GZTP096CCL.01比色法测定聚合物和电子材料中的六价铬含量.pdf

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1、Issue No.:01,Effective Date:2017/09/20 Page 1 of 9 INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB Testing Procedure Location:GZ CCL Document Code:GZ-TP096-CCL Application:Inorganic Issue No.:01 Title:比色法测定聚合物和电子材料中的六价铬含量 Determination of hexavalent chromium(Cr(VI)in

2、 polymers and electronics by the colorimetric method Issue No.Effective Date Amendment Summary 01 Sep 20,2017 -新版本发布 New issue Prepared by Checked by Approved by INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING PROCEDURE GZ-TP096-CCL.01 Issue No.:01,

3、Effective Date:2017/09/20 Page 2 of 9 1.范围(Scope)该方法描述了测量六价铬的步骤，聚合物和电子学样品中的定量。该方法采用有机溶剂溶解或膨胀样品基质，然后用碱性消化法提取六价铬。This method describes a procedure to measure Chromium(VI),quantitatively in samples of polymers and electronics.This method employs organic solvent to dissolve or swell the sample matrix,fo

4、llowed by an alkaline digestion procedure to extract Cr(VI)from samples.2.参考文件(Reference Documents)2.1.IEC 62321-7-2:2017 比色法测定聚合物和电子材料中的六价铬含量 IEC 62321-7-2:2017 Determination of hexavalent chromium(Cr(VI)in polymers and electronics by the colorimetric method 2.2.ISO 3696:1987 分析实验室用水规范和试验方法 ISO 369

5、6:1987,Water for analytical laboratory use-Specification and test methods 3.原理(Principle)溶液中的六价铬将1,5-二苯卡巴肼氧化为1,5-二苯卡巴腙，产生一种紫红色络合物，此络合物可用光度计在540nm处定量检测。The chromium()in solution oxidizes 1,5-diphenylcarbazide to 1,5-diphenylcarbazone to give a red/violet complex with chromium which can be quantified

6、photometrically at 540nm.4.仪器设备与化学试剂(Apparatus,Instrument and Chemicals)4.1 仪器设备(Apparatus,Instrument)4.1.1.电子天平，1 Div.=0.0001g Electronic balance,1 Div.=0.0001g 4.1.2.锥形瓶，50mL带磨口塞 Conical flash,of capacity 50mL,with stopper 4.1.3 紫外可见分光光度计(UV-Vis)，用长度为5cm的石英比色皿 UV-Visible spectrophotometer,with 5cm

7、 quartz photometric cells 4.1.4 pH计，带玻璃电极 pH meter,with glass electrode 4.1.5 可维持消化溶液的加热或微波装置，温度在150到160 Heating or microwave device capable of maintaining the digestion solution at temperatures between 150 and 160 4.1.6 超声波水浴，可保持60至65之间的温度 Ultrasonic water bath,capable of maintaining the temperatur

8、e between 60 and 65 4.1.7 0.45m孔径的薄膜滤器(聚四氟乙烯或尼龙材质)Membrane filter,0.45m pore size(polytetrafluoroethylene or nylon)4.1.8 装有合适反相材料的玻璃或聚丙烯试样筒。如反相(RP)C18 Glass or PP cartridges filled with suitable reversed phrase material.(RP)C18 INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEM

9、ICAL LAB GUANGZHOU-TESTING PROCEDURE GZ-TP096-CCL.01 Issue No.:01,Effective Date:2017/09/20 Page 3 of 9 4.1.9 固相萃取(SPE)系统，带有真空设备 Glass or PP cartridges filled with suitable reversed phrase material 4.1.10 SPEX6870全自动冷冻研磨机 6870 Large freezer/Mill 4.1.11 玻璃分液漏斗，100mL Glass separatory funnel 100mL 4.1.

10、12 容量瓶，25mL,100mL,1000mL Volumetric flasks of capacity 25mL,100mL and 1000mL 4.2 化学试剂(Chemical reagent)4.2.1 pH=4.00,6.86 and 9.18缓冲液 pH=4.00,6.86 and 9.18 buffer solutions 4.2.2 分子筛(4A)，CAS：70955-01-0，干燥剂 Molecular sieves(4A),CAS:70955-01-0,desiccant 4.2.3 N-甲基吡咯烷酮(NMP)，分析纯试剂 N-Methyl-pyrrolidone,a

