complying with european chemical substance regulations · july 22, 2016 onwards july 22, 2017...

Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment / End-of Life Vehicles

RoHS / ELVComplying with European Chemical Substance Regulations

RoHS / ELV

Com

plying with European C

hemical Substance Regulations

GLOBAL NETWORK

SHIMADZU EUROPA GmbH

SHIMADZU (CHINA) CO., LTDSHANGHAI BRANCH

SHIMADZU (ASIA PACIFIC) PTE LTD.

SHIMADZU SCIENTIFIC INSTRUMENTS, INC.

© Shimadzu Corporation, 2017

www.shimadzu.com/an/

For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country.Company names, products/service names and logos used in this publication are trademarks and trade names of Shimadzu Corporation, its subsidiaries or its affiliates, whether or not they are used with trademark symbol “TM” or “®”.Third-party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not they are used with trademark symbol “TM” or “®”.Shimadzu disclaims any proprietary interest in trademarks and trade names other than its own.

The contents of this publication are provided to you “as is” without warranty of any kind, and are subject to change without notice. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication.

First Edition: May 2017, Printed in Japan 3655-05720-10ANS

2 3

RoHS/ELV

EU Regulations for Hazardous SubstancesOverview of Revised RoHS/ELV Directives

The Environmental Problems of the European Union (EU) and Trends in Test Methods

Upon implementation of the European Union’s ELV Directive (End-of-Life Vehicle

Directive), in effect since July 2003, automobiles, automotive parts or materials subject

to the directive cannot be exported to the EU unless they contain no cadmium (Cd),

lead (Pb), mercury (Hg) or Hexavalent chromium (Cr6+). Similarly, the RoHS Directive

(Restriction of Hazardous Substances in Electrical and Electronic Equipment), in effect

since July 1, 2006, restricts the use of electric and electronic equipment containing any

of six specified hazardous substances: two kinds of brominated flame retardants -

polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE), Cd, Pb, Hg,

and Cr6+.

Later, categories 8 (medical devices) and 9 (monitoring and control instruments) were

added to the scope of RoHS Directive, with no additions or changes made with respect

to the restricted substances or thresholds.

The addition of phthalate esters (Bis(2-ethylhexyl) phthalate (DEHP), Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), and Diisobutyl

phthalate (DIBP)) was finalized in 2015. IEC:62321, the international standard test method in this field, has been revised with corresponding

modifications and additions.

Since, in particular, phthalate esters cannot be detected by conventional X-ray fluorescence screening, it is now an urgent necessity to

establish screening methods for restricted organic substances and accurate analysis methods for phthalate esters. Later, it will be necessary to

pay attention to trends in the creation of test methods, and to conduct fact-finding surveys with respect to procurement items.

Regulated Substances and Maximum Allowable Concentration Levels (Threshold Values) ELV RoHS Remarks

Cadmium (Cd) 100 ppm 100ppm

Lead (Pb) 1000 ppm 1000ppm

Mercury (Hg) 1000 ppm 1000ppm

Hexavalent chromium (Cr6+) 1000 ppm 1000ppm

Polybrominated Biphenyls (PBB) Exempt 1000ppm

Polybrominated Diphenyl Ethers (PBDE) Exempt 1000ppm

DIBP, BBP, DBP, and DEHP Exempt 1000 ppm

<RoHS recast, 2011/65/EU>

• The periodic revision of restricted substances by the European Commission was stipulated.

• Restricted substances are now described in the Annex, so that additional substances can be added without revising the directive itself.

• In order to streamline the management of the revised RoHS Directive, the European Commission created a guidance (FAQ), which was published on December 12, 2012 (RoHS 2 FAQ 2012/12/12). The FAQ themselves carry no legislative efficacy, but are given serious consideration as formal documentation from the European Commission.

• The denominator for calculating thresholds for both the ELV and RoHS is Homogeneous Material, the definition of which is specified in the ELV guidance document and the RoHS guidance (FAQ).

• Be aware that both ELV and RoHS include definitions of applicable exemption status.

Key Chemical Substance Regulations in the EU (European Union)

• Council Directive on Batteries and Accumulators Containing Certain Dangerous Substances (91/157/EEC → 2006/66/EC)• Directive on Packaging and Packaging Waste (94/62/EC)• End-of-Life Vehicles Directive (ELV Directive 2000/53/EC)• Waste Electrical and Electronic Equipment Directive (WEEE Directive 2002/96/EC → 2012/19/EU)• Restriction of Hazardous Substances in Electrical and Electronic Equipment Directive (RoHS Directive 2002/95/EC → 2011/65/EU).• Registration, Evaluation, Authorization and Restriction of Chemicals (REACH Controls EC No 1907/2006)• ErP Directive (2009/125/EC)• Energy Labelling Directive (2010/30/EU)

ELV Directive End-of Life Vehicles

In order to prevent the generation of waste from automobiles and to promote the reduction of waste through the reuse or recycling of end-of-life vehicles or their parts, this directive makes sure that automobile materials or parts marketed in member states after July 1, 2003 do not contain lead, mercury, cadmium or Hexavalent chromium.

