有害物质管控教材.ppt

Dans lintrt des entreprises et des Hommes,Control Material or Control Substances?Treating the symptoms,but more to the root cause!Hazardous Substances Deep Control Plan Analysis A plan,which can treat the symptoms,but also the root cause控 材 还 是 管 质？治 标 更 要 治 本！有 害 化 学 物 质 管 控 深 入 方 案 分 析 标 本 兼 治 的 方 案,BureauVeritas 法国国际检验局 BV2008.6,Darryl YunAnalytical,BureauVeritas,RoHS EU Directive 2002/95/EC RoHS不仅仅等于一个欧盟对于电子电器产品有害物质限制指令RoHS=Restricted Hazardous substancesRoHS是各种有害物质限制的意思More and more RoHS regulations are issued in the world,and more complicated to treat with目前世界上越来越多的有害物质限制要求被提出，而且越来越复杂，难以应对。We will meet a world war,the environmental protection war,the hazardous substances prohibition law.我们将面对的是一场战争，一场环保战争，一场有害物质限制战争,它将推倒旧的，您将不得不改变，而且在“为人类的生存和幸福”的旗帜下。So we need to CHANGE AND IMPROVE:所以我们需要改变和进步，从以前应对欧盟2002/95/EC应对方法中跳出来：FROM CONTROL OF MATERIAL TO CONGTROL OF SUBSTANCES 从对材料的控制发展到对于物质的控制 CONTROL FROM MATERIAL SUPPLY CHAIN TO SUBSTANCE SUPPLY CHAIN 从对材料供应链的控制，发展到对物质（配方）供应链的控制 GOT BOM TO BOS 获取的信息：从材料清单转而物质清单，也就是配方物质。,Foreword 前言,control banned phthalates控制禁用邻苯二甲酸酯的使用,-Control Lead or Cadmium stability using 控制铅、镉稳定剂的使用 Control UV320/326/327/328,to prevent Benzotriazole 控制紫外稳定剂(UV320/326/327/328)来避免苯并三唑-Control TPNN to prevent NP 通过控制亚磷酸三壬基苯酯来避免壬基酚,control restricted flame retardants,such as PBB/PBDE 控制限制阻燃剂的使用，如PBB/PBDE,control the concentration of PAHs of Carbonize,such as heating,control the purity of solvents and paste.控制多环芳香烃化合物的浓度，如碳黑，先烘以下！控制溶剂和浆料的纯度。,control the purity of Mineral oils for PAHs通过控制矿物油的纯度来控制多环芳香烃化合物的浓度,At one time,we should also take care:同时，还要注意：Shall know the substances change situation of materials during the production.For example:要了解材料中物质在生产过程中的变异情况，如以下的例子：,Situation 现象：in PCB,found high lead containing in some solder point,but some not 电路板上，有的焊点高铅，有的不是the container contain solders,found the last 1/5 with high lead 盛焊料的焊杯，下部剩下的1/5，会发现高铅buy the solder thread,found one part contain high lead 一起买的焊锡丝，总有一段高铅,Lead separate out because of gravity铅的比重偏析。,Why?为什么？,Possible 可能性：pin contain lead 接脚里有铅the soldering process exist the situation that lead separate out 焊接过程存在偏析想象,Foreword 前言,-Chemical substances control should also be combined with other requirements,such as RoHS verification process should be followed with safety certification(such as GS/CE).化学物质的控制，还要和其他的要求结合在一起，如RoHS的确认过程应该和安规认证(如GS或CE)结合在一起。,Production process control was also very important!For example:生产过程的控制也非常重要。如以下的例子：,Situation 现象：Found PAHs in Plastic with painting;发现在喷了漆的塑料上含有多环芳香烃化合物-no PAHs in base Plastic;塑料里面没有PAHs-low PAHs in Painting;染料里面也没有PAHs,Why?为什么？,Before painting,worker use petrol to clean the surface,and petrol contain high concentration PAHs发现，在喷漆以前，工人用汽油擦拭清洁表面，而汽油中含有大量PAHs.,Foreword 前言,So testing is not the key point,but the material assessment and.deep substances control.因此，检测不是一切的，而应该是材料评价和物质控制,Supervise hazardous substances监控危险物质-some material dont need to test for some restricted items 有的材料不必进行一些禁用项目的测试-some material need to test more 有的材料要加倍进行测试监控,Reduce cost减少费用,PAHs(PAK)+GS多环方向烃化合物新要求,Historical 历史,In 2005 and 2006“Stiftung Warentest”(independent German consumer protection organization)examines consumer goods and found alarming levels of PAH amongst other chemicals 在2005年和2006年间，“Stiftung Warentest”(一家独立的德国消费者保护组织）发现在一些消费产品的以下部件材料中含有多环芳香烃化合物，-in rubber handles of tools 在工具的塑胶手柄上-In plastic handles of pushchairs,electrical appliances and torches 在手推车、电子产品和火把的手柄上,Recall：In Germany and Belgium,from Jul,2005 to Jul,2007,there were a at least US$100M products which were recalled,without any correlative law or directive.