, phthalate esters cannot be detected by conventional X-ray fluorescence screening, it is now an urgent necessity to establish screening methods for restricted organic substances and accurate analysis methods for phthalate esters. Later, it will be necessary to pay attention to trends in the creation of test methods, and to conduct fact-finding surveys with respect to procurement items. Regulated Substances and Maximum Allowable Concentration Levels (Threshold Values) ELV RoHS Remarks Cadmium (Cd) 100 ppm 100ppm Lead (Pb) 1000 ppm 1000ppm Mercury (Hg) 1000 ppm 1000ppm Hexavalent chromium (Cr 6+ ) 1000 ppm 1000ppm Polybrominated Biphenyls (PBB) Exempt 1000ppm Polybrominated Diphenyl Ethers (PBDE) Exempt 1000ppm DIBP, BBP, DBP, and DEHP Exempt 1000 ppm <RoHS recast, 2011/65/EU> The periodic revision of restricted substances by the European Commission was stipulated. Restricted substances are now described in the Annex, so that additional substances can be added without revising the directive itself. In order to streamline the management of the revised RoHS Directive, the European Commission created a guidance (FAQ), which was published on December 12, 2012 (RoHS 2 FAQ 2012/12/12). The FAQ themselves carry no legislative efficacy, but are given serious consideration as formal documentation from the European Commission. The denominator for calculating thresholds for both the ELV and RoHS is Homogeneous Material, the definition of which is specified in the ELV guidance document and the RoHS guidance (FAQ). Be aware that both ELV and RoHS include definitions of applicable exemption status. 2

Key Chemical Substance Regulations in the EU (European Union) Council Directive on Batteries and Accumulators Containing Certain Dangerous Substances (91/157/EEC 2006/66/EC) Directive on Packaging and Packaging Waste (94/62/EC) End-of-Life Vehicles Directive (ELV Directive 2000/53/EC) Waste Electrical and Electronic Equipment Directive (WEEE Directive 2002/96/EC 2012/19/EU) Restriction of Hazardous Substances in Electrical and Electronic Equipment Directive (RoHS Directive 2002/95/EC 2011/65/EU). Registration, Evaluation, Authorization and Restriction of Chemicals (REACH Controls EC No 1907/2006) ErP Directive (2009/125/EC) Energy Labelling Directive (2010/30/EU) ELV Directive End-of Life Vehicles In order to prevent the generation of waste from automobiles and to promote the reduction of waste through the reuse or recycling of end-of-life vehicles or their parts, this directive makes sure that automobile materials or parts marketed in member states after July 1, 2003 do not contain lead, mercury, cadmium or Hexavalent chromium. RoHS Directive Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment The RoHS Directive was officially announced and enacted (RoHS Directive, 2002/95/EC) on February 13, 2003 and implemented from July 2006. It was completely revised and officially announced (RoHS recast, 2011/65/EU) on July 1, 2011. Medical devices and monitoring and control instruments (categories 8 and 9), which were not subject to restriction in the old RoHS Directive (2002/95/EC), became controlled starting in July 2014. The following categories (category 1 to 11) listed in Annex 1 are subject to the directive Implementation date: 1. Large Household Appliances 2. Small Household Appliances Category 8 (excluding in vitro devices) 3. IT and Telecommunications Equipment Category 9 (excluding industrial instruments) 4. Consumer Equipment 5. Lighting Equipment 6. Electrical and Electronic Tools 7. Toys, Leisure and Sports Equipment 8. Medical Devices 9. Monitoring and Control Instruments 10. Automatic Dispensers 11. Other EEE not covered by any of the categories above in vitro diagnostic medical devices (for tests performed outside the human body) Industrial monitoring and control instruments Category 11 Addition of phthalate esters Notification of the World Trade Organization (WTO) by the European Commission of the proposal for a Commission delegated directive, a revision to Annex II of the RoHS Directive (2011/65/EU). Official announcement by the European Commission of the Commission delegated directive (Commission Delegated Directive (EU) 2015/863) regarding the modification of Annex II of the RoHS (II) Directive. Categories 1 to 7, 11 Category 8 (medical devices including in vitro diagnostic medical devices) Category 9 (monitoring and control instruments including industrial monitoring and control instruments) July 22, 2016 onwards July 22, 2017 onwards July 22, 2019 onwards December 17, 2014 June 4, 2015 onwards July 22, 2019 onwards July 22, 2021 onwards July 22, 2021 onwards Obligations of manufacturers: In the RoHS recast, manufacturers are obliged to create technical documentation in accordance with Decision 768/2008/EC Annex II Module A. They must also implement internal production control procedures, prepare declarations of conformity, and affix CE marks. EN50581:2012 EU standards were established by CENELEC (European Committee for Electrotechnical Standardization), and officially announced as standards conforming to the RoHS recast (November 23, 2012). Note 1: The content of this article is as of May 2016. Note 2: For the content of the regulations and their interpretation, be sure to check the officially announced information. 3

