Determination of Levels of Six Regulated Substances Lead, Mercury, Hexavalent Chrominum, Polybromin

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?????????????????Determination of Levels of Six
Regulated Substances (Lead, Mercury, Hexavalent
Chrominum, Polybrominated Biphenyls,
Polybrominated Biphenyl Ether) in
Electrotechnical Products

• ??? ??
• Dr. Zheng Jianguo
• Guangdong Entry-Exit Inspection Quarantine
  Bureau, P.R.China

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Comparisons of Testing methods of ISO/IEC, GB and
SN for RoHS

• 13 methods in ISO/IEC 62321
• 12 methods in GB series standards
• 22 methods in SN series standards
• Details in Table 1.

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SN series Standards for RoHS
Testing Methods
Procedures of the mechanical disjointment for
the determination of regulated substances in
electrotechnical products
Conformity Assessment
General Requirements
lead, mercury, cadmium, chromium
Chromium(VI)
PBB?PBDE
screening
XRF Spot-test Spark IR
GC-MS LC-MS GC-ECD GC-FID HPLC
ICP-AES AAS ICP-MS CVAAS AFS
UV-VIS IC
4
15 methods in SN series standards for RoHS have
been finished

• 1?Determination of Chromium(VI)in electrical and
  electronic equipment1,5-Diphenylcarbohydrazide
  spectrophotometry
• Cr (VI) compound was extracted from sample
  using basic extract solution with shaking at
  90?95? water bath for 1.5 hours, which can react
  with 1,5-Diphenylcarbohydrazide to appear a kind
  of amaranthine complex in acid medium. Then, this
  complex was detected at wavelength 540 nm with UV
  spectrometry.

5
15 methods in SN series standards for RoHS have
been finished

• 2?Determination of mercury in electrical and
  electronic equipmentHydride generation-atomic
  fluorescence spectrometry
• As to metal material in electrical and
  electronic equipment, it was digested with
  routine acid digestion. And to the other
  material, it was digested with airtight
  high-temperature press bomb. After digestion,
  mercury in sample material can be digested into
  dissoluble salt. And finally, obtained digestion
  solution was detected using Hydride
  generation-atomic fluorescence spectrometry.

6
15 methods in SN series standards for RoHS have
been finished

• 3?Determination of lead, cadmium and chromium in
  electrical and electronic equipmentFlame atomic
  absorption spectrometry
• As to metal material in electrical and
  electronic equipment, it was digested with
  routine acid digestion with concentrated nitric
  acid,and for the other material, it was digested
  with concentrated HNO3?H2O2 and HF(specially for
  the glass and chinaware material)at 1805? for 4
  hours by using airtight high-temperature press
  bomb. After digestion, lead, cadmium and chromium
  in sample material can be digested into
  dissoluble salt. And finally, obtained digestion
  solution was detected using flame atomic
  absorption spectrometry.

7
15 methods in SN series standards for RoHS have
been finished

• 4?Qualitative screening of lead, mercury,
  cadmium, chromium and bromine in electrical and
  electronic equipmentWavelength dispersive X-ray
  fluorescence spectrometry
• Based on the lead, mercury, cadmium, chromium
  and bromines characteristic X-ray lines, the
  wavelength dispersive x-ray fluorescence
  spectrometry (WDXRF) can be used for qualitative
  screening the prepared sample. When the elements
  characteristic X-ray peak appears in the
  qualitative screening result, it approve that the
  element exist in the sample. When the elements
  characteristic X-ray peak doesnt appear in the
  qualitative screening result, it approve that the
  elements content is lower than the detection
  limit of WDXRF.

