利用行動可攜式 EDXRF 篩選符合RoHS 規範

Ken SmithInnov-X Systems, Inc.

Woburn, MA USA

as per IEC-ACEA* Procedures for the Determination of Levels of Regulated Substances in Electrotechnical Products

(Version 2005-06-24)

*: International Electrotechnical Commission – Advisory Committee on Environmental Aspects

歡迎來到手提式 XRF 的世界

每個人 都可檢測

任何物品 隨時隋地

任何地方

可檢測任何物品

實際上的應用

每個人都可以

Portable XRF Technology Solves 21st Century Applications Problems

Verifying Plastics 　檢驗塑膠材質

Searching for WMD’s　廢棄物資源的搜尋

Exposing Pollution　放射性汙染

Analyzing Alloys 　分析合金成分

Securing Borders 　邊界安全應用

Conserving Art Treasures 　保存藝術品及貴重物品

Solving Crimes 　解決汙染源問題

Preserving History 　歷史古物的保存

可攜式 XRF 技術解決 21 世紀於應用上的問題

Basics of XRF 基本原理 An Excitation Source (either radioactive isotope or X-ray tube)

ionizes individual atoms 激發源 ( 放射性同位素或 X-ray 管 ) 使原子解離

As the atoms return to their original state, each type of atom emits specific x-ray energies使電子脫離其原本的軌道，並釋放出第二次光

The detector captures this spectrum of x-ray emissions檢測器會截取其第二次光光譜

Software analyzes this spectral signature軟體會分析其光譜信號

System displays quantitative and or qualitative results系統會顯示量化的結果

• X-Rays from source knock out “inner shell” electrons creating an unstable state在電子軌道上的電子接收 X-Rays 的能量會造成電子不穩定

• Outer shell electrons drop down to fill vacancy in inner shell接收能量的電子會跳脫原本電子軌道，外層的電子則會去填補其空缺。

• Characteristic (signature) x-rays from sample are produced and detected不同的樣品會產生不同的結果特性便可提供其檢測

• Each element has several x-ray lines (K, L, etc.)各元素有許多不同的 x-ray 能階可選擇

• Tube (source) X-rays interact with sample producing fluorescent x-rays. X-ray 管 ( 來源 ) 會使樣品產生反射螢光 x-rays

• X-rays emissions from excited elements in the sample are captured by a detector and converted into an energy spectrum.受激的樣品會產生 X-rays 射線被檢測器給截取轉換成為能量圖譜

• Computer software calculates chemistry results based on spectral analysis.電腦軟體利用能量圖譜將其轉換成化學成份

Quantitative Issues 量化的結果• Define a region for counting X-rays

確定 X-rays 計算的區域• Choose / apply a form of background correction – separate signal from

noise

選擇應用的區域背景修正值，將訊號及雜訊分開。• Apply a method of quantitation to the net total number of counts

(elemental intensity)

選擇方法去計算該區域的總計算值 ( 元素強度 )

• Normalize – relative answer – or not

數值化的結果是否符合其相對的成份

Quantitation in 3 Steps 量化的三步驟1. Excite & Capture Spectra 激發和截取光譜

2. Determine net intensity for each element 區域內測出強度及相對的元素1. Define regions 決定區域2. Correct for background – several steps that define elemental

intensity/signal/counts within region – 修正背景 - 幾個步驟定義元素強度 / 信號源 / 計數的範圍

3. Assign a count/intensity value to each element - net of interferences, escape peaks, other extraneous spectral artifacts )指定一個計數 / 每個元素的強度值 - 區域性的干擾，脫離的峰值，外來的光譜影響

3. Apply calibration to corrected signal to quantify應用檢量曲線將信號轉換至數值

In a Perfect World… 在完美的世界中• X-ray tube produces x-rays

X-ray 管會產生 X-ray 光• X-rays strike sample and cause elements in sample to fluoresce x-rays

X-ray 擊中樣品會導至物品產生 X-ray 螢光二次光• Semi-conductor detector within analyzer

半導體檢測器從內部分析• Detector measures energy of each x-ray separately, counts # of x-rays in

specific energy ranges and provides a spectrum檢測器會去測量已分離出的二次光的能量，計數每一特定的能量區域及提供一個頻譜

