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Practical RoHS Compliance Screening with Micro-XRF
Innovation with Integrity
Bruker Nano Analytics, Berlin, GermanyWebinar, August 22, 2018
Falk Reinhardt
Application Scientist Micro XRFBruker Nano Analytics, Berlin, Germany
Presenters / Moderators
Robert Erler
Product Manager Micro-XRFBruker Nano Analytics, Berlin, Germany
Esa Nummi
Director Product ManagementBruker Nano Analytics, Berlin, Germany
• RoHS regulatory update
• XRF Technology
• RoHS Compliance Program
• XRF Screening and Sample Preparation
• Practical RoHS Screening – Live Measurements
• Questions and Answers
XRF RoHS Compliance ScreeningWebinar Outline
RoHS Regulatory Update
RoHS stands for “Restriction of Hazardous Substances”• EU directive (# 2002/95/EC), came into effect in July 2006
• Concerns electrical and electronic equipment (EEE)
• RoHS 2 extension (2011/65/EU)
• RoHS 3 extension (2015/863/EU)
Some Other regulations
• China, Japan, Korea RoHS regulations• ELV: End of Life Vehicles• EN71: European Toy safety standards• EU Packaging directive• Halogen Free• CPSIA California prop 65
What is RoHS?EU Directive for EEE
Substance Symbol Max concentration
Lead 0.1% / 1000 ppm
Mercury 0.1% / 1000 ppm
Cadmium 0.01% / 100 ppm
Hexavalent chromium (Cr) 0.1% / 1000 ppm
PBB (Br)polybrominated biphenyl 0.1% / 1000 ppm
PBDE (Br)polybrominated diphenyl ether 0.1% / 1000 ppm
RoHS restricted substances 2018Maximum concentration limits
Cat Description Examples Status
1 Large householdappliances Washing machine, refrigerator,
RoHS 1Since 2006
2 Small householdappliances Coffee-maker, micro-wave
3 Computing & communication equip. Computer, phone, printer
4 Consumer electronics TV, phone
5 Lighting products Lamp, bulb, fixture
6 Power tools Drill, blowers, saw
7 Toys & sports equipment Drone, game console, treadmills
10 Automatic dispensers Vending machine, ATM
8 Medical devices & equipment
Radiotherapy equipment, cardiology, dialysis
RoHS 2Added
in 2014-2021
9 Control & monitoring equipment
Digital voltmeter, smoke detector, X-ray imager
Product Categories Covered by RoHSRoHS 1, RoHS 2 & 3
RoHS I- 2006 “RoHS II
Medical devices were exempt in the original directive The RoHS 2 directive mandates compliance by July 2016
July 2014Non-industrial control and monitoring instruments
and most medical devices
July 2016In vitro diagnostic medical devices
July 2017Industrial monitoring
and control instruments
July 2019All EEE, except excluded. RoHS 3: Phthalates added to restricted substances list
July 2021Phthalates added to Cat 8 medical devices and Cat 9 industrial and control instruments
RoHS Categories
1-7, 10
RoHS 2 & RoHS 3 TimelineMedical and Industrial Equipment
RoHS III
• Certain phthalates - DEHP, BBP, DBP and DIBP will be restricted from 22 July 2019, 2 year extension for Cat 8 and Cat 9.
• Phthalates are typically used as plasticizers to soften plastics, especially PVC
• The restriction of DEHP, BBP and DBP doesn’t apply to toys which are already subject to the stricter restriction under REACH.
• Phthalates cannot be analyzed with XRF, typically FTIR screening and LC-MS or GC-MS verification analysis is used.
New Restricted Substances limit Possible uses
DEHP: Bis(2-ethylhexyl) phthalate 0.1% Plasticizer, PVC
BBP: Butyl benzyl phthalate 0.1% Plasticizer, vinyl floor
DBP: Dibutyl phthalate 0.1% Plasticizer, adhesive
DIBP: Di-isobutyl phthalate 0.1% Plasticizer, acrylic
DEHP
Upcoming 2019 RoHS 3 extensionPhthalate Restrictions
There are over 80 RoHS exemptions, including
Scope Exclusions - examples
• National security and military equipment
• Trains, aircraft, boats, vehicles
• Photovoltaic panels
• Spare parts for electronic equipment in the market before July, 2006.