11、nalytical reagent grade 添加10g活化分子筛(5.2.2)每100mL新开的NMP，密封盖紧，保持在黑暗中，偶尔摇晃，在首次使用前保持超过12h。存储在20到25与在一个密闭的棕色玻璃容器分子筛和避免强光直接照射。建议的最大贮存期为四周 Add 10g activated molecular sieves(5.2.2)per 100ml of newly opened NMP,seal the cap tightly,keep in the dark,shake occasionally and maintain over 12h before first use.St

12、ore at 20 to 25 with molecular sieves in a tightly sealed brown glass container and avoid direct light exposure.The suggested maximum storage period is four weeks after the opening time of the container 4.2.4 甲苯(Toluene)，分析纯试剂 Analytical reagent grade 4.2.5 硝酸，体积分数为35%Nitric acid,volume fraction of

13、35%用水(5.2.13)稀释50mL的硝酸至100mL容量瓶(5.1.12)。存储在20到25的黑暗中 Dilute 50mL of reagent grade HNO3 to 100mL with water(5.2.13)in a volumetric flask(5.1.12).Store 20 to 25 in the dark 4.2.6 丙酮(Acetone)，分析纯试剂 Analytical reagent grade 4.2.7 无水碳酸钠(Na2CO3)，分析纯 Sodium carbonate,analytical reagent grade 4.2.8 氢氧化钠(NaO

14、H)，分析纯 Sodium hydroxide,analytical reagent grade 4.2.9 消解液，溶解20.0g0.05g NaOH 和30.0g0.05g Na2CO3 在一个1L容量瓶中，稀释至刻度。存储在20到25聚乙烯瓶中，每月配制。使用前应检查消解液的pH值。如果pH11.5，丢弃并重新配制 Digestion solution:Dissolve 20.0g0.05g NaOH and 30.0g0.05g Na2CO3 in a 1L volumetric flask,dilute to the scale.Stored in 20 to 25 polyethy

15、lene bottle,prepared on a monthly basis.The pH Value of the dissolving liquid should be checked before use.If the pH is 11.5,discard and redistribute INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING PROCEDURE GZ-TP096-CCL.01 Issue No.:01,Effective Da

16、te:2017/09/20 Page 4 of 9 4.2.10 无水氯化镁(MgCl2)，分析纯 Magnesium chloride 4.2.11 磷酸缓冲液：pH=7的缓冲液，87.09g 磷酸氢二钾(K2HPO4)和68.04g 磷酸二氢钾(KH2PO4)至700mL水(5.2.13)中，转移至1L容量瓶中并稀释。配制的溶液应含0.5mol/L K2HPO4 和0.5mol/L KH2PO4 Phosphate buffer:To prepare a buffer solution at pH 7,dissolve 87.09g K2HPO4 and 68.04g KH2PO4 int

17、o 700mL of water(5.2.13).Transfer to a 1L volumetric flask(5.1.12)and dilute to volume.As prepared,the solution will contain 0.5mol/L K2HPO4 和0.5mol/L KH2PO4.4.2.12 硫酸，体积分数10%Sulfuric acid,volume fraction of 10%稀释10mL的硫酸至100mL容量瓶(5.1.12)中，用水(5.2.13)稀释至刻度 Dilute 10mL of distilled reagent grade or spe

18、ctroscopic grade H2SO4 to 100mL with water(5.2.12)in a volumetric flask(5.1.13)4.2.13 1,5-二苯卡巴肼溶液 Diphenylcarbazide solution 溶解250mg二苯卡巴肼至50mL丙酮(5.2.4)中。存放在棕色瓶子里，有效期两周。若变色，应丢弃重新配制 Dissolve 250mg 1,5-diphenylcarbazide in 50ml acetone(5.2.4).Store in a brown bottle.Prior to use,check the solution for

19、discoloration.Store for use up to two weeks and if solution becomes discolored,discard it and prepare a fresh batch 4.2.14 ISO 3696:1987 实验室分析用水-规范和试验方法 ISO 3696:1987 Water for analytical laboratory use-Specification and test methods 5.标准溶液(Standard solutions)5.1.100mg/L 六价铬标准溶液 100mg/L chromium()st

20、andard solution 5.2.1mg/L 六价铬标准储备溶液 1mg/L chromium()standard stock solution 移取1mL 100mg/L六价铬标准溶液到100mL容量瓶里，用水(5.2.13)定容至刻度线。(保质期：1个月)Pipette 1mL of 100mg/L chromium()standard stock solution to 100mL volumetric flask,and make up to mark with water（5.2.13）.(Storage period:One month)5.3.0.00 mg/L,0.004