8
15 methods in SN series standards for RoHS have
been finished

• 5?Determination of polybrominated biphenyls and
  polyborminated biphenyl ethers in electrical and
  electronic equipmentHigh Performance Liquid
  chromatography
• Technical flame retardants such as polybromo
  biphenyls and polybromo biphenyl ethers in
  electrical and electronic equipment were
  separated and determined by high performance
  liquid chromatography method. The samples were
  extracted with 150mL toluene in a soxhlet
  apparatus for three hours. The HPLC separation
  was achieved on a reversed-phase C18 column,
  applying gradient elution using a mixture of
  aqueous phosphate buffer and methanol with
  ultraviolet detection in the scanning mode at
  226nm.

9
15 methods in SN series standards for RoHS have
been finished

• 6?Determination of polybrominated biphenyls and
  polyborminated biphenyl ethers in electrical and
  electronic equipmentGas chromatography/Mass
  spectrometry
• The electrical and electronic equipment samples
  were extracted with 150mL toluene in a soxhlet
  apparatus for three hours. The extracted solution
  was purified by silica gel column and then
  concentrated in rotary vacuum evaporator. The
  residue was taken up in 2.0 mL toluene. Polybromo
  biphenyls and polybromo biphenyl ethers were
  separated and determined by Gas
  chromatography/Mass spectrometry.

10
15 methods in SN series standards for RoHS have
been finished

• 7?Determination of polybrominated biphenyls and
  polyborminated biphenyl ethers in electrical and
  electronic equipment-GCFID
• The electrical and electronic equipment samples
  were extracted with 150mL toluene in a soxhlet
  apparatus for three hours. The extracted solution
  was purified by silica gel column and then
  concentrated in rotary vacuum evaporator.
  Internal standard in 1.0 mL toluene was added to
  the residue, polybromo biphenyls and polybromo
  biphenyl ethers in the mixture were separated and
  determined by Gas chromatography with flame ion
  detector.

11
15 methods in SN series standards for RoHS have
been finished

• 8?Qualitative screening of polybrominated
  biphenyls and polyborminated biphenyl ether in
  electrical and electronic equipment by infra-red
  spectrometric method
• The method is to collect the infra-red spectrum
  of plastic part of the electric or electronic
  equipments, analyzing the polymeric component.
  Comparing the spectrum of the sample with the
  reference spectrum of the relative polymer, to
  determine whether the sample spectrum contains
  the characteristic peaks of the C-Br bond within
  the 650cm-1500cm-1 region, and, to figure out
  whether the sample contains PBB or PBDE.

12
15 methods in SN series standards for RoHS have
been finished

• 9?Quantitative Screening of Lead, Mercury,
  Chromium, Cadmium and Bromine in Electrical and
  Electronic Equipment-X-Ray Fluorescence
  Spectrometric Method
• Wavelength dispersive X-ray fluorescence
  spectrometry (WD-XRF) has been applied to the
  direct quantitative screening of lead(Pb),
  mercury(Hg), chromium(Cr), cadmium(Cd),
  bromine(Br) in electrical and electronic
  equipments. It covers all material types such as
  polymers, metals, and other electronic assembly
  materials. A series of six polymers reference
  materials and other matrix reference materials
  were prepared to make calibration curves.
  Determination of the elemental concentrations for
  the references and samples was analyzed by
  WD-XRF.

13
15 methods in SN series standards for RoHS have
been finished

• 10?Determination of polybrominated biphenyls and
  polybrominated diphenyl ethers in electrical and
  electronic equipment With HPLC/MS-MS
• A HPLC/MS-MS method for the determination of
  polybrominated biphenyls and polybrominated
  diphenyl ethers in electrical and electronic
  equipments was established. The polybrominated
  biphenyls and polybrominated diphenyl ethers was
  extracted with toluene using ultrasonator from
  samples and detected by HPLC/MS-MS.