• Each peak represents a unique element每一個波峰代表一個獨立的元素

• Height of peak + calibration + elemental interference corrections yield concentration of elements 有了波峰高點及檢量線及元素的干擾修正，便可計算出該元素的濃度

In the World of Electronics Manufacturers - Non-homogeneity Issues => Qualitative Answers

在這個充滿電子產品的世界，沒有所謂的均質的物質 => 量化後的答案

Specific sample types require specific calibrations to be quantitative不同的樣品需要不同的檢量線方程或去將其量化

Size, shape, & geometry all impact spectral signature大小，型狀，都會有影響其頻譜特性

RoHS Directives

EPA … CALIFORNIA

EU Directives– Restriction of Hazardous Substances from electrical & electronic

equipment 限制下列有毒元素在電子電機產品中的含量• <0. 1% Pb, Cr6+, Hg, Br (as flame retardants, PBB and PBDE)• <0.01% Cd鉛，六價鉻，汞、 溴 (耐燃劑 ( PBB/PBDE ) 的含量須小於 0.1%鎘的含量必須小於 0.01%

– Equipment: household appliances, consumer electronics, electric tools, toys, leisure and sports equipment, IT & telecom equipment, etc.家電用品、消費性電子產品、電工具、玩具、休閒及運動佩件、資訊及通訊產品…等。

– Exemptions: military, biomedical implants, heavy equipment & others免除：軍事，生物醫學插入，重型設備和其它

– Date for Compliance: July 1, 2006– Responsible Parties 應負責任方

• “Producers”: manufacturers, sellers, distributors, exporters, importers 產品：製造商、銷售者、供應者、進出商、出口商

• Compliance is tracked throughout the entire supply chain.供應鍊所有的廠商均需依循

Justification, Method for XRF:使用 XRF 去證明是否符合

• IEC-ACEA (International Electro-technical Commission – Advisory Committee on Environmental Aspects)在環境方面上的國際電技術委員會咨詢委員會

• Published recommendations June 2005. 命今公佈於 2005 年 6月

• Recommends handheld XRF for qualitative and quantitative screening (Chapter 4 in Guide) (在指南裡的第 4 章 ) 建議使用手提式的 XRF

• Committee Representatives:委員會代表HP, Intel, IBM, Microsoft, Samsung, Motorola, Apple,

Sony, GE, Phillips, Toshiba, Dell, Mitsubishi.

Analysis Requirements -IEC-ACEA Recommended Methods分析條件 IEC-ACEA建議使用的方法

Screening篩選

Hg, Pb, Cd, Cr6+(1), PBB(2) ,

PBDE(2)

EDXRF or WDXRF

Verification驗證

Br (PBB/PBDE) GC/MS, HPLC/UV

Verification Cr6+ (metals only)

ISO 3613 Adaptation Spot Test or EPA 3063A/7196A Adaptation Colorimetric Method

Verification Hg ICP-AES, ICP-MS, CV-AAS or AFS

Verification Pb, Cd ICP-AES, AAS or ICP-MS

(1): XRF testing does not distinguish Cr6+ from total Cr, but does identify total Cr. If Cr is found by XRF at inconclusive or failing levels, verification testing should be performed.

(2): XRF testing does not identify PBB or PBDE, but does identify total Br. If Br is found by XRF at inconclusive or failing levels, verification testing should be performed.

XRF無法檢出六價鉻及阻燃劑，僅能測出鉻及溴的總含量，故要驗證其含量則需使用其他的檢驗工具。

Quantitative Screening RequirementsTable 6.2 IEC Guidelines

IEC 指導方針 篩選標準表

Element Polymer Materials聚合物材料

Metallic Materials金屬材料

Electronics電子元件

Cd鎘 P ≤ 70 < X < 130 ≤ F P ≤ 70 < X < 130 ≤ F LOD < X < 250 ≤ F

Pb鉛 P ≤ 700 < X < 1300 ≤ F P ≤ 700 < X < 1300 ≤ F P ≤ 500< X < 1500 ≤ F

Hg汞 P ≤ 700 < X < 1300 ≤ F P ≤ 700 < X < 1300 ≤ F P ≤ 500 < X < 1500 ≤ F

Br溴 P ≤ 300 < X N/A P ≤ 250 < X

Cr鉻 P ≤ 700 < X P ≤ 700 < X P ≤ 500 < X

P=Pass, F=Fail, Inc=Inconclusive顯示 P 為通過， F 為未通過， Inc 為未確定

IEC: Why PASS Only for Br and Cr:• Why PASS Only for Br:

