SAAMF meeting 6 February 2007

1. 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

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

3. Environmental Directives –WEEE, RoHS and ELV • By weight and per homogeneous material shall be tolerated • PBB – Polybrominated biphenyls • PBDE – Polybrominated diphenyl ethers

4. 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)

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

6. 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) www.rohsbyxrf.com

7. 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 • $1 000 000 or more + experienced staff

8. Testing Regime www.niton.com/documents/ThermoRoHSGreenproductflyer.pdf

9. 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 XRF Screening www.spectroscopynow.com/coi/cda/detail.cda?id=14695&type=Feature&chId=8&page=1

10. 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

11. 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

12. Testing Regime (Cont.) www.niton.com/documents/ThermoRoHSGreenproductflyer.pdf

13. 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

14. 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

15. Traceability - CRMs • Aluminium-based

16. Traceability - CRMs • Iron-based

17. Traceability - CRMs • Zinc-based

18. Traceability - CRMs • Polymer

19. Traceability - CRMs • Other

20. Certified Reference Materials (CRMs)

21. 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

22. Development of Standards • IEC (International Electrotechnical Commission) • International – partake through national committees • TC 111 - 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

23. 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

24. Contents of the CDV 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

25. PBBs and PBDE • 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

26. Cr VI in Coatings • Sources • Fasteners (screws, nuts, bolts, etc) • Heat sinkers • AC adapters, variable resistors, • Metal housing/frame (motor, transformer, etc.) • ppm vs µg/cm2 • 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

27. Cr VI in Coatings

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

29. Cr VI Determination

30. 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

31. Round Robins • 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 ? • ?

32. Laboratory Database

33. Laboratory Database (Cont.)

34. Laboratory Database (Cont.)

35. Workshop • Test & Measurement Conference • Emperor’s Palace • 19-21 November 2007 (Mon-Wed) • One day • International experts? • UK-dti • Cr VI • Sponsorship

36. 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.

37. Finally • Contact:Retha Rossouw 012-841 2607 rrossouw@csir.co.za Maré Linsky012-841 3974 mlinsky@csir.co.za