RoHS Compliance Analytical Considerations

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RoHS Compliance - Analytical Considerations

• Sampling and Test Methods for RoHS

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Micro-contamination Testing

• We provide 6 testing services as shown below
• Testing of ban substances as per RoHs Directive
  requirements
• Cleanliness testing of electronic and hard disk
  drive components
• Clean- room consumables testing
• Cleanliness Testing on Ultra- pure Water
  Chemical
• Electrostatic Discharge Test
• Failure Analysis (Surface Analysis)

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RoHS Directive

• Directive 2002/ 95/ EC RoHS is defined as the
  Restriction of the use of certain Hazardous
  Substances in electrical and electronic
  equipment.
• From 1 July 2006, new electrical electronic
  equipment (EEE) put on the market should not
  contain these substances.

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List of Hazardous Substances

• Heavy Metals
• Lead Pb
• Cadmium Cd
• Mercury Hg
• Hexavalent Chromium Cr6
• Brominated Flame Retardants
• Polybrominated biphenyl (PBBs)
• Polybrominated diphenyl ether (PBDEs)

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Other Hazardous Substances

• Polychlorinated biphenyls-mono-ortho (PCB)
• Polychlorinated naphthalenes (PCN), (more than 3
  chlorine atoms)
• Polychlorinated terphenyls (PCT)
• Short chain chlorinated paraffins
• Ozone depleting substances (CFCs etc.)
• Organo Tin Compounds such as Tributyltin (TBT)
  and Triphenyltin (TPT) Tributyltin oxide (TBTO)
  
• Asbestos
• Azo compounds/colorant
• Formaldehyde
• Polyvinyl chloride (PVC) PVC blends

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Why these are banned?
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Where are they used?
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Maximum Concentration Values

• The commission has proposed a draft decisionBy
  weight in homogeneous materials
• Cd 0.01 or 100ppm
• Pb 0.1 or 1000ppm
• Hg 0.1 or 1000ppm
• Cr6 0.1 or 1000ppm
• PBBs 0.1 or 1000ppm
• PBDEs 0.1 or 1000ppm

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Definitions

• Homogeneous material A material that can not be
  mechanically disjointed into different material
  such as plastics, metals and alloys etc.
• Mechanically disjoined Material can, in
  principle, be separated by mechanical actions
  such as unscrewing, cutting, crushing, grinding
  and abrasive processes

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Who should test?

• Product manufactory is responsible to take back
  their products and recycle them if possible.
• Applied Products IT, Telecommunication, consumer
  and lighting equipment Household appliances
  Wire and cable etc.
• Lab test takes about 5 working days

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Sample Preparation for Analysis

• Sample to be tested in component or material
  level.
• Separate the components physically, e.g. PCB
• Component contain plastic and metal part should
  be tested separately. e.g. Wire and cable

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Sample Preparation for Analysis

• Sample size for test is small, from 0.3g to 3g
• Sample homogeneity, e.g. printing on cardboard
  box
• Cut the sample to be as small as possible, e.g.
  packaging material
• Grind the sample to fine powder if possible

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Cryogenic Miller

• To mill the polymer / plastic material / parts to
  fine powder.
• To get homogeneous sample.
• To digest the sample fast and completely.

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Polymer / Plastic Samples After Mill
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Test Instrumentation

• XRF, EDX Energy Dispersive X-Ray Fluorescence
  Spectrometer
• ICP-OES/AES Inductively Coupled Plasma
  Optical/Atomic Emission Spectrometry, Perkin
  Elmer 5300DV.
• UV/Vis Ultraviolet-Visible Spectroscopy,
  Shimadzu.
• FIAS-AAS Flow Injection Analysis System, Atomic
  Adsorption Spectroscopy, Perkin Elmer. Microwave
  digestor, Mars 5.
• GC-MSD Gas Chromatography Mass Selective
  Detector, Thermo PolarisQ Ion Trap GC/MS/MS
• FTIR Fourier Transform InfraRed
  Spectrophotometer, Nicolet 550

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Test Method
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PBBs PBDEs

• PBBs and PBDEs are flame-retardant manufactured
  chemicals found in plastics used in a variety of
  consumer products (computer monitors,
  televisions, textiles, plastic foams, etc.)
• Mixed into plastics rather than bound to them,
  they can leave the plastic and find their way
  into the environment.
• PBBs and PBDEs are similar, but not identical
  compounds
• Both are colorless to off-white solids and
  mixtures of up to 209 individual component
  chemicals called congeners.