– Regulated substance is PBDE (poly brominated diphenyl ethers). For Br <= 300 ppm, any organic form of poly bromides less than 1,000 ppm.聚合物中的聚溴二苯醚是規律性的物質，假如溴測出小於 300ppm ，則溴在聚合物中的含量則小於 1000ppm

– Greater than 300 ppm? Verify with GC/MS if it is the regulated organic form. 大於 300ppm ，則需使用 GC/MS 去驗證

• Why PASS Only for Cr:– If Cr > 700 ppm it could exceed 1,000 ppm factoring in method

accuracy. 假如檢測出超過 700ppm ，則有可能超過 1000ppm 。故需要使用更精確的方法。

– If this is the case, laboratory technique to determine if Cr+6 as Cr+3 is not regulated. 假如得到結果如此，需要實驗室去驗證是否為六價鉻或三價鉻

Non-Desuctive RoHS/WEEE Screening for Polymer & Metalic Materials

Pb, Hg:P≤(700-3σ)<X<(1300+3σ)≤F

Cr(a): P≤(700-3σ)<X

Cd: P≤(70-3σ)<X<(130+3σ)≤F

Br(b): P≤(300-3σ)<X (Br not in metallic materials)

Verification Test Procedure

XRFScreening

Inconclusive

Pass/Fail

Br ( PBB/PBDE):GC/MS, HPLC/UVCr 6+ (Metals only) :ISO 3613 adaptation tests or EPA3060A7196A Colorimetric MethodsHg:ICP-AES, ICP-MS, CV-AAS or AFSPb/Cd:ICP-AES, AAS or ICP-MS

Notes:(a): If Cr is detected at inconclusive or failing levels, a verification test for Cr 6+ should be performed.(b): If Br is detected at inconclusive or failing levels, a verification test for PBB or PBDE should be performed.

Screening Requirements篩選要求

• 1) “PASS” - Result for all elements is lower than the lower limits listed in Table 2 “PASS”.通過 - 檢測出的結果要比表二列舉的元素要低

• 2) “FAIL” - Result for any of the elements higher than the higher limits listed in Table 2: “FAIL”.未通過 - 檢測出的結果要比表二列舉的元素還高

• 3) “INCONCLUSIVE” - If the result of the quantitative analysis, for any of the elements Hg, Pb or Cd, is in the region defined as intermediate, or if the result of the elements Br and Cr is higher than the higher limits listed in Table 2, the analysis is inconclusive. Additional investigation must be performed. The test is “INCONCLUSIVE”.未確定 -假如檢測的結果對於汞、鉛、鎘定義為中間地帶，如果元素溴、鉻檢測的結果高於表二，那檢測出的結果是不確定的，必須要進行另外的分析。

Why Handheld XRF for RoHS Compliance?為何手提式 XRF遵循 RoHS 規範的

Facilitate high-throughput testing at the point of manufacture高產線更容易測試其產品

Non-technical operators 非技術性操作員 Examine in-situ samples for immediate results 原地快速檢測出結果 Simple & immediate results 檢便提供結果

– Identify or Quantify Pb, Hg, Cd, Cr and Br 辦識有無或檢測其鉛、汞、鎘、鉻、溴含量

– Sort or Quantify Pb-substitutes 序列或表示其元素含量• Cu-, Fe-, Ni-, Ti-based alloys, Sn, Ag, Zn, In, Bi, Cd, Sb

– Identify PVC, Br or Sb-based flame retardants, Hg-containing waste 辦識 PVC ， BR ，或其他的防火劑、汞含量消秏

Compliance verification, on-site QC, documented traceabilityQC 可依其檢測出的資訊，做產品的良度追縱