The New Two-stage Screening Method Proposed by Shimadzu Phthalate esters, which are scheduled to be included as additional regulated substances in the next amendment of the RoHS Directive, are compounds consisting solely of C, H, and O. They cannot be detected by conventional X-ray fluorescence screenings. It is highly likely that an increasing number of organic substances will be added to the control list. Therefore, a two-stage screening process is needed for materials and parts containing plastic components. Yes Plastic material Electronic parts (with plastics) Plastics included No Metal material Electronic parts (without plastics) Sample Homogeneous material Metal material Plastic material Electronic parts (boards, components) Yes Screening No Sample preparation (mechanical pulverization) AA-7000 Series ICPE-9800 Series ICPMS-2030 UV-1900 GCMS-QP2020 4

Substances already regulated under RoHS (II) Directive and those for which regulation is anticipated EDX-7000/8000 Lead (Pb) Mercury (Hg) Cadmium (Cd) Chromium (Cr) PBBs PBDEs Phthalate esters (DIBP, DBP, DEHP, BBP) Py-GC/MS (Py-Screener) X-ray fluorescence screening Py-GC-MS screening Controlled concentrations Pass Conforming product X-ray fluorescence screening Fail Yes Accurate measurement No Nonconforming product Pass Conforming product Accurate analysis (multiple analysis methods) Controlled concentrations Fail Nonconforming product IRSpirit Determination Criteria based on the nature of substances 5

Hazardous Metals - Cd, Pb, Hg, Cr and Br Screening Analysis of Hazardous Substances in RoHS/ELV Directive Using EDX For Screening Analysis Energy Dispersive X-ray Fluorescence Spectrometer EDX-7000/8000 EDX-7000/8000 Shimadzu EDX Series systems are able to rapidly screen for the six substances, comprised of five elements, environmentally regulated under EU electrical and electronic product waste directives (RoHS), and the four substances, comprised of four elements, environmentally regulated under end-of-life vehicle regulations (ELV). The EDX Series has captured an overwhelming share of the RoHS compliance business in the electrical and electronic equipment industry. The series has built quite a track record and enjoys a great reputation. In order to support compliance with these regulations, Shimadzu has established a worldwide analytical consulting and maintenance capability. In this current business environment, which demands a global business plan that encompasses overseas offices, Shimadzu s highest goal is to offer a high operation rate for all regions throughout the world and achieve the same level of performance as offered in Japan. Features EDX-7000/8000 Optimal for General Analysis in Addition to RoHS/ELV and Various Control Screenings Reduces routine maintenance (no liquid nitrogen necessary) Industry-leading detection sensitivity and resolution Fast, high-sensitivity measurements of even trace elements High-precision measurements, even of multi-element compounds EDX Series Screening Applicability Note: The symbols, and do not indicate a comparison of instrument functionality. ELV Textile s Quality Labeling Regulations Target Regulations RoHS Halogen CPSIA REACH EN-71 (Toy Safety) Element Cl Br Hg Cr Pb Cd Sb As Ba Se Co Sn S Ni EDX-7000 / 8000 : Supported as an option : Applicable depending on the analysis conditions * Introduction of an additional function kit is required. 6

