An Update: the NML’s Project to Assist the Automotive Industry in the Testing of Components for Substances of Concern SAAMF meeting 6 February 2007

Overview  Introduction  Compliance and Laboratories Testing Regime Reference Materials Standard Procedures NML Laboratory database Workshop  Summary

Environmental Directives – WEEE, RoHS and ELV EU Directive Recycling / Re-use Targets Substances of Concern (SOCs) Maximum limits (%) * CdCr(VI)HgPbPBBPBDE WEEE  RoHS  0,010,10 ELV  0,010,10 -- CancerLung cancer Psychologic al disorders Blindness Thyroid disorders Liver tumours By weight and per homogeneous material shall be tolerated PBB – Polybrominated biphenyls PBDE – Polybrominated diphenyl ethers

Brominated Flame Retardants – ELV?  Polystyrene (PS), high impact polystyrene (HIPS), Acrylonitrile/Butadiene/Styrene (ABS), etc.  Printed circuit boards (PBDE and Pb)  Plastic parts, housings, fasteners, clips, screws, etc. (Pb, Cd, PBDEs)

 Toyota (4 May 2006)  GMSA (29 Nov 2006)  VW (30 Nov 2006)  DC (1 Dec 2006) OEM Visits

ELV Compliance  Screen for violations in your own supply chain  Demand declarations of conformity from your suppliers (cannot always be trusted, the liability is still yours)  Audit suppliers by sending parts to independent test labs (always a good idea)

Laboratories  Independent laboratory Unbiased, useful information about the samples Demand proof that the laboratory can analyse the materials that they are testing (right methods followed) Question “not detected” results Accreditation – scope Sample prep Grinding! Contamination Dilution! Validation (CRMs) False claims and bad science (wrong methods quoted) No out-sourcing  Own laboratory $ or more + experienced staff

Testing Regime

XRF Screening  Qualitative screening to check just for the presence of restricted elements and compounds  Quantitative Screening to determine the concentration of restricted elements and provide fast answers  Quantitative Analysis to evaluate concentrations close to the limit values with a second independent analytical method only in case of doubt

EDXRF – Types  Handheld Portable (various locations) Fundamental Parameters (FP)  Micro Spot Product Mapping Fundamental Parameters (FP)  Bulk Analyser Grinding / milling Improved detection limits (1 ppm level) ED and WD

Quantification and Verification  Screening (20 to 1000 ppm) and Quantification Impractical or impossible to perform proper uncertainty budget Assume a relative uncertainty of 30 % - define confidence interval  Sample parameters Sample thickness Sample complexity Sample uniformity Size, shape and location of target measurement field Instrument limits of detection  Sample preparation  More precise test techniques  Lower level, more exact measurements

Testing Regime (Cont.)

Quantification and Verification  XRF Fundamental parameters: “semi-quantitative” Suitable CRMs for validation: matrix, concentration  ICP / AAS Traceability to SI through certified calibration standards Suitable CRMs for validation: matrix, concentration  UV-Vis Traceability to SI through certified calibration standards Suitable CRMs for validation: matrix, concentration  FT-IR database  GC-MS CRMs  HPLC CRMs

Other techniques  GD-OES CRMs Depth profiling Bulk analysis NIST possible colaboration  SEM/EDX 1 mass % detection limit mapping  XPS FP reduction  TOF-SIMS Not quantitative, only relative

Traceability - CRMs  Aluminium-based

Traceability - CRMs  Iron-based

Traceability - CRMs  Zinc-based

Traceability - CRMs  Polymer

Traceability - CRMs  Other

Certified Reference Materials (CRMs)

Development of Standards  ASTM International Multinational – participation as company or individual Committee F40 on Declarable Substances in Material F40.01 Test Methods WK9866 – Solder alloys by ICP-OES WK9895 – Screening materials WK11200 – SOCs in polymers by XRF Current Status