招回案例：在德国和比利时，从2005年7月到2007年7月份已经至少有超过1亿美金的产品 在没有明确指令和法律的情况下涉及被商家招回。PAHs被认为有致癌作用。From April 1st 2008,GS Mark certified will have to comply with new requirements covering Polycyclic Aromatic Hydrocarbons(PAHs).从2008年4月1日开始，GS产品认证都必须加入新的要求 多环芳香烃化合物。This GS is as well as the relevant safety standards.GS是相应安全标准的认证。Previously the voluntary PAH requirement becomes mandatory.以前自愿性的多环芳香烃化合物PAHs的要求变成强制性的了。The requirement and test method will be added to the ZLS standard ZEK 01-08 相应的要求和检测方法：ZEK 01-08,Historical 历史,Limits for PAH in consumer products 消费产品中多环芳香烃化合物的限量指标,*If the limits of category 1 are surpassed but the limits of category 2 still met,the confirmation of suitability of contact with foodstuff or the oral mucosa can be verified by an additional migration test of the PAH components according to DIN EN 1186 and 64 LFBG 80.30-1.The results of the migration test shall be evaluated according to law criteria for foodstuff.*如果检测结果超过了1类的限制但又不超过2类，对于食品接触性材料或口腔粘膜接触性材料的适当的确认工作应该进行，相关验证工作是通过增加迁移测试来进行，方法为根据DIN EN1186和 64 LFBG 80.30-1对PAH的迁移量进行测试；相应的结果将根据食品法律来判定。,Health Hazards/Environment 危害健康和环境物质 Mutagenic,carcinogenic,reprotoxic 诱导有机体突变物质、致癌物和生殖毒性物质 Persistent Organic Pollutants(POP)under United Nations Economic Commission for Europes(UN ECE)Protocol on POP and subject to obligation to reduction 持久稳定有机污染物（POP）(根据欧共体协议）,In body BaP is converted to compound above leading to DNA distortion and cancer 在生物体内，苯并(a)芘 被改变为一类物质能够导致DNA发生变化而容易得癌症。,Example Benzo(a)pyrene:苯并(a)芘 First chemical carcinogen to be discovered 被发现的第一个化学致癌物质 Class II carcinogen,mutagen and reprotoxic II级诱导有机体突变物质、致癌物和生殖毒性物质 Highly toxic 高毒性,BaP,What is PAH?什么是PAH,Harmful Hammer handle：2200 mg/kg PAH,transfer to skin=3520 cigarettes.锤柄有2200毫克/公斤的PAHs,转移到皮肤的相当于3520根香烟。PAHs show fluorescence blue under UV light PAHs在紫外灯下呈荧光蓝,What is PAH?什么是PAH,PAHs are widespread persistent organic pollutants in air,soil and water PAH是广泛持久稳定的有机污染物，存在在空气、土壤和水中 Directly found in Crude oil,coal,coal tar,creosote 直接可以在原油、煤炭、煤焦油和杂芬油 Formation from incomplete burning of hydrocarbons 碳氢化合物的不完全燃烧 Coal,gas,oil,wood,tobacco and charcoal meat,naturally occurring fires including wood burning stoves and fireplaces 煤炭、汽油、油、木材、烟草和烤肉，Survivor of combustion from automobiles and airplanes 汽车和飞机燃油的燃烧残留 Pyrolysis of organic matter,refining oil 有机物和精炼油的裂解产物 Commercial Usage-Pharmaceuticals,dyes,plastics，pesticides 商业用途 药品、颜料染料、塑料、杀虫剂 PAHs,specific refined products are widely used in the field of electronics,functional plastics and liquid crystals.PAHs广泛用于电子/功能塑料/液晶的生产.Acenaphthene:Intermediate for naphthalic acids,naphthalic anhydride(intermediate for pigments)and for acenaphthylene(intermediate for resins);Intermediate for dyes,soaps,pigments,pharmaceuticals,insecticide,fungicide,herbicide and plant growth hormones.It is used to manufacture plastics and as an agent for inducing polyploidy.苊:萘酸/萘酐(颜料的中间体)/亚苊(树脂的中间体)的中间体,染料/肥皂/颜料/药品/杀虫剂/杀真菌剂/除草剂和植物生长激素的中间体.