A Product Line Designed for Analysis and Inspection Applications General-purpose model supporting general analysis in addition to RoHS/ELV and various control screenings General-purpose model featuring high sensitivity to light elements, supporting fluorine (F) analysis in addition to RoHS/ELV and various control screenings EDX-7000 EDX-8000 Characteristics and Operating Principle of X-ray Fluorescence Spectroscopy Samples are irradiated with x-rays and the energy level and intensity of second-order x-rays (x-ray fluorescence) generated from the samples are measured. This allows non-destructive measuring of the constituent elements (qualitative analysis) and their respective concentration levels (quantitative analysis). Furthermore, since no chemical pretreatment is required and multiple elements can be analyzed simultaneously, analysis can be performed rapidly, which is a major benefit of x-ray fluorescence. In addition, systems are compact, require minimal maintenance, and are able to measure samples of any shape by simply placing them in the measurement chamber. Consequently, EDX systems are ideal for acceptance inspection, production screening analysis and defect analysis. First-Order X-rays X-ray Tube Sample X-ray Fluorescence Semiconductor Detector Operating Principle of Energy Dispersive X-ray Fluorescence (EDX) Systems Multichannel Analyzer MCA Features of the EDX-7000/8000 High Sensitivity - Lower Limit of Detection Improved 1.5 to 5 Times - EDX-7000/8000 Previous model The high-performance SDD detector and combination of optimized optics and primary filters achieve previously unheard-of levels of sensitivity. The sensitivity is higher than the previous Si (Li) semiconductor detector across the entire range from light to heavy elements. High Speed - Throughput Increased by up to 10 Times - The high fluorescent X-ray count per unit time (high count rate) of the SDD detector permits highly precise analysis in a shorter measurement time. This feature is achieved to the maximum when analyzing samples that generate a lot of fluorescent X-rays, such as samples with a metal as the main component element. Previous model EDX-7000/8000 10.0 11.0 12.0 13.0 Comparison of Profiles for Lead (Pb) in Copper Alloys Approx. 1 10 measurement time Measurement time Measurement Time Required to Achieve Target Analysis Accuracy RoHS/ELV 7

Hazardous Metals - Cd, Pb, Hg, Cr and Br For Screening Analysis Note: The EDX-7000 and 8000 are equipped with PCEDX Navi as standard. To perform RoHS/ELV screenings, however, an optional screening analysis kit must be added. Features of Screening Software (PCEDX Navi) Making the Difficult Simple Screening Software Designed for Easy Operation Start sample measurement from [Screening Analysis] using simple steps. The selection of measurement conditions, which typically relies on the judgment of the experimenter, is determined automatically. This means that even first-time users can effectively use the system. 1st step 2nd step Place the Sample Select Analysis Conditions/ Enter Sample Name After placement, the sample observation camera observes the sample and confirms the sample's analysis position. Set the analysis area to 3 mm, 5 mm, or 10 mm diameter. Close the sample chamber. The [Measurement Preparation] window displays the current sample image. Use this window to select analysis conditions and enter a sample name. Start measurement with a single click. Features of Screening Software Even faster measurement! A single click in the [Screening Analysis] window automatically performs everything from measurement to the display of results, in accordance with pre-registered analysis conditions. Unknown sample All the following are user-determined steps Metal Conventionally Is this metal? Plastic? Condition settings Plastic EDX-7000/8000 8 Brass? Al alloy? Solder? PVC? PE? Decide analysis conditions (calibration curve) depending on main component. Start measurement with a single Automatically determines main component, selects the optimal calibration curve, click! and performs measurement. Requires no user decisions. Results (If a user cannot determine the main component, selecting the optimal calibration curve is difficult.)