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PBB PBDE Screening by FTIR

• FTIR can be used to investigate the presence of
  bromine flame retardant
• Diamond ATR technique will be used.
• Detection limit is approximately a few percent.
• The effective content of Bromine flame retardant
  in plastic is about 5 to 10.
• The distinct peak of bromine flame retardant in
  FTIR spectrum is about 1250cm-1 to 1450cm-1.

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PBB PBDE Analysis by GCMS

• Sampling Cutting and grinding
• Solvent Extraction Methylene Chloride or
  Toluene Soxhlet extraction
• Cleaning Silica gel to remove interference if
  necessary
• Analysis GCMS with DB-5MS Capillary column

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GCMS/MS
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PBDEs--GCMS Chromatogram
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PBBs--GCMS Chromatogram
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PBB Calibration Curve 1
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PBB Calibration Curve 2
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PBB Calibration Curve 3
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PBDE Calibration Curve 1
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PBDE Calibration Curve 2
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PBDE Calibration Curve 3
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Elemental Screening by XRF

• X-ray fluorescence spectrometer with WDX and EDX
• Cd, Pb, Hg Total Cr
• Bromine for PBBs and PBDEs
• Rapid, direct and non-destructive test
• Hard to get standard.
• High detection limit

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BS EN 1122 2001 Cadmium Extraction

• Procedure for Cadmium Extraction
• Weigh about 1- 2 gram of the sample
• Cut the sample into smaller pieces preferably in
  pieces less than 0.1gram
• Mix to homogeneity
• Add 10ml of concentrated H2SO4 and cover reflux
• Add 5ml H2O2 and reflux until bubbling subsides
• Cool to room temperature, filter then make to
  volume
• Analyze by ICP- OES

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US EPA 3050BCd, Pb Total Cr

• Weigh about 1 gram of the sample and mix to
  homogeneity
• Add 10ml-concentrated HNO3 and cover reflux for
  15 minutes cool
• Add 5ml-concentrated HNO3 and cover reflux for 30
  minutes cool and repeat twice.
• Add 2ml water and 3ml 30 H2O2 repeat and
  evaporate to 5ml, cool
• Add 10ml concentrated HCl to the digest and cover
  reflux for 15 minutes
• Filter then make to volume, 50ml.
• Analyze by ICP- OES

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US EPA 3052 Cd, Pb, Total Cr Hg

• Weigh about 0.25 gram of the sample and mix to
  homogeneity
• Add 2ml 30 H2O2, 3ml concentrated HCl and
  7ml-concentrated HNO3
• Place in the microwave furnace and digest
  according to the following program.
• Heat to 120C, time period 3-4 minutes
• Heat to 200-220C, time period 15-20 minutes
• Maintain temperature at about 200C for 10
  minutes
• Cool, filter then make to volume, 50ml
• Analyze by ICP- OES

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Microwave Digestion
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ICP-OES
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AAS
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Hexavalent Chromium Chromium (VI)

• Chromium exists in 2 common forms, Chromium (III)
  and Chromium (VI)
• The Chromium (VI) form is carcinogenic
• Diphenylcarbazide selectively forms a red/violet
  color complex with Cr6, without reacting with
  Cr3.
• An absorption curve is obtained with a peak in
  vicinity of 540nm.

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UV-VIS
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US EPA 3060A Alkaline Extraction for Cr6

• Weigh about 2.5 /- 0.10 gram of the sample
• Add 50 ml 0.5M NaOH/ 0. 28M Na2CO3 digestion
  solution, 400 mg MgCl2 and 0.5 ml 1.0M phosphate
  buffer
• Heat at 90C for 60 minutes
• Cool and adjust pH to 7.5 /-0.5 with nitric
  acid.
• Filter through 0.45um filter
• Bring to final volume, ready for color
  development.
• Analyze by UV- Vis

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Quality Control ---CRM
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Detection Limit
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Questions?

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• Singapore 608 925
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• Lei Zhi Pei
• H/P (65) 97979622
• DID (65) 68950688
• Fax [phone]
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