21、mg/L,0.01mg/L,0.04mg/L,0.1mg/L 和0.2mg/L六价铬标准工作溶液 移取0.0,0.2,0.5,2.0,5.0 和 10.0mL 1mg/L六价铬标准储备溶液到50mL容量瓶，加入1.25mL 1,5-二苯卡巴肼(5.2.12)到上述50mL容量瓶里，缓慢加入10%(V/V)硫酸(5.2.11)，调节pH值至2.00.5，用水(5.2.13)定容至刻度线。注意：溶液需现配，均匀混合并静置(5-10)min。用水(5.2.13)配制，使用后丢弃。0.00,0.004mg/L,0.01mg/L,0.04mg/L,0.1mg/L and 0.2mg/L chromium

22、()standard solutions Pipette 0.0,0.2,0.5,2.0,5.0 and 10.0mL 1mg/L chromium()standard solution into 50mL INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING PROCEDURE GZ-TP096-CCL.01 Issue No.:01,Effective Date:2017/09/20 Page 5 of 9 volumetric flask.Res

23、pectively add 1.25ml 1,5-Diphenylcarbazide solution(5.2.12)with pipette into the above mentioned 50 ml volumetric flasks.Slowly add H2SO4 solution(5.2.11)to the vessel and adjust the pH of the solution to 2.00.5 and make up to the mark with water(5.2.13).Note:The solution is freshly prepared and all

24、owed to stand for(5-10)min as the samples.Run the solutions against water(5.2.13)and discarded after use.校正点 标液浓度(mg/L)加标体积(mL)定容体积(mL)最终浓度(mg/L)1-0 2 1 0.2 50 0.004 3 1 0.5 50 0.01 4 1 2.0 50 0.04 5 1 5.0 50 0.1 6 1 10.0 50 0.2 5.4.0.04mg/L六价铬QCS标准溶液(0.04mg/L chromium()Intermediate standard solutio

25、n）移取2mL 1mg/L 六价铬标准储备溶液(5.2)到50mL 容量瓶里，加入1.25mL 1,5-二苯卡巴肼(5.2.12)到50mL容量瓶里，加入10%(V/V)硫酸(5.2.11)，调节pH值至2.00.5，用水(5.2.13)定容至刻度线。注意：溶液需现配，均匀混合并静置(5-10)min。用水(5.2.13)配制，使用后丢弃。Pipette 2mL 1mg/L chromium()standard solution(5.2)into 50mL volumetric flask,Respectively add 1.25mL 1,5-Diphenylcarbazide soluti

26、on(5.2.12)with pipette into the above mentioned 50mL volumetric flasks.Slowly add H2SO4 solution(5.2.11)to the vessel and adjust the pH of the solution to 2.00.5 and make up to the mark with water(5.2.13)Note:The solution is freshly prepared and allowed to stand for(5-10)min as the samples.Run the s

27、olutions against water(5.2.13)and discarded after use.6.流程(Procedure)6.1 可溶性聚合物(ABS、PC和PVC基体)中六价铬的提取 Extraction of Cr(VI)in soluble polymers-ABS,PC and PVC matrixes 6.1.1 称取0.1g样品到50mL锥形瓶中。Weigh a sample of 0.1g into 50mL conical flask.6.1.2 将10mL的NMP(4.2.3)加入锥形瓶中，盖紧瓶塞。Place 10ml of NMP(4.2.3)into t

28、he conical flask and seal the cap tightly.6.1.3 在60水浴中超声溶解样品样品1h，用手摇动约10s，继续超声1h。在进行下一步之前，样品必须全部溶解。Dissolve sample by ultrasonication at 60 for 1h,shake the sample by hand for about 10s,then ultrasonication at 60 for 1h again.The sample matrix has to be completely dissolved before proceeding to the

29、next step.6.1.4 摇动锥形瓶，加入200mg MgCl2(4.2.9)，0.5mL 0.5 mol/L磷酸盐缓冲液(4.2.10)和20mL消解液INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING PROCEDURE GZ-TP096-CCL.01 Issue No.:01,Effective Date:2017/09/20 Page 6 of 9 (4.2.8)，充分混匀。Shake the conical flask,add 200

30、mg MgCl2（4.2.9）,0.5ml 0.5 mol/L phosphate buffer（4.2.10）and 20ml digestion solution（4.2.8）,mix well.6.1.5 在60水浴中再超声1h。(0.5h用手摇动锥形瓶)Ultrasonication above solution at 60 for 1h.(shake the conical flask by hand and mix well after 0.5h)6.1.6 将溶液转移到150mL烧杯中，不断搅拌，加入硝酸(4.2.4)，调节溶液pH值至7.50.5。即使样品溶液浑浊或絮状沉淀物存