RoHS Directive Restriction of the Use of Certain Hazardous Substancesin Electrical and Electronic Equipment

The RoHS Directive was officially announced and enacted (RoHS Directive, 2002/95/EC) on February 13, 2003 and implemented from July 2006.It was completely revised and officially announced (RoHS recast, 2011/65/EU) on July 1, 2011.Medical devices and monitoring and control instruments (categories 8 and 9), which were not subject to restriction in the old RoHS Directive (2002/95/EC), became controlled starting in July 2014.

The following categories (category 1 to 11) listed in Annex 1 are subject to the directive

1. Large Household Appliances

2. Small Household Appliances

3. IT and Telecommunications Equipment

4. Consumer Equipment

5. Lighting Equipment

6. Electrical and Electronic Tools

7. Toys, Leisure and Sports Equipment

8. Medical Devices

9. Monitoring and Control Instruments

10. Automatic Dispensers

11. Other EEE not covered by any of the

categories above

Implementation date:

Category 8 (excluding in vitro devices)

Category 9 (excluding industrial instruments)

in vitro diagnostic medical devices (for tests performed outside the human body)

Industrial monitoring and control instruments

Category 11

Addition of phthalate esters

Notification of the World Trade Organization (WTO) by the European Commission

of the proposal for a Commission delegated directive, a revision to Annex II of the RoHS Directive (2011/65/EU).

Official announcement by the European Commission of the Commission delegated directive

(Commission Delegated Directive (EU) 2015/863) regarding the modification of Annex II of the RoHS (II) Directive.

Categories 1 to 7, 11

Category 8 (medical devices including in vitro diagnostic medical devices)

Category 9 (monitoring and control instruments including industrial monitoring and control instruments)

Obligations of manufacturers: In the RoHS recast, manufacturers are obliged to create technical documentation in accordance with Decision 768/2008/EC Annex II Module A. They must also implement internal production control procedures, prepare declarations of conformity, and affix CE marks.EN50581:2012 EU standards were established by CENELEC (European Committee for Electrotechnical Standardization), and officially announced as standards conforming to the RoHS recast (November 23, 2012).

July 22, 2016 onwards



December 17, 2014

June 4, 2015 onwards




Note 1: The content of this article is as of May 2016.

Note 2: For the content of the regulations and their interpretation, be sure to check the officially announced information.

The New Two-stage Screening Method Proposedby ShimadzuPhthalate esters, which are scheduled to be included as additional regulated substances in the next amendment of the RoHS

Directive, are compounds consisting solely of C, H, and O. They cannot be detected by conventional X-ray fluorescence

screenings. It is highly likely that an increasing number of organic substances will be added to the control list. Therefore, a

two-stage screening process is needed for materials and parts containing plastic components.

Plastics included

Plastic materialElectronic parts(with plastics)

Metal materialElectronic parts

(without plastics)

Sample preparation(mechanical pulverization)

Accurate analysis(multiple analysis methods)

X-ray fluorescencescreening

Criteria based on thenature of substances

X-ray fluorescencescreening

Conformingproduct

Nonconformingproduct

Conformingproduct

Nonconformingproduct

Py-GC-MSscreening

SampleHomogeneous material

Metal materialPlastic materialElectronic parts

(boards, components)

Screening

Controlledconcentrations

Accuratemeasurement

Controlledconcentrations

Determination

Yes

Yes

No

No

NoYes

Fail

Pass

Pass

Fail

AA-7000 Series ICPE-9800 Series UV-1900ICPMS-2030 GCMS-QP2020

EDX-7000/8000Py-GC/MS(Py-Screener)

IRSpirit

Lead (Pb)

Mercury (Hg)

Cadmium (Cd)

Chromium (Cr)

PBBs

PBDEs

Phthalate esters(DIBP, DBP, DEHP, BBP)

Substances already regulated under RoHS (II) Directiveand those for which regulation is anticipated

4 5

6 7RoHS/ELV

Energy Dispersive X-ray Fluorescence Spectrometer

EDX-7000/8000

EDX-7000/8000

Hazardous Metals - Cd, Pb, Hg, Cr and Br

Screening Analysis of Hazardous Substancesin RoHS/ELV Directive Using EDX

Features

Optimal for General Analysis in Addition toRoHS/ELV and Various Control Screenings

EDX-7000/8000

Reduces routine maintenance (no liquid nitrogen necessary)

Industry-leading detection sensitivity and resolution

Fast, high-sensitivity measurements of even trace elements

High-precision measurements, even of multi-elementcompounds

For Screening Analysis

Shimadzu EDX Series systems are able to rapidly screen for the six substances, comprised of five elements, environmentally regulated under EU electrical and electronic product waste directives (RoHS), and the four substances, comprised of four elements, environmentally regulated under end-of-life vehicle regulations (ELV). The EDX Series has captured an overwhelming share of the RoHS compliance business in the electrical and electronic equipment industry. The series has built quite a track record and enjoys a great reputation.In order to support compliance with these regulations, Shimadzu has established a worldwide analytical consulting and maintenance capability. In this current business environment, which demands a global business plan that encompasses overseas offices, Shimadzu’s highest goal is to “offer a high operation rate for all regions throughout the world and achieve the same level of performance as offered in Japan”.

