An Update: the NML’s Project to Assist the Automotive Industry in the Testing of

Components for Substances of Concern

SAAMF meeting6 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 (%) *

Cd Cr(VI) Hg Pb PBB PBDE

WEEE - - - - - -RoHS 0,01 0,10 0,10 0,10 0,10 0,10ELV 0,01 0,10 0,10 0,10 - -

Cancer Lung cancerPsychological disorders Blindness Thyroid

disordersLiver

tumours

• By weight and per homogeneous material shall be toleratedPBB – Polybrominated biphenylsPBDE – 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)

www.rohsbyxrf.com

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

Testing Regime

www.niton.com/documents/ThermoRoHSGreenproductflyer.pdf

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

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

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.)

www.niton.com/documents/ThermoRoHSGreenproductflyer.pdf

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

Cd Cr Hg PbBAM 311 CRM 2.5x6 cm 0.001270 0.10370 0.050400BAM 312 CRM 2.5x6 cm 0.002260 0.02760 0.004390BAM 313 CRM 2.5x6 cm 0.000740 0.12240 0.00041 0.004330BAM 314 CRM 2.5x6 cm 0.001300 0.05170 0.221000AL 116/03 CRM 60x25 mm 0.001000 0.00520 0.00410 0.001500AL 121/05 CRM 60x25 mm 0.002100 0.01020 0.00030 0.005100AL 122/04 CRM 60x25 mm 0.004900 0.01910 0.00870 0.007600AL 124/03 CRM 60x25 mm 0.019000 0.05300 0.017000R A 19 SUS 50x50 mm 0.010000 0.20000 0.002R A 16 SUS 50x40 mm 0.00500 0.100164X ALSUS 8 SUS 50x20 mm 0.06000 0.001164X ALSUS 6 SUS 50x20 mm 0.030000 0.02000 0.050

Traceability - CRMs Iron-based

Cd Cr Hg PbSRM 1262b CRM 34x 19 mm 0.3000 0.000400SRM 1263a CRM 31x19 mm 1.3100 0.002200SRM 1264a CRM 31x19 mm 0.0660 0.024000SRM 1265a CRM 31x19 mm 0.0072 0.000015SRM 1269 CRM 31x19 mm 0.2010 0.005000SRM 1270 CRM 32x19 mm 2.3400 -0.001600SRM 1271 CRM 32x19 mm 0.5520SRM 1765 CRM 32x19 mm 0.051 0.000300SRM 1766 CRM 34x19 mm 0.024 0.003000

Traceability - CRMs Zinc-based

Cd Cr Hg PbERM-EB324 CRM 0.7 kg disc 48.6 26.1ERM-EB325 CRM 0.7 kg disc 94.7 142BCR-327 CRM 0.7 kg disc 301.4 409.4BCR-353 CRM 0.7 kg disc 10.44 24.4BCR-354 CRM 0.7 kg disc 29.7 30.8BCR-355 CRM 0.7 kg disc 58.1 56.9BCR-358 CRM 0.7 kg disc 10.22 22.5BCR-359 CRM 0.7 kg disc 29.8 36.2BCR-360 CRM 0.7 kg disc 59.5 73.9

Traceability - CRMs Polymer

Number Matrix Form Br Cd Cr Hg PbJSAC 0601-2 polyester chip 4.8 9.8 1.1 10.4JSAC 0602-2 polyester chip 47.2 99.8 11.8 102JSAC 0611 polyester 10 x 4 mm <1 <1 <1JSAC 0612 polyester 10 x 4 mm 4.5 25.5 26.1JSAC 0613 polyester 10 x 4 mm 10 52 54.6JSAC 0614 polyester 10 x 4 mm 98.6 23.8 106.8JSAC 0615 polyester 10 x 4 mm 43.4 212.8 202.2NMIJ CRM 8102-A ABS pellets 10.77 27.87 108.9NMIJ CRM 8103-A ABS pellets 106.9 269.5 1084ERM-EC680 polyethylene 100 g 808 140.8 114.6 25.3 107.6ERM-EC681 polyethylene 100 g 98 21.7 17.7 4.5 13.8

Traceability - CRMs Other

Br Cd Cr Hg PbBCR-545 Cr VI filter

BCR-664trace elements in glass plate 5.7 2.65 53.1

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 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

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/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

Cr VI in Coatings

Cr VI in CoatingsMethod Testing window Boiling

water extrac-tion time (min)

Sample storage

Standard for comparison or DL

DL verifi-cation

units Verification

Spot Boiling water

Spot Boiling water

IEC 62321

Within 30 days

Within 30 days

10 ambient 0,5 mg/kg

0,02 mg/kg, total 1 µg Cr VI in 50 ml extract

No mg/kg (50 cm2 used)

twice

ISO 3613

Between 1 and 3 days

Between 1 and 3 days

5 No require-ment

No No No µg/cm2 Not available

DIN EN 15205

N/A No require-ment

10 No require-ment

N/A 0,1 µg/cm2, total 5 µg Cr VI in 50 ml extract

No µg/cm2 Not available

GMW 3034

N/A No require-ment

5 No require-ment

N/A 0,1 µg/cm2, total 0,5 µg Cr VI in 50 ml extract

No µg/cm2 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 DeterminationMetals Plastics Electronics

Spot testBoiling water extraction test

Alkaline digestionColorimetric method

Alkaline digestionColorimetric 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.)

Laboratory Database (Cont.)

Workshop Test & Measurement Conference

• Emperor’s Palace• 19-21 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 Rossouw012-841 2607rrossouw@csir.co.za

Maré Linsky012-841 3974mlinsky@csir.co.za