31、在，也不要过滤样品溶液。转移到100mL容量瓶，用水(4.2.13)定容。Transfer above content to a 150mL beaker.With constant stirring white monitoring the pH,add HNO3（4.2.4）dropwise to the beaker.Adjust the pH of the solution to 7.50.5.Even if the sample solution is turbid or flocculent precipitates are present,do not filter the sa

32、mple solution.Transfer to 100ml volumetric flask with water（4.2.13）fixed.6.1.7 分别移取10.0mL溶液，一个加0.5mL 1,5-二苯卡巴肼(4.2.12)，用10%(V/V)硫酸(5.2.11)调节pH值至2.00.5，用水(5.2.13)定容至25mL。另一个则不加1,5-二苯卡巴肼(4.2.12)，做样品空白。Remove 10.0mL of solution separately,add 0.5mL 1,5-diphenyl(4.2.12)carbamide to vessel,slowly add H2S

33、O4(5.2.11)solution to the vessel and adjust the pH of the solution to 2.50.5,use water to 25mL.The other one does not add 1,5-diphenyl carbamide,and does the sample blank.6.1.8 显色(5-10)min，有颜色样品用0.45m滤膜(4.1.7)过滤上机，在波长540nm处用UV-Vis(4.1.3)测定。Let stand 5-10min for full color development,filter the colo

34、red sample solution using the 0.45m syringe filter,measure its absorbance at 540nm with UV-Vis.6.2 不溶性/未知聚合物和电子材料(没有锑)中的六价铬 Extraction of Cr(VI)in insoluble/unknown polymers and electronics-Without Sb 6.2.1 称取0.15g样品到50mL锥形瓶中。Weigh a sample of 0.15g into 50mL conical flask.6.2.2 添加10mL消解液(4.2.8)和5mL

35、甲苯(4.2.4)，加入400mg MgCl2(4.2.9)和0.5mL 0.5mol/L磷酸盐缓冲液(4.2.10)，混合均匀。Add 10mL of digestion solution（4.2.8）and 5mL of toluene（4.2.4）,then add 400mg MgCl2,（4.2.9）0.5mL 0.5mol/L phosphate buffer（4.2.10）,mix well.6.2.3 微波装置(4.1.5)保持(1555)消解1.5h，使样品溶液冷却到室温。Maintain temperature(4.1.5)at(1555)for 1.5h,allow sa

36、mple to cool to room temperature.6.2.4 分离有机相从样品中用分液漏斗(4.1.11)分离。水相经0.45m滤膜(4.1.7)过滤，用水(4.2.13)冲洗锥形瓶三次。滤纸可用于过滤样品。Separate the organic phase from the vessel using a separatory funnel and discard it.The INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING P

37、ROCEDURE GZ-TP096-CCL.01 Issue No.:01,Effective Date:2017/09/20 Page 7 of 9 aqueous phase is filtered through a 0.45m membrane filter(4.1.7),rinse the conical flask three times with water(4.2.13)and filter.A large pore size filter paper may be used to filter the sample.6.2.5 将溶液转移到150mL烧杯中，不断搅拌，加入硝酸

38、(4.2.4)，调节溶液pH值至7.50.5。转移到50mL容量瓶，用水(4.2.13)定容。Transfer above content to a 150mL beaker.With constant stirring white monitoring the pH,add HNO3(4.2.4)dropwise to the beaker.Adjust the pH of the solution to 7.50.5.Transfer to 50mL volumetric flask with water(4.2.13)fixed.6.2.6 如果溶液是浑浊或絮状沉淀物存在，通过0.45m

39、滤膜(4.1.7)过滤。如果样品溶液中有颜色，用C18柱(4.1.8)脱色。If the solution is turbid or flocculent precipitates are present,filter the sample,through a 0.45m membrane filter.If color is present in the sample solution,filter the solution with a C18 syringe cartridge(4.1.8).6.2.7 分别移取10.0mL溶液，一个加0.5mL 1,5-二苯卡巴肼(4.2.12)，用1

40、0%(V/V)硫酸(5.2.11)调节pH值至2.00.5，用水(5.2.13)定容至25mL。另一个不加1,5-二苯卡巴肼(4.2.12)，做样品空白。Remove 10.0mL of solution separately,add 0.5mL 1,5-diphenyl(4.2.12)carbamide to vessel,slowly add H2SO4(5.2.11)solution to the vessel and adjust the pH of the solution to 2.50.5,use water(5.2.13)to 25mL.The other one does n