EDX Series Screening Applicability Note: The symbols , and do not indicate a comparison of instrument functionality.

BrCl Hg Cr Pb Cd Sb As Ba Se Co Sn S Ni

Textile Goods QualityLabeling Regulations

Element

TargetRegulations

EDX-7000 / 8000

RoHS

ELV

Halogen CPSIA REACH

EN-71 (Toy Safety)

: Supported as an option : Applicable depending on the analysis conditions * Introduction of an additional function kit is required.

A Product Line Designed for Analysis and Inspection Applications

General-purpose model featuring high sensitivity to light elements,supporting fluorine (F) analysis in addition to RoHS/ELV and various control screenings EDX-8000

General-purpose model supporting general analysis in addition to RoHS/ELV and various control screenings EDX-7000

Characteristics and Operating Principle of X-ray Fluorescence Spectroscopy

MCA

MultichannelAnalyzer

X-ray Tube

X-rayFluorescence

SemiconductorDetector

First-OrderX-rays

Sample

Operating Principle of Energy Dispersive X-ray Fluorescence

(EDX) Systems

Samples are irradiated with x-rays and the energy level and intensity of second-order x-rays (x-ray fluorescence) generated from the samples are measured. This allows non-destructive measuring of the constituent elements (qualitative analysis) and their respective concentration levels (quantitative analysis). Furthermore, since no chemical pretreatment is required and multiple elements can be analyzed simultaneously, analysis can be performed rapidly, which is a major benefit of x-ray fluorescence. In addition, systems are compact, require minimal maintenance, and are able to measure samples of any shape by simply placing them in the measurement chamber. Consequently, EDX systems are ideal for acceptance inspection, production screening analysis and defect analysis.

Features of the EDX-7000/8000

Comparison of Profiles for Lead (Pb) in Copper Alloys

EDX-7000/8000Previous model

10.0 11.0 12.0 13.0

The high-performance SDD detector and combination of optimized optics and primary filters achieve previously unheard-of levels of sensitivity.The sensitivity is higher than the previous Si (Li) semiconductor detector across the entire range from light to heavy elements.

The high fluorescent X-ray count per unit time (high count rate) of the SDD detector permits highly precise analysis in a shorter measurement time.This feature is achieved to the maximum when analyzing samples that generate a lot of fluorescent X-rays, such as samples with a metal as the main component element.

Measurement Time Required to Achieve Target Analysis Accuracy

Measurement time

Approx. 1⁄10 measurement timeEDX-7000/8000

Previous model

High Sensitivity - Lower Limit of Detection Improved 1.5 to 5 Times -

High Speed - Throughput Increased by up to 10 Times -

98

Making theDifficult Simple Start sample measurement from [Screening Analysis] using simple steps. The selection of

measurement conditions, which typically relies on the judgment of the experimenter, is determined automatically. This means that even first-time users can effectively use the system.

■

■

■

After placement, the sample observation camera observes the sample and confirms the sample's analysis position.Set the analysis area to 3 mm, 5 mm, or 10 mm diameter.Close the sample chamber.

Place the Sample

■

■

The [Measurement Preparation] window displays the current sample image. Use this window to select analysis conditions and enter a sample name. Start measurement with a single click.

Select Analysis Conditions/Enter Sample Name ■

■

After measurements are completed, [Pass/Fail Judgment], [Concentration], and [3σ(Measurement Variance)] are displayed for all 5 elements in an easy-to-understand layout.Display the [Result List] and [Individual Report] with a single click.

Display of Analysis Results

Screening Software Designed for Easy Operation

Features of Screening Software (PCEDX Navi)

Features of Screening Software

1st step 2nd step 3rd step

A single click in the [Screening Analysis] window automatically performs everything frommeasurement to the display of results, in accordance with pre-registered analysis conditions.

PVC Wire-jacket Material

X-r

ay F

luor

esce

nce

Inte

nsity

X-r

ay F

luor

esce

nce

Inte

nsity

X-r

ay F

luor

esce

nce

Inte

nsity

22 24 10 12 5 6Energy (keV)

Cd

-C

dka

-C

rkb

-C

rka

-Pb

LL

-Pb

Ln

-Pb

La -Pb

Lb1

-Br

ka

-H

gLa

Pb Cr

Energy (keV) Energy (keV)

3σ (ppm)

Cd

OK

Not detected

7.1

Pb

NG

25500

790

Hg

OK

23.4

19

Br

OK

26.1

12

Cr

Grey zone

901

120

To check theresults to date…

Result List: Lists data of completed measurements (with photographs)

If you want tocreate a report…

Individual Report: Displays a report of the current sample

RoHS/ELV

Measurement Example of a Plastic Sample (PVC Wire-jacket Material)Pass, fail, or indeterminate judgment results with respect to the control criteria are easily obtained.

Note: The control criteria in these results are set to the maximum permitted concentrations in the RoHS Directive.

Simpleprocedures

ensure worry-freeoperation, even

for first-timeusers

Even fastermeasurement!

Res

ult

sAll the following are user-determined steps

(If a user cannot determine the main component, selecting the optimal calibration curve is difficult.)