There’s High Value in Screening篩選的高價值如下

IEC Recommendations for XRF:

• Sample must be homogenous產品必須為均質

• Portable EDXRF analysis requires that sample covers analyzer window if possible. 樣品盡可能能覆蓋住其檢驗窗口

• Recommended minimum samples thickness建議的最小樣品厚度– Polymers & light alloys: 5mm 聚合物和輕合金： 5mm– Liquids: 15mm 液體： 15mm– Other alloys: 1mm 其他合金： 1mm

• Portable EDXRF analyzers require minimum instrument performance specifications – detection limits and precision可攜式 EDXRF 分析需要最少的儀器便能執行檢測及其精密性

3 Types of XRFs for RoHS/WEEEXRF 的三種檢測是否符合 RoHS/WEEE

#1. Handheld (HH): 手提式• High-throughput screening following IEC. • Very portable, easy to use. 方便攜帶，容易使用#2. Micro-Focus:微焦點式• Small x-ray spot (200 um) for components.較小的測試點

• Raster around circuit boards. 光柵環繞在電路附近

• Standard beam size (1.5 cm) superior LODs compared to HH.與手提式相比，擁有較標準規格 (1.5cm)

• Example: Cd, other metals at 5 ppm for Packaging Directive (Cr + Cd + Pb + Hg) < 100 ppm例如：在包裝中的鎘，及其他的金屬在 5ppm( 鉻 + 鎘 + 鉛 + 汞 )<100ppm

• Any specific metal < 5 or 10 ppm任何標式的金屬小於 5 或 10ppm

#3. Mobile Work Station行動工作站

• Hands free docking test stand allows safe, streamlined handling of small, thin, bagged, or cupped samples檢測較小或較細或袋裝樣品時。使用行動工作站可避免以手持樣品。可顧及安全。

• Run on AC or Battery可使用交流電或一般電池

• Carry in 1 hand from work site to work site單手即可將其移動到其他地點

Test Results 檢測結果• Lists RoHS Elements

列出 RoHS 要檢測的元素• Classifies as Positive, Negative,

Inconclusive (INC)以正，負，未確定表示通過否

• Set Desired Screening levels for polymers, electronics, metallics可設定要檢測的材質，如聚合物，電子元件，金屬。

• Simple Pass/Fail Display簡易的通過或未通過顯示

XRF Screening Guidelines

Homogeneous Samples 均勻材質的樣品

Quantitative Analysis (IEC Table 6.2)定量分析

Non-Homogeneous Samples非均勻材質的樣品

Qualitative Screening Methods利用量化篩選的方式

Single Biggest Analytical Challenge: Non-Homogeneous Samples檢測非均勻物質的的挑戰

IEC Guidelines Definition for Homogeneous: “均質物質”的定義

– Cannot separate into distinct parts using standard mechanical methods. 用機械方法拆分到不能再拆分的最小單元

– Homogenous alloy, no coatings or non-metallic materials. 均勻的金屬材質，沒有鍍層或非金屬的物質部份

– Plastic (PC board, consumer item, etc.) that is same material throughout analysis volume塑膠 (主機板，消費品等 )整體是同樣材質的聚合物組成。

The real world of samples is not homogenous現實世界無均勻材質的樣品

An IC consisting of multiple components: wafer, metal coating, plastic substrate, etc.

IC由多個部份組成：晶元、金屬底層、塑膠底層

Circuit board 電路板

What’s not homogeneous:什麼是非均勻物質

Cable if it is copper wire with rubber insulation. Must separate insulation to make homogeneous. 纜線是由銅線及橡塑絕緣層組成。必須將其分開成同材質

Surface mount resistor: Internally is ceramic, plastic, and 85% lead solder (which is exempt currently). 表面鍍層：內部是陶磁，塑膠，及85% 為焊接物 (目前為免除條款 ) 。

Plated Samples NOT Homogeneous鍍的樣品也同屬非均勻材質

Cr Coating(typically 100% Cr)

Substrate (Cr-free)

Top View

Side View

For non-uniform samples, it is nearly impossible to get quantitative results:對非相同的樣品，得到相同的定量結果是不大可能的

But you can screen effectively!