Development of Standards  IEC (International Electrotechnical Commission) International – partake through national committees TC Environmental standardization for electrical and electronic products and systems Working Group 1: Material declaration for electrical and electronic equipment Working Group 2: Environmentally conscious design for electrical and electronic products and systems Working Group 3: Test methods of hazardous substances PT 3: HWG 3: Sample disjointment PT 62476: Guidance for assessing compliance of finished goods with respect to restriction of use of hazardous substances

WG3: Test methods  IEC 62321: Procedures for the determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers) in electrotechnical products  Status: CDV  But of the 23 NCs voting, only 12 were in favour  Next International Inter-Laboratory Study (IIS3) Currently underway

7.Determination of PBB and PBDE in Polymers by GC-MS 8.Test for the Presence of Hexavalent Chromium (Cr VI) in Colourless and Coloured Chromate Coating on Metals 9.Determination of Hexavalent Chromium (Cr VI) by Colorimetric Method in Polymers and Electronics Contents of the CDV

 Samples: UP and TUT  (Identify polymer – FT-IR)  Solvent extraction Soxhlet (and maybe microwave) Particle size Extraction time Temperature Etc.  GC-MS analysis  CPT routine analysis  Experts: Necsa and TUT PBBs and PBDE

 Sources Fasteners (screws, nuts, bolts, etc) Heat sinkers AC adapters, variable resistors, Metal housing/frame (motor, transformer, etc.)  ppm vs µg/cm 2  Layer thickness varies between 20 nm to 1 µm  Cr VI detected  > 1000 ppm Cr VI (Japan)  Spot test vs boiling water test (> 200 nm)  Qualitative vs quantitative Coating layer not stable Environmetal conditions Storage time RSD Cr VI in Coatings

MethodTesting windowBoiling water extrac- tion time (min) Sample storage Standard for comparison or DL DL verifi- cation unitsVerificati on SpotBoiling water SpotBoiling water IEC Within 30 days 10ambient0,5 mg/kg 0,02 mg/kg, total 1 µg Cr VI in 50 ml extract Nomg/kg (50 cm 2 used) twice ISO 3613 Betwee n 1 and 3 days 5No require- ment No µg/cm 2 Not available DIN EN N/ANo require- ment 10No require- ment N/A0,1 µg/cm 2, total 5 µg Cr VI in 50 ml extract Noµg/cm 2 Not available GMW 3034 N/ANo require- ment 5 N/A0,1 µg/cm 2, total 0,5 µg Cr VI in 50 ml extract Noµg/cm 2 Not available

 Quantitative method  Alkaline digestion  Colorimetric measurement  Works well for PVC, other matrices?  Promising for glass  Total Cr by ICP Cr VI in Polymers and Electronics

Cr VI Determination MetalsPlasticsElectronics Spot test Boiling water extraction test Alkaline digestion Colorimetric method Alkaline digestion Colorimetric method

IEC IIS3  Cr VI in coatings on metals Spot test Boiling water extraction Synergy with automotive: Dr Christoph Bauspiess (DC)  Cr VI in polymers Extraction: alkaline digestion Reaction with 1,5-diphenylcarbazide – measured UV-Vis  PBB and PBDE in polymers ABS, HIPS, PS Soxhlet extraction GC-MS analysis  Benchmark NML’s analytical capabilities Round robin South African laboratories

 Method validation at NML  Homogeneous material  Involve as many laboratories as possible  Laboratory visits Innoventon, NMMU, PE (Dec 2006) Setpoint M&L UIS Scooby’s Durban University of Technology ? ? Round Robins

Laboratory Database

Laboratory Database (Cont.)

Workshop  Test & Measurement Conference Emperor’s Palace November 2007 (Mon-Wed) One day International experts? UK-dti Cr VI Sponsorship

Summary  Method development and validation (IEC and automotive)  Laboratory round robin (BFRs, Cr VI, ICP)  Standards development (IEC and ASTM) Meeting May, Chicago Meeting November  Laboratory database (NLA)  Awareness Roadshows Seminars Workshop Website Etc.

Finally  Contact: Retha Rossouw Maré Linsky