41、ot add 1,5-diphenyl(4.2.12)carbamide,and does the sample blank.6.2.8 显色(5-10)min，在波长540nm处用UV-Vis(4.1.3)测定。Let stand(5-10)min for full color development,measure its absorbance at 540nm with UV-Vis(4.1.3).6.3 重复 6.1.2-6.1.8 和 6.2.2-6.2.7 程序，不加样品做方法空白。Repeat 6.1.2-6.1.8 and 6.2.2-6.2.7,but without add

42、ing sample for method blank.6.4 回收率(The recovery rate)添加1.0mL 1mg/L六价铬标准储备溶液(5.2)到样品溶液中，按照 6.1.1-6.1.8 程序操作，添加1.5mL 1mg/L六价铬标准储备溶液(5.2)到样品溶液中，按照 6.2.1-6.2.7 程序操作，充分混合均匀。在波长540nm处用UV-Vis(4.1.3)测定。Add 1.0 mL 1mg/L chromium(VI)standard solution(5.2)by Pipette in sample solution,follow 6.1.1-6.1.8 opera

43、tion,add 1.5 mL 1mg/L chromium(VI)standard solution(5.2)by Pipette in sample solution,follow 6.2.1-6.2.7 operation,mixed well.The solution will be rested for(5-10)min.Measure its absorbance at 540nm with UV-Vis(4.1.3).7.计算(Calculation)7.1.样品中六价铬含量(Sample hexavalent chromium concentration):CCr(VI)=MF

44、VC 式中(Where)：INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING PROCEDURE GZ-TP096-CCL.01 Issue No.:01,Effective Date:2017/09/20 Page 8 of 9 CCr(VI)=样品中Cr(VI)的含量(g/g)The sample Cr(VI)concentration in g/g C=测试消解液的浓度(g/mL或g/g)The Cr(VI)concentration obse

45、rved in the digestate in g/mL;or g/g F=稀释因子 The dilution factor V=最终消解液体积(mL)，或最终消解质量(g）The final volume of the digestate in mL;or the final mass of the digestate in g;M=样品初始质量(g）The initial sample mass in g 7.2.相对百分偏差(Relative percent difference(RPD)R=100)(5.0DSDS 式中(Where)：R=相对百分偏差 The relative pe

46、rcent difference in%S=最终样品结果(g/g)Initial sample result in g/g D=重复样品结果 Duplicate sample result in g/g 7.3.加标回收率(Spike recovery)SR=100SAUSSS 式中(Where)：SR=加标回收率(%)The spike percent recovery in%SS=加标样品测试结果(g/g)The Cr(VI)concentration in the spiked sample in g/g US=未加标的样品测试结果(g/g)The Cr(VI)concentration

47、 in the unspiked sample in g/g SA=加入标准物质的量(g/g)The Cr(VI)concentration used in the spike solution in g/g 8.质量控制(Quality Control)项目 Item 浓度 Concentration(mg/L)接受标准 Acceptance criteria Frequency 频率 INTERTEK TESTING SERVICES SHENZHEN LIMITED GUANGZHOU BRANCH CENTRAL CHEMICAL LAB GUANGZHOU-TESTING PROCE

48、DURE GZ-TP096-CCL.01 Issue No.:01,Effective Date:2017/09/20 Page 9 of 9 校正曲线 Calibration curve 见条款 5.3 See 5.3 R 20.995 Every week 每周 CCV 见条款 5.4 See 5.4 （0.040.004）mg/L 每20个样品/次 Every 20 sample 方法空白 Method blank 见条款 6.3 See 6.3 0.004mg/L 每批次 Each batch 加标回收 Spike recovery 见条款 6.4 See 6.4 回收率：80%-12

49、0%Recovery:80%-120%每批次 Each batch 平行样 Duplicate sample /相对标准偏差小于20%RSD（%）less than 20%每批次 Each batch 9.报告限(Report Limit)元素Elements 报告限Report Limit(mg/kg)Cr6+10 10.记录(Record)编号NO.记录名称 Record Name 记录编号 Record Number 10.1 标准储备溶液配制记录 Standard Stock Solution Preparation Record FM-QP008-04-CN-CCL.01 10.2 标准工作溶液配制记录 Standard Work Solution Preparation Record FM-QP008-05-CN-CCL.01 10.3 六价铬数据记录表 Chromium(VI)Analysis Worksheet(2)FM-QP005-IO003-GZ-CCL.01 -END-