14
15 methods in SN series standards for RoHS have
been finished

• 11?Determination of Lead and Cadmium in in
  electrical and electronic equipment by AFS
• The method is used for he determination of lead
  and Cadmium in a) polymers b) metal materials
  made from aluminium, iron and zinc matrices and
  c) electronics. The sample is digested and heated
  to exhausting the acids, then diluted properly.
  Ionic Cd in the sample solution reacts with KBH4
  and generates volatile gas, which is introduced
  to atomizer with carrier gas (Ar). The content of
  cadmium is determined on the basis of
  fluorescence intensity of the element.
• Ionic Pb(?) in the sample solution is oxidized
  into Pb(?) by potassium ferricyanide, then reacts
  with KBH4 and generates volatile hydride PbH4,
  which is introduced to atomizer with carrier gas
  (Ar). The content of lead is determined on the
  basis of fluorescence intensity of the element.

15
15 methods in SN series standards for RoHS have
been finished

• 12?Determination of Lead, Cadmium, Chromium and
  Mercury in electrical and electronic
  equipmentInductively coupled plasma atomic
  emission spectrometry
• The samples of polymer materials (such as PP,
  PE, PS, ABS, PVC, etc.) and electronics (such as
  glasses and ceramics, etc.) from Electronic and
  electrical equipment were digested under pressure
  with nitric acid, tetrafluoroborate solution and
  hydrogen peroxide in a tightly sealed PTFE vessel
  which was then put into the corrosion resisting
  steel pressure dissolution can. The pressure
  dissolution can as a whole was heated at 180? for
  4h in a constant temperature heating oven. The
  samples of metallic materials (such as iron
  alloys, copper alloys, aluminum alloys, zinc
  alloys and solder alloys, etc.) from Electronic
  and electrical equipment were digested by heating
  with reflux cooler and absorption vessels. The
  samples of polymer materials and electronics from
  Electronic and electrical equipment were digested
  under pressure with microwave sample preparation
  system. The method for the simultaneous
  determination of Pb, Cd, Cr, Hg in polymer
  materials, metallic materials and electronics
  from Electronic and electrical equipment have
  been developed

16
15 methods in SN series standards for RoHS have
been finished

• 13?Determination Of Mercury In Electrical And
  Electronic Equipment
• -Cold Vapor Atomic Absorption Spectrometry
• This standard provides the procedure for the
  determination of materials used in Electrical And
  Electronic Equipment. These materials are polymer
  materials, metal materials and electronics. Metal
  materials in electrotechnical equipment are
  treated by traditional digestion using acids.
  Other materials, such as polymers and
  electronics, were digested with acids, in
  microwave oven or in a sealed and high pressure
  autoclave. The mercury in the digestion solution
  is reduced to the atomic state before it is
  analyzed, then mercury is determined by Cold
  Vapor Atomic Absorption Spectrometry.

17
15 methods in SN series standards for RoHS have
been finished

• 14?Technical Requirements for the Conformity
  Assessment of Certain Hazardous Substances in
  Electrical and Electronic Equipment
• This standard specifies the general technical
  requirements for the conformity assessment of
  certain hazardous substances in electrical and
  electronic equipments. For the purpose of
  determining the conformity of the products with
  relevant laws and regulations and evaluating the
  validity of the test results, the following items
  should be assessed and certified to be fully in
  compliance with specific technical requirements.

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15 methods in SN series standards for RoHS have
been finished

• 15?Procedures of the mechanical disjointment for
  the determination of regulated substances in
  electrotechnical products
• This part specifies the procedures and
  requirements of the mechanical disjointment of
  electrotechnical products into test units for
  chemical determination of certain regulated
  substances.
• This part deals with the mechanical disjointment
  of electrical and electronic products (including
  their parts and components) with rated voltage
  not exceeding 1 000 volts for alternating current
  and 1 500 volts for direct current

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• Thank you for your attention!

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• This part deals with but is not limited to the
  following categories of products
• large household electrical appliances
• small household electrical appliances
• information technology equipment and
  telecommunication equipment
• Consumer equipment
• Lighting equipment
• Electrical and electronic tools
• Toys, leisure and sports equipment
• Medical devices
• Monitoring and control instruments
• Automatic dispensers