Is this metal? Plastic?

Condition settings

Brass? Al alloy? Solder?

PVC?PE?

Conventionally

Requires no user decisions.Automatically determines main component, selects the optimal calibration curve,

and performs measurement.

Plastic

Metal

Start measurement with a single

click!

Decide analysis conditions

(calibration curve) depending on

main component.

Unknownsample

EDX-7000/8000

Note: The EDX-7000 and 8000 are equipped with PCEDX Navi as standard. To perform RoHS/ELV screenings, however, an optional screening analysis kit must be added.

Create reports in Excel or HTML format.Reports can also be created for non-RoHS 5 element data.*Note that this requires installation of Microsoft Office Excel before use.

Hazardous Metals - Cd, Pb, Hg, Cr and Br For Screening Analysis

Element

Determination Results

Quantitative Value (ppm)

98

Making theDifficult Simple Start sample measurement from [Screening Analysis] using simple steps. The selection of

measurement conditions, which typically relies on the judgment of the experimenter, is determined automatically. This means that even first-time users can effectively use the system.

■

■

■

After placement, the sample observation camera observes the sample and confirms the sample's analysis position.Set the analysis area to 3 mm, 5 mm, or 10 mm diameter.Close the sample chamber.

Place the Sample

■

■

The [Measurement Preparation] window displays the current sample image. Use this window to select analysis conditions and enter a sample name. Start measurement with a single click.

Select Analysis Conditions/Enter Sample Name ■

■

After measurements are completed, [Pass/Fail Judgment], [Concentration], and [3σ(Measurement Variance)] are displayed for all 5 elements in an easy-to-understand layout.Display the [Result List] and [Individual Report] with a single click.

Display of Analysis Results

Screening Software Designed for Easy Operation

Features of Screening Software (PCEDX Navi)

Features of Screening Software

1st step 2nd step 3rd step

A single click in the [Screening Analysis] window automatically performs everything frommeasurement to the display of results, in accordance with pre-registered analysis conditions.

PVC Wire-jacket Material

X-r

ay F

luor

esce

nce

Inte

nsity

X-r

ay F

luor

esce

nce

Inte

nsity

X-r

ay F

luor

esce

nce

Inte

nsity

22 24 10 12 5 6Energy (keV)

Cd

-C

dka

-C

rkb

-C

rka

-Pb

LL

-Pb

Ln

-Pb

La -Pb

Lb1

-Br

ka

-H

gLa

Pb Cr

Energy (keV) Energy (keV)

3σ (ppm)

Cd

OK

Not detected

7.1

Pb

NG

25500

790

Hg

OK

23.4

19

Br

OK

26.1

12

Cr

Grey zone

901

120

To check theresults to date…

Result List: Lists data of completed measurements (with photographs)

If you want tocreate a report…

Individual Report: Displays a report of the current sample

RoHS/ELV

Measurement Example of a Plastic Sample (PVC Wire-jacket Material)Pass, fail, or indeterminate judgment results with respect to the control criteria are easily obtained.

Note: The control criteria in these results are set to the maximum permitted concentrations in the RoHS Directive.

Simpleprocedures

ensure worry-freeoperation, even

for first-timeusers

Even fastermeasurement!

Res

ult

s

All the following are user-determined steps (If a user cannot determine the main component, selecting the optimal calibration curve is difficult.)

Is this metal? Plastic?

Condition settings

Brass? Al alloy? Solder?

PVC?PE?

Conventionally

Requires no user decisions.Automatically determines main component, selects the optimal calibration curve,

and performs measurement.

Plastic

Metal

Start measurement with a single

click!

Decide analysis conditions

(calibration curve) depending on

main component.

Unknownsample

EDX-7000/8000

Note: The EDX-7000 and 8000 are equipped with PCEDX Navi as standard. To perform RoHS/ELV screenings, however, an optional screening analysis kit must be added.

Create reports in Excel or HTML format.Reports can also be created for non-RoHS 5 element data.*Note that this requires installation of Microsoft Office Excel before use.

Hazardous Metals - Cd, Pb, Hg, Cr and Br For Screening Analysis

Element

Determination Results

Quantitative Value (ppm)

RoHS/ELV10 11

Liquid samples are suctioned up by a nebulizer, sprayed into a burner, heated and atomized. Then the sample is irradiated by light from a hollow cathode lamp. Light wavelengths that are characteristic for the element being measured are absorbed by those atoms. This absorption is measured and used for the quantitative analysis of the element.

What is Atomic Absorption Spectrophotometry?

High-temperature plasma is generated by ionizing argon gas using a high frequency. Liquid samples are suctioned up by a nebulizer, vaporized and injected into the plasma, which excites the atoms within the sample. ICP Atomic Emission spectrometry measures the characteristic light emitted from the excited atoms, whereas ICP mass spectrometry puts the ionized atoms in a vacuum and analyzes their masses.

What is ICP Atomic Emission Spectrometry and ICP Mass Spectrometry?