Simple procedures ensure worry-free operation, even for first-time users To check the results to date Result List: Lists data of completed measurements (with photographs) 3rd step If you want to create a report Individual Report: Displays a report of the current sample Display of Analysis Results Create reports in Excel or HTML format. Reports can also be created for non-rohs 5 element data. After measurements are completed, [Pass/Fail Judgment], [Concentration], and [3σ(Measurement Variance)] are displayed for all 5 elements in an easy-to-understand layout. Display the [Result List] and [Individual Report] with a single click. *Note that this requires installation of Microsoft Office Excel before use. Measurement Example of a Plastic Sample (PVC Wire-jacket Material) Pass, fail, or indeterminate judgment results with respect to the control criteria are easily obtained. Note: The control criteria in these results are set to the maximum permitted concentrations in the RoHS Directive. Cr Element Cd Pb Hg Br Determination Results OK NG OK OK Grey zone 25500 23.4 26.1 901 790 19 12 120 Quantitative Value (ppm) Not detected 7.1 X-ray Fluorescence Intensity -PbLa 10 -Crkb PVC Wire-jacket Material -PbLn -Brka -HgLa X-ray Fluorescence Intensity -PbLL X-ray Fluorescence Intensity -Cdka 22 24 Energy (kev) Cr -PbLb1 Pb Cd -Crka 3σ (ppm) 12 Energy (kev) 5 6 Energy (kev) RoHS/ELV 9

Hazardous Metals Cd, Pb and Hg For Precise Quantitative Analysis Leave the Precision Analysis of Metals to AA and ICP Atomic Absorption Spectrophotometer AA-7000 What is Atomic Absorption Spectrophotometry? Liquid samples are suctioned up by a nebulizer, sprayed into a burner, heated and atomized. Then the sample is irradiated by light from a hollow cathode lamp. Light wavelengths that are characteristic for the element being measured are absorbed by those atoms. This absorption is measured and used for the quantitative analysis of the element. Features of Atomic Absorption Spectrophotometers High Sensitivity (ppb) Convenient to Use Comparison of ICP and AA Methods Sensitivity Dynamic Range Precision Spectral Interference Chemical Interference Physical Interference Low Price Compact Size Analysis Speed Simultaneous Analysis of Multiple Analytes Operability Maintenance Fair Fair 422.7 nm Light Burner Head Flame Atomizer Chamber Fair Fair Drain Flame Atomization Method Acetylene Flame AAS Furnace AAS ICP-OES ICP-MS ppb to ppm 2 digits Not Possible ppt to ppb 2 digits Fair Not Possible ppb to % 5 digits Possible Nebulizer Fair Note: It is important to select the optimal analysis method for the testing objectives, or use a combination of methods. Items Applicable for ICP or AA Analysis ppt to ppm 9 digits Fair Possible Sample Solution Metals (ferrous and non-ferrous) Chemicals, drugs, petroleum, polymers, ceramics Biological samples, pharmaceuticals, foods Environmental samples (drinking water system, environmental waters, effluents, soil, atmospheric dust) Other metal content can be analyzed in a variety of samples Note: Solid samples require pretreatment (dissolved into solution). Air Major Pretreatment Methods Dilution Dissolve the sample in purified water, weak acid or organic solvent. Examples: Uniform samples, such as plating solutions, food products (dairy products, etc.), drugs, or biological samples (blood, urine, etc.) Dry Digestion Heat the sample at a high temperature (400 500 C). Decomposition requires a short time (several hours) and operations are simple. Appropriate for decomposition of organic matter. Elements with low boiling points, such as Hg, As, Se, Te or Sb, risk being volatilized. Wet Digestion (Standard method of sample treatment) Heat samples and acid at a low temperature (up to 300 C). Requires a long time for decomposing organic matter (several hours to several days). Cautions must be observed in case of contamination from the working environment, such as containers or atmosphere, or from the acid. 10