但是你可以有效率的篩選

Case Study #1: Screening Surface Mount Products案例 1：檢測表面塗層的產品

Contract manufacturer using surface mount resistors.

使用表面塗層與製造商簽訂合約。

Requirement: 須求

• Develop an incoming testing program to screen surface mount components as Pb-free (< 1,000 ppm). 發展測試程式篩選表面塗層無鉛的元件 (<1 ， 000 ppm) 。

• Must test 500 (typically) samples/day.每天須測試 500件樣品

• XRF used by incoming inspector (non-technical)必須使用 XRF 去檢測！ (非技術性 )

Case Study #1, Cont’d

Challenges:挑戰• Surface mount components are not homogeneous.

表面塗層的元件並非均勻物質• Impractical to dis-assemble

將其分開是不實際的• Contain small lead solder component (85% Pb) that is

exempt, so you do get Pb detected with XRF. 包括小的焊接部位 (85% 鉛 )那是被免除的，所以用XRF 會得到檢測到鉛的值。

• XRF tests vary depending upon what side of the component is tested. XRF 測試相當依賴於被檢測的部位

Screening Protocol Developed:檢測的協議發展

• For each type of component:對於組成部份的每種類型而言：– Select samples known to be Pb-free (by lab results)

選擇已知無鉛的樣品 (由實驗室的結果 )– Perform repeated XRF tests on same side to determine typical

results. Typically results were 300 – 400 ppm.反覆利用 XRF 在同一個位址做檢測求得結果。基本結果介在300-400ppm

– Use this as a baseline. 使用所得到的做為基準– Operator tests other components (same type) and whenever they

get a lead result >> 400, they flag that component as non-compliant. 檢測同類型的原件，當他得到的結果大於 400 ，則表示這個樣品並不符合其標準。

Case Study #1: Innov-X CommitmentsInnov-X 的承諾

• Recommended test protocol 推薦測試的標準

• Trained operators, assisted with developing testing plan訓練操作員，參與發展的測試計劃

• Provided software upgrade that allowed operator to pick component type from a menu, and an “cutoff” threshold was automatically used for pass/fail, based on the setup testing performed.提供軟體升級服務及提供選用所需的功能

• Supports hundreds of different types of surface mount resistors, capacitors, etc. 提供數百種不同的型態於表面塗層，

Case Study #2: Screening Circuit Boards案例 2：檢測電路板

Case Study #2: The Problem案例 2：問題

• Rapidly screen circuit boards for either Pb in solder or components, or Br in the boards. 快速檢測在電路板或元件其中的鉛含量或溴含量

• Must test thousands of boards per week.每週須檢測數千件的電路板

• Not homogeneous.並非均勻材質

• Cannot disassemble.無法再拆卸至更小的部份

• Production line environment. 生產線環境

Innov-X PC Board Screening Procedure:檢測電路板的做法

• Test multiple locations on board. 在電路板測試許多不同的點

• Any detected Pb, Br -> Fail or seek supplier assurance.任何檢測到鉛，溴表示錯誤。找供應商所提供的保證。

• Non-detects -> PASS. 沒有檢測到則表示通過

• Verify on a sub-sample of boards that are known (via lab analysis) to be RoHS compliant. 拿一塊已知成份的電路板 ( 實驗室分析 ) 符合 RoHS 來驗證

• Screen large quantities of boards檢驗大量的電路板

Case Study #2: Supporting Arguments支持辦論

• Detection limit for Pb and Br is about 5-10 ppm.檢測鉛及溴的最小極限約 5-10ppm

• This DL << Compliance level (1,000 ppm),最小的極限遠小於規定的 1000ppm

• An XRF non-detect is very unlikely to exceed 1,000 ppm due to shielding effects of other materials.非 XRF 檢測未必超過 1000PPM ，原因來自其他物質的遮避效應

• High confidence screening approach to circuit boards. 高信賴的檢測方法於電路板

Note: • This approach can produce occasional false positives if exempted lead solder

is present.這個方法可以明確表示出焊接存在時偶然產生的錯誤。

• Exempted solder generally well documented. 排除焊接處，通常用文件證明

Case Study #3: Cable Insulation絕緣電纜

Case Study #3: The Problem• Large cable and connector manufacturer

大量的電纜和接頭製造廠• Receiving cable, connectors from suppliers stating RoHS compliant.