Comparison of ICP and AA Methods

Hazardous Metals – Cd, Pb and Hg For Precise Quantitative Analysis

Leave the Precision Analysis of Metals to AA and ICP

Atomic Absorption Spectrophotometer

AA-7000Simultaneous ICP Atomic Emission Spectrometers

ICPE-9800 SeriesICP Mass Spectrometer

ICPMS-2030

FlameAtomizationMethod

Features of Atomic Absorption Spectrophotometers

Drain

Nebulizer

SampleSolution

Flame

422.7 nmLight

AcetyleneAtomizerChamber

BurnerHead

■ High Sensitivity (ppb)

■ Convenient to Use

■ Low Price

■ Compact Size

Major Pretreatment Methods

ExcellentExcellent

Spectral InterferenceChemical Interference Physical Interference

ExcellentGoodGood

ExcellentFair

Good

FairExcellent

Fair

Good Excellent

Fair

FairGood

GoodGood

GoodGood

Analysis SpeedSimultaneous Analysis of Multiple Analytes

Good Not Possible

FairNot Possible

ExcellentPossible

ExcellentPossible

OperabilityMaintenance

Precision Excellent

Flame AAS Furnace AAS ICP-OES ICP-MS

Fair Excellent Excellent

SensitivityDynamic Range

ppb to ppm2 digits

ppt to ppb 2 digits

ppb to %5 digits

ppt to ppm9 digits

Dissolve the sample in purified water, weak acid or organic solvent.Examples: Uniform samples, such as plating solutions, food products (dairy products, etc.), drugs, or biological samples (blood, urine, etc.)

Heat the sample at a high temperature (400 – 500°C). Decomposition requires a short time (several hours) and operations are simple.Appropriate for decomposition of organic matter. Elements with low boiling points, such as Hg, As, Se, Te or Sb, risk being volatilized.

Note: It is important to select the optimal analysis method for the testing objectives, or use a combination of methods.

Heat samples and acid at a low temperature (up to 300°C). Requires a long time for decomposing organic matter (several hours to several days).Cautions must be observed in case of contamination from the working environment, such as containers or atmosphere, or from the acid.

Heat samples and acid in a closed Teflon™ container at about 100–190°C and decompose under high pressure. Decomposition in a closed system means volatilization of elements with low boiling points is low. Provides a fast decomposition operating environment. Contamination from reagents is low. Acid usage is low.Examples: Sediment, soil, dust, ceramics, biological samples, food products, etc.

Fuse samples and alkaline flux are fused by heating at a high temperature (1000°C). Applicable for hard-soluble samples such as metal compounds and ceramics. Cautions must be observed in case of interference and contamination as samples become highly saline.

Items Applicable for ICP or AA Analysis ■ Metals (ferrous and non-ferrous) ■ Chemicals, drugs, petroleum, polymers, ceramics ■ Biological samples, pharmaceuticals, foods■ Environmental samples (drinking water system, environmental waters, effluents, soil, atmospheric dust)■ Other – metal content can be analyzed in a variety of samplesNote: Solid samples require pretreatment (dissolved into solution).

■ Dilution ■ Dry Digestion ■ Wet Digestion (Standard method of sample treatment)

■ High Pressure Digestion and Microwave High Pressure Digestion ■ Alkali Fusion

Features of ICP Atomic Emission Spectrometry■ High Sensitivity (ppb) ■ Wide Dynamic Range (ppb to %)■ Allows qualitative analysis and simultaneous multiple-element

quantitation■ Solutions analysis makes it easy to prepare the sample for a

calibration curve

Features of ICP Mass Spectrometry■ Ultra High Sensitivity (ppt) ■ Wide Dynamic Range (ppt to ppm)■ Allows qualitative analysis and simultaneous multiple-element

quantitation■ Solutions analysis makes it easy to prepare the sample for a

calibration curve■ Allows measurement of isotope ratio

Element

Cd

Pb

Cr

Hg

As

Pretreatment Dry Ash Kjerdahl Certified Dry Ash Kjerdahl Certified

141 140 140.8 21.0 21.4 21.7

105 <1 107.6 13.1 <1 13.8

105 112 114.6 16.2 17.2 17.7

<0.5 24.0 25.3 <0.5 4.3 4.5

27.7 31.0 30.9 3.6 4.1 3.93

ERM-EC680Sample ERM-EC681

Method EN1122A Method EN1122A

Lower Detection Limits in Plastics (µg/g) Quantitation Example of Polyethylene (µg/g)

ICP-AES

Furnace AAS

ICP-MS

Reasons forlow values

—Hg is volatilized during dry ashing

—Pb precipitates as lead sulfide during Kjerdahl method

Note: Reduction vaporization method

Cd

0.1

0.05

0.0003

Pb

1

0.1

0.0001

Cr

0.2

0.1

0.001

Hg

0.5

0.001*

0.001

As

1

0.1

0.001

Ions are separated by mass

ICP-MS

Sample

3rd stage (up to 0.0001 Pa) 2nd stage (up to 0.1 Pa) 1st stage (up to 100 Pa)

Cyclone chamber cooled by a peltier element

Differential vacuum system

Turbomolecular pump (Splitflow)

Rotary pump Peristaltic pump

Collision gas(He)