Simultaneous ICP Atomic Emission Spectrometers ICPE-9800 Series ICP Mass Spectrometer ICPMS-2030 What is ICP Atomic Emission Spectrometry and ICP Mass Spectrometry? High-temperature plasma is generated by ionizing argon gas using a high frequency. Liquid samples are suctioned up by a nebulizer, vaporized and injected into the plasma, which excites the atoms within the sample. ICP Atomic Emission spectrometry measures the characteristic light emitted from the excited atoms, whereas ICP mass spectrometry puts the ionized atoms in a vacuum and analyzes their masses. Mass Spectrum Detector ICP-MS Ions are separated by mass Turbomolecular pump (Splitflow) Quadrupole mass filter Off-axis lens Collision cell Collision gas (He) Rotary pump Converging lens Plasma Skimmer cone 3rd stage (up to 0.0001 Pa) 2nd stage (up to 0.1 Pa) 1st stage (up to 100 Pa) High-frequency power supply Sampling nozzle Mini torch Nebulizer Peristaltic pump Cyclone chamber cooled by a peltier element Sample Differential vacuum system Features of ICP Atomic Emission Spectrometry High Sensitivity (ppb) Wide Dynamic Range (ppb to %) Allows qualitative analysis and simultaneous multiple-element quantitation Solutions analysis makes it easy to prepare the sample for a calibration curve Lower Detection Limits in Plastics (µg/g) Features of ICP Mass Spectrometry Ultra High Sensitivity (ppt) Wide Dynamic Range (ppt to ppm) Allows qualitative analysis and simultaneous multiple-element quantitation Solutions analysis makes it easy to prepare the sample for a calibration curve Allows measurement of isotope ratio Quantitation Example of Polyethylene (µg/g) ICP-AES Furnace AAS ICP-MS Cd 0.1 0.05 0.0003 Pb Cr Hg As 1 0.2 0.5 1 0.1 0.1 0.001* 0.1 0.0001 0.001 0.001 0.001 Note: Reduction vaporization method Sample Pretreatment Dry Ash Kjerdahl Certified Dry Ash Kjerdahl Certified Method EN1122A Method EN1122A Element Cd Pb Cr Hg As ERM-EC680 ERM-EC681 141 140 140.8 21.0 21.4 21.7 105 <1 107.6 13.1 <1 13.8 105 112 114.6 16.2 17.2 17.7 <0.5 24.0 25.3 <0.5 4.3 4.5 27.7 31.0 30.9 3.6 4.1 3.93 Reasons for low values Hg is volatilized during dry ashing Pb precipitates as lead sulfide during Kjerdahl method High Pressure Digestion and Microwave High Pressure Digestion Heat samples and acid in a closed Teflon container at about 100 190 C and decompose under high pressure. Decomposition in a closed system means volatilization of elements with low boiling points is low. Provides a fast decomposition operating environment. Contamination from reagents is low. Acid usage is low. Examples: Sediment, soil, dust, ceramics, biological samples, food products, etc. Alkali Fusion Fuse samples and alkaline flux are fused by heating at a high temperature (1000 C). Applicable for hard-soluble samples such as metal compounds and ceramics. Cautions must be observed in case of interference and contamination as samples become highly saline. RoHS/ELV 11

Hazardous Substances - Brominated Flame Retardants For Precise Quantitative Analysis Analysis of Brominated Flame Retardants using GCMS Gas Chromatograph Mass Spectrometer GCMS-QP2020 The GCMS-QP2020 can be used to accurately quantify polybrominated biphenyls (PBB) and polybrominated diphenyl ether (PBDE), both of which are regulated under the RoHS Directive. It can also accurately quantify four substances to be added as restricted substances i.e., Bis(2-ethylhexyl)phthalate (DEHP), Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), and Diisobutyl Phthalate (DIBP). To accommodate these controls, Shimadzu has prepared a structure to provide after-sales support internationally, at the same level as in Japan, in addition to providing analytical instruments. GCMS-QP2020 Features GC-MS System Featuring Highly Stable MS Calibration Scale Which is Vital for Measurement of Brominated Flame Retardants There are two bromine isotopes, 79 Br and 81 Br. With decabb and decabde, the molecular ion isotope peaks ( 12 C 12 81 Br 10 and 12 C 12 81 Br 10O) have m/z ratios of at most 954 and 970 respectively. Accordingly, the GC-MS system used for their measurements must be able to measure up to a high m/z, and be capable of correctly and stably adjusting the calibration scale even in the high mass region. Equipped with a high-performance metal quadrupole with pre-rod, the GCMS-QP2020 provides a maximum measurable m/z of 1090, and is capable of adjusting the calibration scale in the high mass region at m/z 1066. Accordingly, the system is more than capable of measuring brominated flame retardants. In addition, it can maintain a stable MS calibration scale without temperature control of the quadrupole. Capable of Measuring Brominated Flame Retardants and Phthalate Esters Without Column Replacement When the optional Twin Line MS system is used, two column outlets can be inserted directly into the mass spectrometer (MS) interface. In addition, the large-capacity differential vacuum pump provides a sensitivity equivalent to that when a single column is used. Therefore, columns suitable for brominated flame retardants and phthalate esters, respectively, can be simultaneously installed in the MS, and both substances can be analyzed without compromising the MS vacuum. Furthermore, since the Twin Line MS system does not use a flow restrictor that can cause adsorption and degradation, it can achieve column switching suitable for analysis of brominated flame retardants that have a high boiling point and are prone to adsorption. Global After-Sales Support Structure In order to accommodate these controls, Shimadzu has prepared a structure to provide after-sales support internationally, at the same level as in Japan. For Japanese businesses engaged in global business development, Shimadzu provides after-sales support at the same level as in Japan. System Configuration GCMS-QP2020, GCMSsolution workstation Twin Line MS System NIST or Wiley mass spectral library AOC-20i+s Inserts and columns (for brominated flame retardants and phthalate esters) 12

