Practical RoHS Compliance Screening with Micro-XRF

Transcription

1 Practical RoHS Compliance Screening with Micro-XRF Bruker Nano Analytics, Berlin, Germany Webinar, August 22, 2018 Innovation with Integrity

2 Presenters / Moderators Esa Nummi Director Product Management Bruker Nano Analytics, Berlin, Germany Robert Erler Product Manager Micro-XRF Bruker Nano Analytics, Berlin, Germany Falk Reinhardt Application Scientist Micro XRF Bruker Nano Analytics, Berlin, Germany

3 XRF RoHS Compliance Screening Webinar Outline RoHS regulatory update XRF Technology RoHS Compliance Program XRF Screening and Sample Preparation Practical RoHS Screening Live Measurements Questions and Answers

4 RoHS Regulatory Update

5 What is RoHS? EU Directive for EEE 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

6 RoHS restricted substances 2018 Maximum concentration limits Substance Symbol Max concentration Lead 0.1% / 1000 ppm Mercury 0.1% / 1000 ppm Cadmium 0.01% / 100 ppm Hexavalent chromium (Cr) PBB (Br) polybrominated biphenyl PBDE (Br) polybrominated diphenyl ether 0.1% / 1000 ppm 0.1% / 1000 ppm 0.1% / 1000 ppm

7 Product Categories Covered by RoHS RoHS 1, RoHS 2 & 3 Cat Description Examples Status Large household appliances Small household appliances Computing & communication equip. Washing machine, refrigerator, Coffee-maker, micro-wave 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 RoHS 1 Since Automatic dispensers Vending machine, ATM 8 9 Medical devices & equipment Control & monitoring equipment Radiotherapy equipment, cardiology, dialysis Digital voltmeter, smoke detector, X-ray imager RoHS 2 Added in

8 RoHS 2 & RoHS 3 Timeline Medical and Industrial Equipment RoHS Categories 1-7, 10 July 2016 In vitro diagnostic medical devices July 2019 All EEE, except excluded. RoHS 3: Phthalates added to restricted substances list July 2014 Non-industrial control and monitoring instruments and most medical devices July 2017 Industrial monitoring and control instruments July 2021 Phthalates added to Cat 8 medical devices and Cat 9 industrial and control instruments RoHS I RoHS II Medical devices were exempt in the original directive The RoHS 2 directive mandates compliance by July 2016 RoHS III

9 Upcoming 2019 RoHS 3 extension Phthalate Restrictions 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. DEHP 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

10 RoHS Scope Exclusions and Exemptions 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, 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

11 X-ray Fluorescence (XRF) Technology

12 XRF RoHS Screening Capabilities 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) PBB and PBDE (Br) Phthalates 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. 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. XRF is not able to identify phthalates, phthalates primarily exist in soft plastics. Yes Yes No No No No

13 Examples of different Bruker XRF Instruments for Regulatory Compliance Screening Micro-spot XRF Typical max. sample size 30 cm Typical spot size 20 um to 1.5 mm Programmable XYZ stage and mapping Micro-spot: M1 MISTRAL & M4 TORNADO 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 Laboratory: S2 PUMA & S8 TIGER Portable XRF Unlimited sample size Typical spot size 3 8 mm Field portable and battery operated Portable: S1 TITAN & CTX

14 M1 MISTRAL Micro-spot XRF Key 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

15 M1 MISTRAL Limit of Detection (LOD) Element RoHS limit Plastic M1 Mistral LOD Sn solder Pb 1000 ppm 5 20 Hg 1000 ppm 5 30 Cd 100 ppm Cr * 1000 ppm Br ** 1000 ppm 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

16 RoHS Testing Program

17 RoHS Testing Program Typical Goals 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

18 RoHS Testing Program XRF 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 for reference

19 Risk assessment Probability of the presence of substances 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 Examples Restricted substances Component PBB/ Hg Cd Pb Cr 6 PBDE Plastics L M M L M Fasteners L M M H NA Glass L M H L NA LCD panel H L H H L Lamps H L H M NA Connector M L H L H Solder L M H L NA External cables L H H L L Rubber L M M L M H: High probability - Historically used, there are no common alternatives or alternatives are not always used M: Medium probability - Historical use, but alternative substances are currently used. L: Low probability - No known historical use NA: Not applicable

20 RoHS Testing Program Testing Process Example XRF screening Lab verification Review Documentation Audit Processes Test and Verification - BOMs - Drawings - Test reports - Mat. declarations - Validate mfg. process - Identify high risk parts - Screen with XRF Test high risk materials that can not be verified using XRF Product Certification - Certifications