Plasma Mini torch

Quadrupole mass filterDetector

Off-axis lens Converging lens

Skimmer cone

High-frequencypower supply

Nebulizer

Collision cell

Sampling nozzleMass Spectrum

Air

RoHS/ELV12 13

Hazardous Substances - Brominated Flame Retardants For Precise Quantitative Analysis

Analysis of Brominated Flame Retardants using GCMS

Gas Chromatograph Mass Spectrometer

GCMS-QP2020The GCMS-QP2020 can be used to accurately quantify polybrominated biphenyls (PBB) and polybrominated diphenyl ether (PBDE), both of which are regulated under the RoHS Directive. It can also accurately quantify four substances to be added as restricted substances i.e., Bis(2-ethylhexyl)phthalate (DEHP), Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), and Diisobutyl Phthalate (DIBP).To accommodate these controls, Shimadzu has prepared a structure to provide after-sales support internationally, at the same level as in Japan, in addition to providing analytical instruments.

GCMS-QP2020

Features

■ GC-MS System Featuring Highly Stable MS Calibration Scale Which is Vital for Measurement of Brominated Flame RetardantsThere are two bromine isotopes, 79Br and 81Br. With decaBB and decaBDE, the molecular ion isotope peaks (12C12

81Br10 and 12C1281Br10O)

have m/z ratios of at most 954 and 970 respectively. Accordingly, the GC-MS system used for their measurements must be able to measure up to a high m/z, and be capable of correctly and stably adjusting the calibration scale even in the high mass region. Equipped with a high-performance metal quadrupole with pre-rod, the GCMS-QP2020 provides a maximum measurable m/z of 1090, and is capable of adjusting the calibration scale in the high mass region at m/z 1066. Accordingly, the system is more than capable of measuring brominated flame retardants. In addition, it can maintain a stable MS calibration scale without temperature control of the quadrupole.

■ Capable of Measuring Brominated Flame Retardants and Phthalate Esters Without Column Replacement

When the optional Twin Line MS system is used, two column outlets can be inserted directly into the mass spectrometer (MS) interface. In addition, the large-capacity differential vacuum pump provides a sensitivity equivalent to that when a single column is used.Therefore, columns suitable for brominated flame retardants and phthalate esters, respectively, can be simultaneously installed in the MS, and both substances can be analyzed without compromising the MS vacuum. Furthermore, since the Twin Line MS system does not use a flow restrictor that can cause adsorption and degradation, it can achieve column switching suitable for analysis of brominated flame retardants that have a high boiling point and are prone to adsorption.

■ Global After-Sales Support Structure

In order to accommodate these controls, Shimadzu has prepared a structure to provide after-sales support internationally, at the same level as in Japan. For Japanese businesses engaged in global business development, Shimadzu provides after-sales support at the same level as in Japan.

System Configuration

• GCMS-QP2020, GCMSsolution workstation• Twin Line MS System• NIST or Wiley mass spectral library• AOC-20i+s• Inserts and columns (for brominated flame retardants and phthalate esters)

Principles of Gas Chromatograph Mass Spectrometers

A gas chromatograph mass spectrometer (GC-MS) is a combined analytical system in which compounds separated by the GC are ionized by the MS, after which these ions are separated by their mass-to-charge ratios (m/z).

He Gas

Gas Inlet(Vaporizing Chamber)

Column(Length: 30m)

SeparationDetection


Chromatography (Separation) Mass Spectrometry

GC UnitA sample is heated and vaporized at the GC inlet, and is then injected to the GC column using helium gas. The inner walls of the column contain a liquid phase. As the injected components move within the column together with the helium gas, they are repeatedly subject to dissolution into the liquid phase and transition into the gas phase (helium gas). The time they are retained in the liquid phase differs depending on the component, so the time before they exit the column (the retention time) also differs for each component, leading to their separation.

MS UnitThe components separated by the column are loaded into the MS. In the MS, accelerated electrons from a filament within the ion source strip electrons from the molecules of the compound exiting from the column. As a result, the molecules lose one electron, and become ions with a positive charge. At the same time, they are subject to cleavage, generating fragments (fragment ions) with a positive charge (electron ionization). Ions generated in this way are fed into a quadrupole (QP) to which a high-frequency voltage is applied. The ions are then separated and detected according to their m/z ratios by scanning the applied high-frequency voltage.In actual measurements, the m/z ratios of ions characteristic of the targets components are monitored in order to perform a quantitative analysis utilizing the mass chromatogram obtained.

Pretreatment Procedures for Brominated Flame Retardants (IEC62321)

After extraction, dilute the solution to 100 mL.

Pulverize the polymer.

Weigh out 100 mg of the pulverized polymer.

Perform pre-extraction to clean the Soxhlet extraction apparatus (70 mL of toluene for 2 hours).

Add an internal standard.

Perform measurement by GC-MS.

After adding the surrogate, perform Soxhlet extraction (60 mL for at least 2 hours).

(Polymer to dissolve (PS-HI or HIPS))

Add 9.0 mL of a solvent that cannot dissolve polymers but can dissolve PBDE and PBB.

Pulverize the polymer, and weigh out 100 mg.

Add 200 µL of a surrogate, then dissolve it using ultrasonic waves (30 minutes).