Exemptions – examples
• Certain Copper alloys, containing up to 4% Pb
• Certain high temperature solders, containing Pb
• Electronic components containing Pb in a glass or ceramic
• Limited amounts of Hg in fluorescent light bulbs
• Cd in photoresistors
RoHS ScopeExclusions and Exemptions
X-ray Fluorescence (XRF) Technology
• XRF is a versatile and easy to use elemental analysis technique• XRF can analyze most of the restricted elements, but it is not able to
identify specific compounds.
Compound XRF Screening capability Pass Fail
Pb, Hg, Cd Can be measured by XRF at restricted levels Yes Yes
Cr (VI) ED-XRF can’t uniquely identify Cr (VI), although a total Cr concentration can be measured. If total Cr is under limit then also Cr (VI) is.
Yes No
PBB and PBDE (Br)
XRF can’t identify the exact substances, but XRF can measure Br as an indicator that further tests for the specific substances may be required.
Yes No
Phthalates XRF is not able to identify phthalates, phthalates primarily exist in soft plastics. No No
XRF RoHS ScreeningCapabilities
Micro-spot XRF
• Typical max. sample size 30 cm
• Typical spot size 20 um to 1.5 mm
• Programmable XYZ stage and mapping
Laboratory XRF (ED-XRF & WD-XRF)
• Typical max. sample size 5 cm
• Typical spot size 1 to 30 mm
• Auto sampler for fast routine analysis
Portable XRF
• Unlimited sample size
• Typical spot size 3 – 8 mm
• Field portable and battery operated
Portable: S1 TITAN & CTX
Laboratory: S2 PUMA & S8 TIGER
Micro-spot: M1 MISTRAL & M4 TORNADO
Examples of different Bruker XRF Instrumentsfor Regulatory Compliance Screening
M1 MISTRAL Micro-spot XRFKey Features
• Benchtop small spot XRF spectrometer
• Element range from P to U (including Cr, Pb, Cd, Br, As, Ba and many others)
• Collimator changer, spot size from 0.2 mm to 1.5 mm
• Top view video camera (30x)
• Programmable X-Y-Z-stage (range 200x175x80) mm.
• RoHS methods for plastics, alloys, solders, glass, ceramics and organics
• Thickness compensation down to 1 mm
• Method editor for fast method setup and calibration
Element RoHS limitM1 Mistral LOD
Plastic Sn solder
Pb 1000 ppm 5 20
Hg 1000 ppm 5 30
Cd 100 ppm 10 25
Cr* 1000 ppm 10 100
Br** 1000 ppm 5 - - -
LODs for
M1 Mistral, SDD
W tube
50 kV, 800 µA
1.5 mm collimator
300 s
* - energy-dispersive XRF is not capable of distinguishing Cr-III and Cr-VI
** - the organic part of PBB/PBDE with the restricted Br does not occur in solders
Note: Detection limits are given for „infinitely thick“ samples
M1 MISTRALLimit of Detection (LOD)
RoHS Testing Program
• Reasonable assurance that product meet requirements
• Part of the overall compliance program
• Supplement what is known about components and manufacturing
• Ensure supply chain compliance
• Compliant parts and raw materials
• Documentation review
• Test finished products for compliance
Assess Requirements
Test and Verify Certify
RoHS Testing ProgramTypical Goals
RoHS Testing ProgramXRF Screening
• Determine what will be tested• Incoming QC of parts• Inventory control• Process control• Finished products, final QC
• Determine frequency of testing• Scrutinize new suppliers• High risk materials
• Select analytical techniques• Screening: XRF, test kits• Verification: Lab-based
• Testing methodology • Develop SOP• Standard Operating Procedure IEC 62321 for
reference
Risk assessmentProbability of the presence of substances
ComponentRestricted substances
Hg Cd Pb Cr 6 PBB/PBDE
Plastics L M M L MFasteners L M M H NA
Glass L M H L NALCD panel H L H H L
Lamps H L H M NAConnector M L H L H
Solder L M H L NAExternal cables L H H L L
Rubber L M M L M
Examples
Lamp, glass and solder may contain Pb
Plastic connector and insulation may contain lead or cadmium
Lead in solder or termination coating
Plastic housing may contain PBB, PBDE, Cd or Pb