電纜和接頭自供應者須符合 RoHS 規範• Rented an XRF to spot check suppliers for 1 month.

用 XRF 抽查供應者 1 個月。 • Result: 20-30% of cable insulation NOT RoHS compliant (high Pb or

Br) despite material certs stating compliance. 結果： 20-30% 的絕緣電纜仍不符合 RoHS 規範 (較高的鉛或溴 )即使供應商提供的原料符合規範。

• Put a Hold on affected suppliers. Required them to implement XRF testing. 要求供應商應用 XRF 去做原料測試

Sample Types

• Not Homogeneous: Rubber insulation over metal wire or connector非均勻材質：橡膠絕緣體穿過電線或接頭

• Analysis includes “mass” of rubber and wire. 檢測時會包括電線部份及絕緣體部份

• Effects: Copper appears at high percentages (80+%)影響：銅會出現高於 80%

XRF Protocol for Pb:• Test cables or connectors “as is.”

測試電纜或接頭如下示• If no detected Pb or Br -> PASS如果沒有檢測出鉛或溴表示通過

• If detected Pb:如果檢測出鉛– Remove insulation from wire

將絕緣部份移去留下線材部– Insulation now a homogeneous sample絕緣部份便是均勻的樣品

– Retest 重新檢測– If Pb > 1,300 ppm (IEC Guidelines) FAIL.假設鉛大於 1300ppm 則表示未通過

– If Pb < 700 ppm, PASS假如鉛小於 700ppm 表示通過

– Else: Inconclusive, seek lab verification.其他：不確定，實驗室型檢測

Note: See next slide for Br

XRF Protocol for BrBromine Protocol: 溴的檢測方法• If no detected Br -> PASS

沒有檢測到溴表示通過• If detected Br: 有檢測到溴的話

– Remove insulation from wire移去絕緣層

– Insulation now a homogeneous sample絕緣層現為均勻材質樣品

– Retest 重新測試– If Br < 300 ppm (IEC Guidelines) PASS.

假如溴小於 300ppm 則通過– If Br > 300 ppm, FAIL or lab test for

PBDE form. 假如溴仍大於表示未通過，或使用實驗室方法去檢驗

Note: XRF measures elemental Br. RoHS regulates poly-brominated diphenyl ethers. If XRF test < 300 ppm, then any molecular form of PBDE is < 1,000 ppm, thus a PASS.

Result:結論

• Customer eliminated non-compliant products at incoming inspection.用戶進貨時排除掉不符合的產品

• Required vendors to use XRF testing to test materials prior to shipping. 要求賣方使用 XRF 測試其材料

• No longer sending non-compliant products to their customers. 不再將不符合的產品銷售給客戶

Case Study #4: Cr Plating鉻鍍層

Application: 應用• Substrate, typically alloy, with Cr

plating.基底，基本合金，帶有鍍鉻層

• Is the plating hexavalent Cr (Cr+6)?鍍層是六價鉻嗎？

• Is the Cr concentration in the plating only in excess of 1,000 ppm? 鉻的濃度在鍍層超過 1000ppm嗎？

Case Study #4 The Challenge: 挑戰

• Plating + Substrate NOT homogeneous sample. 鍍層 +基底 非均勻材質

• EU Directives treat plating as separate sample.歐盟指令對待鍍層為各別的樣品

• Often Cr plating is 100% Cr clearly violating 1,000 ppm limit. (If hexavalent).通常鉻鍍層為 100% 的鉻明確超過 1000ppm 的限制 (假如是六價鉻 )

Cr Coating(typically 100% Cr)

Substrate (Cr-free)

Top View

Side View

Case Study #4: XRF Challenge

• X-rays analyze both plating and substrate (if plating < 0.5 to 1 mm). 利用 X-ray 分析時會同時分析到鍍層及基底部份 (假如鍍層小於0.5 至 1mm)