Principles of Gas Chromatograph Mass Spectrometers A gas chromatograph mass spectrometer (GC-MS) is a combined analytical system in which compounds separated by the GC are ionized by the MS, after which these ions are separated by their mass-to-charge ratios (m/z). GC Unit A sample is heated and vaporized at the GC inlet, and is then injected to the GC column using helium gas. The inner walls of the column contain a liquid phase. As the injected components move within the column together with the helium gas, they are repeatedly subject to dissolution into the liquid phase and transition into the gas phase (helium gas). The time they are retained in the liquid phase differs depending on the component, so the time before they exit the column (the retention time) also differs for each component, leading to their separation. Gas Inlet (Vaporizing Chamber) Column (Length: 30m) He Gas Separation Gas Chromatograph Chromatography (Separation) Detection Mass Spectrometer Mass Spectrometry MS Unit The components separated by the column are loaded into the MS. In the MS, accelerated electrons from a filament within the ion source strip electrons from the molecules of the compound exiting from the column. As a result, the molecules lose one electron, and become ions with a positive charge. At the same time, they are subject to cleavage, generating fragments (fragment ions) with a positive charge (electron ionization). Ions generated in this way are fed into a quadrupole (QP) to which a high-frequency voltage is applied. The ions are then separated and detected according to their m/z ratios by scanning the applied high-frequency voltage. In actual measurements, the m/z ratios of ions characteristic of the targets components are monitored in order to perform a quantitative analysis utilizing the mass chromatogram obtained. Pretreatment Procedures for Brominated Flame Retardants (IEC62321) Soxhlet Extraction-GC-MS Method Solvent Dissolution Method (Polymer to dissolve (PS-HI or HIPS)) Pulverize the polymer. Pulverize the polymer, and weigh out 100 mg. Perform pre-extraction to clean the Soxhlet extraction apparatus (70 ml of toluene for 2 hours). Add 9.8 ml of a solvent capable of dissolving the polymer. Weigh out 100 mg of the pulverized polymer. Add 200 µl of a surrogate, then dissolve it using ultrasonic waves (30 minutes). After adding the surrogate, perform Soxhlet extraction (60 ml for at least 2 hours). Fractionate 1.0 ml of the solution. After extraction, dilute the solution to 100 ml. Add 9.0 ml of a solvent that cannot dissolve polymers but can dissolve PBDE and PBB. Add an internal standard. Filter the polymer precipitate. Perform measurement by GC-MS. Add an internal standard. Perform measurement by GC-MS. RoHS/ELV 13