H: High probability - Historically used, there are no common alternatives or alternatives are not always usedM: Medium probability - Historical use, but alternative substances are currently used.L: Low probability - No known historical use NA: Not applicable
Review Documentation
- BOMs- Drawings- Test reports- Mat. declarations- Certifications
AuditProcesses
- Validate mfg. process- Identify high risk parts- Screen with XRF
Test andVerification
Test high risk materials that can not be verified using XRF
Product Certification
XRF screening Lab verification
RoHS Testing ProgramTesting Process Example
XRF Screening and Sample Preparation
Element distribution map of RoHS elements
Bruker M4 Application Example: Examination of Electronic Components
• Examination of RoHS compliance of a digital watch PCB• Measurement: scan resolution 400x440 pixels, step size 80 µm, 1 h total
Optical image
XRF RoHS Screening Elemental mapping with M4 Tornado
• IEC – International Electrotechnical Commission
• IEC 62321 series of RoHS measurement standards
• Multiple standards covering XRF and other methods and sample preparation
• Standards can be downloaded from the IEC webstore https://webstore.iec.ch/searchform&q=IEC%2062321#
Generally accepted RoHS Screening MethodIEC 62321 Standards
Document Description
IEC RoHS overview
IEC 62321-1:2013 Determination of certain substances in electrotechnical products - Part 1: Introduction and overview
IEC RoHS XRF screening
IEC 62321-3-1:2013: Determination of certain substances in electrotechnical products - Part 3-1: Screening - Lead, mercury, cadmium, total chromium and total bromine using XRF spectrometry
IEC RoHS Sample preparation
IEC 62321-2:2013: Determination of certain substances in electrotechnical products - Part 2: Disassembly, disjunction and mechanical sample preparation
Key IEC standards concerning RoHS screening
The RoHS regulations are for each homogeneous material in the product using any technique, i.e. for any single substance that can not be separated mechanically.
Examples:
1. Consumer Electronics• Housing• Mechanics• Wires• PCBs
2. PCB • ICs• Resistors, capacitors• Switches• Wires• Solders• Screws• Paint
XRF RoHS Screening Sampling Examples
Screening ?
≥ 130 ppm Cd or≥ 1300 ppm Pb, Cr, Hg, Br
≤ 70 ppm Cd or≤ 700 ppm Pb, Cr, Hg, Br
VerificationTests
RoHS non-compliant
RoHS non-compliant
RoHS compliant
RoHS compliant
≤ 100 ppm Cd or≤ 1000 ppm Pb, Cr, Hg,
Br
no
yes
yes
yes
no
no
yes
SamplesHomogeneous
Materials
EDXRF Screening
XRF RoHS Screening Recommended Test Process
Pb: ICP-AES
Hg: ICP-AES; AAS
Cr6+: UV-VIS, wet chemistry
PBB: IR; MS, HPLC/GC
PBDE: IR; MS, HPLC/GC
Cd: ICP-AES
Phthalates: IR; MS, HPLC/GC
• It is recommended to use 30%-50% confidence limits for pass-fail criteria
• Below limit/Pass if reading is < Regulatory Limit – 30% - 3*STD
• Over limit/ Fail if reading is > Regulatory Limit + 30% + 3*STD
• Inconclusive if between Pass and Fail Additional testing is required
ElPolymers Metals Composite
Pass Fail Pass Fail Pass Fail
Cd ≤ (70-3σ) >(130+3σ) ≤(70-3σ) >(130+3σ) ≤ (50-3σ) >(150+3σ)
Pb ≤(700-3σ) >(1300+3σ) ≤(700-3σ) >(1300+3σ) ≤(500-3σ) >(1500+3σ)
Hg ≤(700-3σ) >(1300+3σ) ≤(700-3σ) >(1300+3σ) ≤(500-3σ) >(1500+3σ)
Br ≤(300-3σ) Not applicable Not applicable Not applicable ≤(250-3σ) Not applicable
Cr ≤(700-3σ) Not applicable ≤(700-3σ) Not applicable ≤(500-3σ) Not applicable
Recommended pass/fail limits
XRF RoHS ScreeningRecommended Pass/Fail Limits
Sampling strategy
Product or partMeasure-
mentpossible as
it is
Decide sampling strategy
XRF / Other Measurements
Sampling / disassembly
Satisfactory results
NO
YES
NO YES
• The sampling strategy depends on the objective of analysis
• Before sampling, the following questions needs to be addressed:
• Can any sections/parts be identified that are likely to contain restricted substances
• Is it practical to analyze any of these sections/parts without disassembly?
