Upload
ashley-jordan
View
214
Download
1
Tags:
Embed Size (px)
Citation preview
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 0,10
ELV 0,01 0,10 0,10 0,10 - -
Cancer Lung cancerPsychological disorders Blindness
Thyroid disorders
Liver 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)
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
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 Determination
Metals Plastics Electronics
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
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.