Hazardous Substances - Phthalate Esters For Screening Analysis Analysis of Phthalate Esters and Brominated Flame Retardants Using Py-GC-MS Screening System for Phthalate Esters Py-Screener Making the Difficult Simple The Py-Screener system is designed to screen for phthalate esters in polymers. The use of phthalate esters in toys and food packaging is currently restricted. Moving forward, they are expected to be regulated as restricted substances under the RoHS (II) Directive. The Py-Screener system consists of special software, special standard samples, and a sampling toolkit, which supports the entire process from sample preparation to data acquisition, data analysis, and maintenance. It provides an environment in which operations are simple, even for novices. Features Organics Solvents Are Not Required for Sample Preparation Analytical standards and test samples can be prepared without using organic solvents. To prepare a sample, just use the cutter to remove a portion from the test material, place it in the sample cup, and weigh it. Sample preparation videos provide support so that even novices can easily prepare samples. Preparation of a Phthalate Ester Standard Preparation of a Test Sample Sample Preparation Videos Sample preparation videos: http://www.shimadzu.com/an/gcms/py-screener.html Easy to Operate Using Special Software The special software leads you through the required procedures, so even novices can perform the operations in accordance with the software instructions. The Py and GC-MS analysis conditions are preset. To automatically start continuous analyses, just place the prepared standard samples and test samples in the autosampler, and enter the number of samples, the sample names, and their weights. Continuous measurements can be performed overnight, so approximately 30 samples can be measured per day. Measurement Schedule Window Special Py-Screener Software 14

Tabular Display of Concentrations and Criteria Clarifies the Results With LabSolutions Insight multi-analyte quantitative analysis software, the concentrations of target components detected by the continuous measurements are displayed in a table, and are subject to pass/fail determinations based on concentration ranges. The results for the continuously measured test samples can be confirmed at a glance. In addition, the system is equipped with accuracy control functions to ensure the reliability of blank concentrations, instrument sensitivity and other data. As a result, even novices can feel confident that they are reporting highly reliable measurement results. Everything Required Is Prepared The standard samples for this system were developed in cooperation with SGS Japan, the market leader in RoHS tests. Samples for sensitivity confirmation, quantitation, and blank tests can be prepared simply by punching out a portion of a standard sample using the micro puncher. A kit of the tools used for sample preparation has been created in cooperation with Frontier Laboratories Ltd. Standard Samples Contained Phthalate Esters Used for Py-GC/MS Sampling Tool Kit Maintenance Support The maintenance navigator enables simple, confident maintenance of the pyrolyzer and GC-MS. In addition, the checks performed when a leak has occurred are also guided by the software, so the source of the problem can be pinpointed easily. Furthermore, thanks to the periodic replacement parts kit, which provides parts prone to contamination with extended use, the system can be operated with confidence, even for extended periods. Maintenance Navigator Window Basic Principles of Pyrolyzers Resin Sample In a pyrolyzer, polymer samples are dropped into a pyrolysis furnace maintained at a high temperature. The polymer undergoes pyrolysis, and the products generated are then loaded into the GC-MS. If the temperature of the furnace is set lower than the polymer's pyrolysis temperature, the PBB, PBDE, and phthalate esters in the polymer can be subjected to thermal extraction without decomposing the polymer. (Thermal desorption method) Sample Cup Carrier Gas Pyrolysis Thermal Extraction MS GC RoHS/ELV 15

Shimadzu Overseas Customer Support To support customers engaged in analyses of hazardous substances governed by the RoHS and ELV directives, Shimadzu has established a global service network incorporating customer support, training and service centers in the USA, Germany, China and Singapore, as well as in Japan. Shimadzu provides comprehensive support services including instrument maintenance, training workshops and the provision of relevant information to meet customer needs regarding both software and hardware. GLOBAL NETWORK RoHS / ELV Complying with European Chemical Substance Regulations SHIMADZU EUROPA GmbH SHIMADZU (CHINA) CO., LTD SHANGHAI BRANCH SHIMADZU SCIENTIFIC INSTRUMENTS, INC. SHIMADZU (ASIA PACIFIC) PTE LTD. www.shimadzu.com/an/ For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country. Company names, products/service names and logos used in this publication are trademarks and trade names of Shimadzu Corporation, its subsidiaries or its affiliates, whether or not they are used with trademark symbol TM or. Third-party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not they are used with trademark symbol TM or. Shimadzu disclaims any proprietary interest in trademarks and trade names other than its own. The contents of this publication are provided to you as is without warranty of any kind, and are subject to change without notice. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. Shimadzu Corporation, 2017 First Edition: May 2017, Printed in Japan 3655-05720-10ANS