• Can the selected part considered as homogeneous material?
• Does the sample fulfil the criteria of minimum mass, area, thickness or volume required by the chosen analytical methods?
Sampling StrategyDisassembly and Mechanical Sample Preparation
Meas. Cd, ppm1 1572 1533 1504 1525 156
Average 1543σ 9
• Pass ≤(70-3σ) <X <(130+3σ) ≤ Fail
• Below limit/Pass if reading is < 70 ppm – 9 ppm = 61 ppm
• Over limit/ Fail if reading is > 130 ppm + 9 ppm = 139 ppm
• Inconclusive if between 61 ppm and 139 ppm
Measurement result 154 ppm is over Cd limit. Part is not RoHS compliant
Connector housing, polymer
XRF Screening LimitsCd in Plastic Example
Test part Test result
Meas. Br, ppm1 5302 5103 5344 5225 520
Average 5233σ 28
• Pass ≤ (300-3σ) <X
• Below limit/Pass if reading is < 300 ppm – 28 ppm = 272 ppm
• Inconclusive if over 272 ppm
Measurement result 523 ppm is inconclusive. Additional testing/verification is required
Connector housing, polymer
Test part Test result
XRF Screening LimitsBr in Plastics Example
Solder
End termination coating
Glaze – exempt(lead in glass)
Resistive layer below glaze – exempt
(lead in ceramic)
Screening process
1. Screen the whole component
2. Verify if any lead Pb and or cadmium Cd is found
3. If found, determine the exact source
4. Check if the source material is RoHS exempt
Laser Cut Marking
End termination
Inner electrode
Resistive layer
Primary glass CeramicProtective
coating
Solder
XRF Screening Example Thick film resistor
A
15%
B
50%
C
35%
• It is possible to analyze composite material containing multiple material by homogenizing it
• Makes confirmation of RoHS compliance more challenging
Weighted Average: 445 ppm
Question• What is the maximum Pb result that would
confirm RoHS compliance for composite sample containing three materials (A,B,C)?
Sample information• XRF screen pass limit 500 ppm - 3 sigma for
composite material (~470 ppm)• Weight fraction of the smallest material: 15%
Answer• Maximum allowed Pb concentration =
Wight fraction of the smallest component * compliance limit
0.15 * 470 ppm = 70 ppm
A
15%
Pb 0.2%
B
50%
Pb 10 ppm
C
35%
Pb 400 ppm
XRF RoHS ScreeningExample - Sample preparation
Document Description Link
RoHS 2 directive RoHS 2 Directive: Restriction of Hazardous Substances in Electrical and Electronic Equipment
https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX:32011L0065
IEC RoHS standard overview
IEC 62321-1:2013 Determination of certain substances in electrotechnical products - Part 1: Introduction and overview
https://webstore.iec.ch/publication/6828
IEC standard XRF method
IEC 62321-3-1:2013: Determination of certain substances in electrotechnical products - Part 3-1: Screening - Lead, mercury, cadmium, total chromium and total bromine using X-ray fluorescence spectrometry
https://webstore.iec.ch/publication/6830
IEC standard Sample preparation
IEC 62321-2:2013: Determination of certain substances in electrotechnical products - Part 2: Disassembly, disjunction and mechanical sample preparation
https://webstore.iec.ch/publication/6829
ASTM XRF standard
ASTM F2617–15: Standard Test Method for Identification and Quantification of Chromium, Bromine, Cadmium, Mercury, and Lead in Polymeric Material Using Energy Dispersive X-ray Spectrometry
https://www.astm.org/Standards/F2617.htm
RoHS 2 and XRF Measurement MethodsMore Information
Measurement Examples
According IEC standard - sample preparation
IEC 62321-2:2013Determination of certain substances in electrotechnical products - Part 2: Disassembly, disjunction and mechanical sample preparation
RoHS ScreeningLive Measurements – PC Mouse
X-Ray Fluorescence of Restricted ElementsQuestions and Answers
Questions, Thoughts, or Comments?
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comments and questions within the session!
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in another Webex meeting.
More Information
For more information, please contact us:
https://www.bruker.com/products/x-ray-diffraction-and-elemental-
analysis/micro-xrf-and-txrf/m1-mistral/overview.html
Innovation with Integrity
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