21 XRF Screening and Sample Preparation

22 XRF RoHS Screening Elemental mapping with M4 Tornado Bruker M4 Application Example: Examination of Electronic Components Optical image Element distribution map of RoHS elements Examination of RoHS compliance of a digital watch PCB Measurement: scan resolution 400x440 pixels, step size 80 µm, 1 h total

23 Generally accepted RoHS Screening Method IEC Standards IEC International Electrotechnical Commission IEC series of RoHS measurement standards Multiple standards covering XRF and other methods and sample preparation Standards can be downloaded from the IEC webstore Key IEC standards concerning RoHS screening Document IEC RoHS overview IEC RoHS XRF screening IEC RoHS Sample preparation Description IEC :2013 Determination of certain substances in electrotechnical products - Part 1: Introduction and overview IEC :2013: Determination of certain substances in electrotechnical products - Part 3-1: Screening - Lead, mercury, cadmium, total chromium and total bromine using XRF spectrometry IEC :2013: Determination of certain substances in electrotechnical products - Part 2: Disassembly, disjunction and mechanical sample preparation

24 XRF RoHS Screening Sampling Examples 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

25 XRF RoHS Screening Recommended Test Process EDXRF Screening 130 ppm Cd or 1300 ppm Pb, Cr, Hg, Br yes RoHS non-compliant yes no Samples Homogeneous Materials Screening? 70 ppm Cd or 700 ppm Pb, Cr, Hg, Br yes RoHS compliant no Pb: Cd: ICP-AES ICP-AES RoHS non-compliant no Verification Tests Cr 6+ : UV-VIS, wet chemistry PBB: IR; MS, HPLC/GC PBDE: IR; MS, HPLC/GC 100 ppm Cd or 1000 ppm Pb, Cr, Hg, Br Hg: ICP-AES; AAS Phthalates: IR; MS, HPLC/GC yes RoHS compliant

26 XRF RoHS Screening Recommended Pass/Fail Limits 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 Recommended pass/fail limits Polymers Metals Composite El 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

27 Sampling Strategy Disassembly and Mechanical Sample Preparation 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 strategy YES Product or part Decide sampling strategy Measurement possible as it is NO Sampling / disassembly XRF / Other Measurements Satisfactory results YES NO

28 XRF Screening Limits Cd in Plastic Example Test part Connector housing, polymer Test result Meas. Cd, ppm Average 154 3σ 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

29 XRF Screening Limits Br in Plastics Example Test part Connector housing, polymer Test result Meas. Br, ppm Average 523 3σ 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

30 XRF Screening Example Thick film resistor Screening process Solder 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 End termination coating Glaze exempt (lead in glass) Inner electrode Resistive layer Laser Cut Marking Resistive layer below glaze exempt (lead in ceramic) Primary glass Protective coating Ceramic End termination Solder

31 XRF RoHS Screening Example - Sample preparation It is possible to analyze composite material containing multiple material by homogenizing it Makes confirmation of RoHS compliance more challenging Question What is the maximum Pb result that would confirm RoHS compliance for composite sample containing three materials (A,B,C)? A 15% Pb 0.2% B 50% Pb 10 ppm C 35% Pb 400 ppm Sample information XRF screen pass limit 500 ppm - 3 sigma for composite material (~470 ppm) Weight fraction of the smallest material: 15% Weighted Average: 445 ppm Answer Maximum allowed Pb concentration = Wight fraction of the smallest component * compliance limit 0.15 * 470 ppm = 70 ppm

32 RoHS 2 and XRF Measurement Methods More Information Document Description Link RoHS 2 directive IEC RoHS standard overview IEC standard XRF method IEC standard Sample preparation ASTM XRF standard RoHS 2 Directive: Restriction of Hazardous Substances in Electrical and Electronic Equipment IEC :2013 Determination of certain substances in electrotechnical products - Part 1: Introduction and overview IEC :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 IEC :2013: Determination of certain substances in electrotechnical products - Part 2: Disassembly, disjunction and mechanical sample preparation ASTM F : Standard Test Method for Identification and Quantification of Chromium, Bromine, Cadmium, Mercury, and Lead in Polymeric Material Using Energy Dispersive X-ray Spectrometry ELEX:32011L ublication/ ublication/ ublication/ andards/f2617.htm

33 Measurement Examples

34 RoHS Screening Live Measurements PC Mouse According IEC standard - sample preparation IEC :2013 Determination of certain substances in electrotechnical products - Part 2: Disassembly, disjunction and mechanical sample preparation

35 X-Ray Fluorescence of Restricted Elements Questions and Answers Questions, Thoughts, or Comments? To contact us during the Webinar please type your questions, thoughts, or comments in the Q&A box and press Submit. Please accept our sincere apologies if we can t discuss all comments and questions within the session! We will of course answer and discuss those later on by or in another Webex meeting.

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