Add 9.8 mL of a solvent capable ofdissolving the polymer.

Filter the polymer precipitate.



Fractionate 1.0 mL of the solution.

RoHS/ELV12 13

Hazardous Substances - Brominated Flame Retardants For Precise Quantitative Analysis

Analysis of Brominated Flame Retardants using GCMS


GCMS-QP2020The GCMS-QP2020 can be used to accurately quantify polybrominated biphenyls (PBB) and polybrominated diphenyl ether (PBDE), both of which are regulated under the RoHS Directive. It can also accurately quantify four substances to be added as restricted substances i.e., Bis(2-ethylhexyl)phthalate (DEHP), Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), and Diisobutyl Phthalate (DIBP).To accommodate these controls, Shimadzu has prepared a structure to provide after-sales support internationally, at the same level as in Japan, in addition to providing analytical instruments.

GCMS-QP2020

Features

■ GC-MS System Featuring Highly Stable MS Calibration Scale Which is Vital for Measurement of Brominated Flame RetardantsThere are two bromine isotopes, 79Br and 81Br. With decaBB and decaBDE, the molecular ion isotope peaks (12C12

81Br10 and 12C1281Br10O)

have m/z ratios of at most 954 and 970 respectively. Accordingly, the GC-MS system used for their measurements must be able to measure up to a high m/z, and be capable of correctly and stably adjusting the calibration scale even in the high mass region. Equipped with a high-performance metal quadrupole with pre-rod, the GCMS-QP2020 provides a maximum measurable m/z of 1090, and is capable of adjusting the calibration scale in the high mass region at m/z 1066. Accordingly, the system is more than capable of measuring brominated flame retardants. In addition, it can maintain a stable MS calibration scale without temperature control of the quadrupole.

■ Capable of Measuring Brominated Flame Retardants and Phthalate Esters Without Column Replacement

When the optional Twin Line MS system is used, two column outlets can be inserted directly into the mass spectrometer (MS) interface. In addition, the large-capacity differential vacuum pump provides a sensitivity equivalent to that when a single column is used.Therefore, columns suitable for brominated flame retardants and phthalate esters, respectively, can be simultaneously installed in the MS, and both substances can be analyzed without compromising the MS vacuum. Furthermore, since the Twin Line MS system does not use a flow restrictor that can cause adsorption and degradation, it can achieve column switching suitable for analysis of brominated flame retardants that have a high boiling point and are prone to adsorption.

■ Global After-Sales Support Structure

In order to accommodate these controls, Shimadzu has prepared a structure to provide after-sales support internationally, at the same level as in Japan. For Japanese businesses engaged in global business development, Shimadzu provides after-sales support at the same level as in Japan.

System Configuration

• GCMS-QP2020, GCMSsolution workstation• Twin Line MS System• NIST or Wiley mass spectral library• AOC-20i+s• Inserts and columns (for brominated flame retardants and phthalate esters)

Principles of Gas Chromatograph Mass Spectrometers

A gas chromatograph mass spectrometer (GC-MS) is a combined analytical system in which compounds separated by the GC are ionized by the MS, after which these ions are separated by their mass-to-charge ratios (m/z).

He Gas

Gas Inlet(Vaporizing Chamber)

Column(Length: 30m)

SeparationDetection


Chromatography (Separation) Mass Spectrometry

GC UnitA sample is heated and vaporized at the GC inlet, and is then injected to the GC column using helium gas. The inner walls of the column contain a liquid phase. As the injected components move within the column together with the helium gas, they are repeatedly subject to dissolution into the liquid phase and transition into the gas phase (helium gas). The time they are retained in the liquid phase differs depending on the component, so the time before they exit the column (the retention time) also differs for each component, leading to their separation.

MS UnitThe components separated by the column are loaded into the MS. In the MS, accelerated electrons from a filament within the ion source strip electrons from the molecules of the compound exiting from the column. As a result, the molecules lose one electron, and become ions with a positive charge. At the same time, they are subject to cleavage, generating fragments (fragment ions) with a positive charge (electron ionization). Ions generated in this way are fed into a quadrupole (QP) to which a high-frequency voltage is applied. The ions are then separated and detected according to their m/z ratios by scanning the applied high-frequency voltage.In actual measurements, the m/z ratios of ions characteristic of the targets components are monitored in order to perform a quantitative analysis utilizing the mass chromatogram obtained.

Pretreatment Procedures for Brominated Flame Retardants (IEC62321)

Soxhlet Extraction-GC-MS Method

After extraction, dilute the solution to 100 mL.

Pulverize the polymer.

Weigh out 100 mg of the pulverized polymer.

Perform pre-extraction to clean the Soxhlet extraction apparatus (70 mL of toluene for 2 hours).



After adding the surrogate, perform Soxhlet extraction (60 mL for at least 2 hours).

Solvent Dissolution Method(Polymer to dissolve (PS-HI or HIPS))

Add 9.0 mL of a solvent that cannot dissolve polymers but can dissolve PBDE and PBB.

Pulverize the polymer, and weigh out 100 mg.

Add 200 µL of a surrogate, then dissolve it using ultrasonic waves (30 minutes).