• Effect is to “dilute” the Cr percentage by mass ratio substrate to coating. 基底效應會讓檢測鍍鉻層的結果下降！

• Lab analysis: Same effect unless Cr coating is scrapped off and separately analyzed.實驗室檢測：相同的效應除非鉻薄層被分離開各別分析。

Cr Coating(typically 100% Cr)

Substrate (Cr-free)

Top View

Side View

X-rays in

X-rays out

Case Study #4: Recommended XRF Procedure案例 4：建議利用 XRF 檢測的作法

• Screen for any Cr content 檢測任何鉻含量• If detectable Cr then: 假如檢測出鉻：

– FAIL the material as likely 100% Cr plating未通過即表示含有 100% 的鉻鍍層

– Perform laboratory analysis to determine of hexavalent (banned) or trivalent Cr (allowed). 利用實驗室型檢測是否含有六價鉻或是三價鉻

• No detectable Cr -> PASS 未檢測出鉻即表示通過

• Most plating applications switch to non-Cr platings so they are not regularly testing for hex-Cr. Why?大部份的鍍層應用轉向使用非鉻鍍層，因此無須定期檢測六價鉻。為什麼

– Easy to mix up Cr types 容易與其他類型的鉻混洧– Tests for hexavalent Cr are time consuming and expensive.

測試六價鉻是費時且昂貴的。

Case #5: Comparison to Laboratory. 與實驗室檢測做比對Example: Component Leads 例：元件接腳

Leads

Solder layer (t) Copper Lead R

•According to RoHS, copper wire and solder must be analyzed separately.按照 RoHS 的規定，銅線和其焊料必須分別分析•Lab must remove solder layer and analyze separately.實驗室必須移去焊料並分別分析•Lab/ICP: If digest entire component, result is low – potential false negative! 實驗室 /ICP 化驗：假如檢測全部份，結果是低 -

Example:

•10 um solder layer on 200 um copper wire

•May read up to 6X low so 3,000 ppm Lead is reported < 500 ppm.

Conclusions 結論• IEC Guidelines recommend homogeneous samples.

IEC建議使用均勻材質• Very often impossible to obtain these.

不大可能獲得這些• In nearly all cases with some background effort, screening

programs can be developed.在大部份的狀況下都會有背景影響，篩選可能被發展

• Laboratory Analysis: Be sure the “sample” is clearly defined. 實驗室分析：確定該樣品被明確的被定義

• Innov-X has hundreds of RoHS customers and vast experience developing XRF screening programs. Innov-X 有數百個 RoHS 用戶和豐富的經驗於 XRF 篩檢。

Technical Data 技術資訊• Accuracy準確性

• Detection Limits (Sensitivity)檢測極限 (敏感性 )

• Effect of Sample Thickness樣品厚度的影響

• Effect of High Bromine on Lead Results高溴對結果的影響

Accuracy準確性

• On Standards: 5 – 10% Relative:5-10% 的相對誤差– 1,000 ppm +/- 100 ppm (10%)– Flat, uniform standards, not the real world

統一的標準，並非真實的世界• For XRF screening purposes: Borderline concentrations

around the action level.XRF 檢測目標：邊界濃度– Typically 25%標準 25%– Example: 750 – 1,250 ppm for Pb, Hg, Cr

• Larger range incorporates real-world sample shapes/sizes, interferences. 更大範圍包括現實世界實例形狀 / 尺寸，干擾。

Tube-based Portable XRF Detection Limits in PPM for Regulated Metals in Polymers and Replacement Metals of Pb Solder

Element LOD (ppm) Element LOD (ppm)

Pb 10 Cd 25

Cr 40 Hg 10

Br 5 Sb 45

Sn 80 Ag 40

Ti 150 Co 6

Cu 43 Ni 45

As 9 Zn 20

Pb in Plastics

Comparison of XRF Results with Assayed Values Containing Pb, 120 sec

Lead (Pb)

0

500

10001500

2000

2500

3000

35004000

4500

5000

0 1000 2000 3000 4000 5000

Assayed ppm

Mea

sure

d p

pm

Cd in Plastics

Comparison of XRF Results with Assayed Values Containing Cd, 120 sec

Cadmium (Cd)

0

200

400

600

800

1000

1200

0 200 400 600 800 1000 1200

Assayed ppm

Hg in Plastics

Comparison of XRF Results with Assayed Values Containing Hg, 120 sec msmt.