Add 9.8 mL of a solvent capable ofdissolving the polymer.

Filter the polymer precipitate.



Fractionate 1.0 mL of the solution.

RoHS/ELV14 15

Hazardous Substances - Phthalate Esters For Screening Analysis

Analysis of Phthalate Esters and Brominated FlameRetardants Using Py-GC-MS

Screening System for Phthalate Esters

Py-Screener

Making the Difficult Simple

The Py-Screener system is designed to screen for phthalate esters in polymers.The use of phthalate esters in toys and food packaging is currently restricted. Moving forward, they are expected to be regulated as restricted substances under the RoHS (II) Directive.The Py-Screener system consists of special software, special standard samples, and a sampling toolkit, which supports the entire process from sample preparation to data acquisition, data analysis, and maintenance. It provides an environment in which operations are simple, even for novices.

Features

■ Organics Solvents Are Not Required for Sample Preparation

Analytical standards and test samples can be prepared without using organic solvents. To prepare a sample, just use the cutter to remove a portion from the test material, place it in the sample cup, and weigh it. Sample preparation videos provide support so that even novices can easily prepare samples.

Preparation of a Phthalate Ester Standard Preparation of a Test Sample

Sample Preparation Videos

Sample preparation videos: http://www.shimadzu.com/an/gcms/py-screener.html

■ Easy to Operate Using Special Software

The special software leads you through the required procedures, so even novices can perform the operations in accordance with the software instructions. The Py and GC-MS analysis conditions are preset. To automatically start continuous analyses, just place the prepared standard samples and test samples in the autosampler, and enter the number of samples, the sample names, and their weights. Continuous measurements can be performed overnight, so approximately 30 samples can be measured per day.

Special Py-Screener Software

Measurement Schedule Window

■ Tabular Display of Concentrations and Criteria Clarifies the Results

With LabSolutions Insight multi-analyte quantitative analysis software, the concentrations of target components detected by the continuous measurements are displayed in a table, and are subject to pass/fail determinations based on concentration ranges. The results for the continuously measured test samples can be confirmed at a glance. In addition, the system is equipped with accuracy control functions to ensure the reliability of blank concentrations, instrument sensitivity and other data. As a result, even novices can feel confident that they are reporting highly reliable measurement results.

Everything Required Is Prepared

The standard samples for this system were developed in cooperation with SGS Japan, the market leader in RoHS tests. Samples for sensitivity confirmation, quantitation, and blank tests can be prepared simply by punching out a portion of a standard sample using the micro puncher. A kit of the tools used for sample preparation has been created in cooperation with Frontier Laboratories Ltd.

Standard Samples Contained PhthalateEsters Used for Py-GC/MS

Sampling Tool Kit

Excellent Maintenance Support

The maintenance navigator enables simple, confident maintenance of the pyrolyzer and GC-MS. In addition, the checks performed when a leak has occurred are also guided by the software, so the source of the problem can be pinpointed easily.Furthermore, thanks to the periodic replacement parts kit, which provides parts prone to contamination with extended use, the system can be operated with confidence, even for extended periods.

Maintenance Navigator Window

Basic Principles of Pyrolyzers

In a pyrolyzer, polymer samples are dropped into a pyrolysis furnace maintained at a high temperature. The polymer undergoes pyrolysis, and the products generated are then loaded into the GC-MS. If the temperature of the furnace is set lower than the polymer's pyrolysis temperature, the PBB, PBDE, and phthalate esters in the polymer can be subjected to thermal extraction without decomposing the polymer.(Thermal desorption method)

Resin Sample

Sample Cup Carrier Gas

Pyrolysis

Thermal Extraction

MS GC

Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment / End-of Life Vehicles

RoHS / ELVComplying with European Chemical Substance Regulations

RoHS / ELV

Com

plying with European C

hemical Substance Regulations

Shimadzu Overseas Customer SupportTo support customers engaged in analyses of hazardous substances governed by the RoHS and ELV directives, Shimadzu has established a global service network incorporating customer support, training and service centers in the USA, Germany, China and Singapore, as well as in Japan. Shimadzu provides comprehensive support services including instrument maintenance, training workshops and the provision of relevant information to meet customer needs regarding both software and hardware.

GLOBAL NETWORK

SHIMADZU EUROPA GmbH

SHIMADZU (CHINA) CO., LTDSHANGHAI BRANCH

SHIMADZU (ASIA PACIFIC) PTE LTD.

SHIMADZU SCIENTIFIC INSTRUMENTS, INC.

© Shimadzu Corporation, 2017

www.shimadzu.com/an/

For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country.Company names, products/service names and logos used in this publication are trademarks and trade names of Shimadzu Corporation, its subsidiaries or its affiliates, whether or not they are used with trademark symbol “TM” or “®”.Third-party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not they are used with trademark symbol “TM” or “®”.Shimadzu disclaims any proprietary interest in trademarks and trade names other than its own.

The contents of this publication are provided to you “as is” without warranty of any kind, and are subject to change without notice. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication.

First Edition: May 2017, Printed in Japan 3655-05720-10ANS

complying with european chemical substance regulations · july 22, 2016 onwards july 22, 2017...

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