Mercury (Hg)

0

200

400

600

800

1000

1200

1400

0 500 1000 1500Assayed ppm

Mea

sure

d p

pm

R2 = 0.996

Br in Plastics

Comparison of XRF Results with Assayed Values Containing Br, 120 sec msmt.

Bromine

0

1000

2000

3000

4000

5000

6000

0 1000 2000 3000 4000 5000 6000

Assayed ppm

Mea

sure

d pp

m

R2 = 0.998

Portable EDXRF Analysis and Sample Thickness Variation

1010 ppm Pb

100 ppm Cd

960 ppm Br

390 ppm Sb

0

250

500

750

1000

1250

1500

0 1 2 3 4 5 6 7 8 9

Sample Thickness (mm)

XR

F M

ea

su

red

Co

nc

en

tra

tio

n (

pp

m)

Sample Thickness: Conclusion樣品厚度：結論

• Combining fundamental parameters with empirical corrections is least sensitive to sample thickness根據經驗去調較程式參數可以對樣品的厚度敏感度降低

• Generally good results even for very small components甚至對較小部份元件都擁有較佳的結果。

• Longer test times to meet same precision.較長的測試時間才能得到相同精確度– If sample is 4X smaller,than test 2X longer to get same precision,假如樣品是原來的四分之一，測試時間為原的二倍可得到相同的精確度

– Same test time to get 1/2X as good precision.相樣的測試時間僅能得到原來的一半(scales as square root) 以平方根做為計算方法

Printer Output: 列表輸出方式Declaration of Compliance

Plastic Samples with/without High Bromine80 ppm Pb Present in 0.056% Br (Blue) and 5.2% Br (Yellow)

0.01

0.1

1

10

100

1000

10000

0 2 4 6 8 10 12 14

X-ray Energy (keV)

Inte

nsity

(cps

)

0.056% Br

5.2% Br

Pb La

Pb LaPb La

Pb Lb

Effect of high bromine: Reduced Pb sensitivity. 高溴的影響：對鉛的靈敏度低

XRF “Bromine Alert”: Senses high Br, automatically uses lead L-alpha line for improved sensitivity XRF 會自動修正其靈敏度

Overview – Competitive Advantages• PDA generally well received • Use multiple PDAs• PC software• Ergonomics:

– Alpha smaller, lighter– Not required to hold in the trigger for long tests.

• Color display, not b/w• Analyze single surface mount components.• Rear display• IEC protocol programmed in already• Test Stand superior• Hawk-i • Connect customer with consultants, software data management, panel

discussions with their peers.

Reference List (Partial)• HP• Intel• Dell• Microsoft• Hitachi• Samsung• Samjing• Amphenol• Leviton• G-tech• GE• L3 Communications• Alpha Wire (Belden)• Mt Vernon Picture Display• Rolls Systems• BASF

Summary: Portable EDXRF for RoHS Screening

• Suggested tool for RoHS Directive compliance被 RoHS 指定使用的工具

– Quantifies ppm levels: Pb, Hg, Cr, Cd, Br可檢測至 ppm 的微量

– Applicable throughout the supply chain可應用至生產鍊中

• During manufacture, recycling, disposal製造，回收，處理期間

• Compliance verification, on-site QC, documented traceability符合的證明，現場的 QC ，文件的追蹤

• Best Application: Where high volume testing is important 最佳的應用：非常需要高密度的測試場合

• Readily available analyzers with off-the-shelf upgrades容易升級得到較好的分析能力

• RoHS Testing Challenges:– Non-homogeneous samples 非均勻材質的樣品– Coated materials 鍍層物質

More Information

• IEC Guidelines pdf available.• Innov-X RoHS Guidelines for portable

XRF• RoHS/WEEE Seminars:

– Alliance of Service Providers and Manufacturers

– http://www.innov-xsys.com/RoHS-WEEE/index.html

• http://www.rohswell.com/