它也作为一种产生多倍诱导作用的助剂用于塑料生产.,What is PAH?什么是PAH,Anthracene:Its oxidation yields anthraquinone,the parent substance of a large class of dyes and pigments;.diluent for wood preservatives;scintillant(for detection of high-energy radiation)蒽:它的氧化生成物蒽醌,蒽的姐妹物质是广泛的染料和颜料物质;木材防腐剂的稀释剂,发光物(高能量放射性的检测)Fluoranthene:manufacturing fluorescent and vat dyes,pharmaceuticals and agrochemicals.荧蒽:荧光和还原染料的生产,药品和农业化学品.Fluorene:basic substance for production of dyes,pigments,pesticides,thermoset plastic and pharmaceuticals;manufacturing fluorenone(mild oxidizing agent)芴:染料/颜料/杀虫剂/热固塑胶和药品生产的基本物质;芴酮的生产(弱氧化剂)Naphthalene:In the production of phthalic anhydride,carbaryl insecticide,beta-naphthol,tanning agents,moth repellent,and surfactants-naphthalene:main use:production of phthalic anhydride(intermediate for polyvinyl chloride plasticizers);also,production of azo dyes,surfactants and dispersants,tanning agents,carbaryl(insecticide),alkylnaphthalene solvents(for carbonless copy paper),and use without processing as a fumigant(moth repellent)萘:邻苯二甲酸酐/胺甲萘杀虫剂/beta-萘酚/鞣革剂/防蛀剂/表面活性剂的生产;主要用途:邻苯二甲酸酐(PVC塑胶的中间体);也用于:生产偶氮染料/表面活性剂/分散剂/鞣革剂/胺甲萘(杀虫剂)/烷基萘溶剂(无碳铜版纸的制造),和熏剂.Phenanthrene:manufacturing phenanthrenequinone(intermediate for pesticides);manufacturing diphenic acid(intermediate for resins)菲:生产菲醌(农药的中间体),生产二菲酸(树脂的中间体).Pyrene:manufacturing perinon pigments 芘:颜料的生产,Banned PAHs list 禁用的多环芳香烃目录,Banned PAHs list 禁用的多环芳香烃目录,How do PAH come into the product?PAHs如何进入产品的？,During the production of rubber(and plastic)fillings are used to get a higher mass of product.This turns the product hard.To re-soften the material mineral oils are added.Often these mineral oil contain PAH as an impurity.在橡胶（和塑料）的生产过程中会加入一些填充物以增强产品的强度，这样会使产品变得很硬，为了使产品重新变软，会加入软化剂矿物油。不纯的矿物油经常会导致PAHs问题。Conservation agents(Naphthalene,etc)贮存剂（如萘等防腐剂）Carbon black as dying agent 染料中碳黑含有PAHs Solvent 溶剂 Dis-mould oil or agent 脱模油 Paste 浆料 The following materials are examples that could contain PAHs:以下的材料是有可能含有PAHs的一些材料-Elastomers(plastic and rubber material),and soft plastics and rubbers.弹性（软性）的塑料和橡胶材料-Black or dark colored Polymer 黑色或深色聚合物-Coatings and varnish，and glue.油漆和清漆层,和胶水。-Materials treated with conservation agents(Naphthalene)(e.g.Leather products,wood,bast and natural bristle).经过防腐处理的材料，如皮革、木材、树皮和天然猪鬃。,As the ZLS decision EK1-374-08e PAH guideline for Electrical Products Components need to be touched,during the actual use.Forget the components which cannot be touched easily in normal time.Give up the possible skin contact during installation,repairing,waste treatment,etc Material policy:-soft plastic,rubber,with all colors-black and dark color plastic or rubber.-painting and coating-natural material,Test Policy for GS Which kind of components need to be tested？GS的测试准则 哪些需要进行测试,Check raw materials for PAH content检查原材料中是否有PAHs Use“clean“raw materials 使用清洁的原材料 Avoid the usage of uncontrolled materials避免使用非受控的材料 Spread information about PAH了解PAH传播的信息 Knowledge about raw materials了解原材料的知识 Knowledge about impact了解相应的影响BOM to BOS 从材料清单走向物质清单Material control to Substances control 从对材料的控制走向对于配方的控制,How to control?如何控制,New situation of RoHSRoHS 的新情况,IEC 62321 ED1-new version:IEC 111/95CDV（published in Dec.,2007)新的版本：IEC111/95CDV(2007年12月发表）It replaces document 111/54/CDV(rejected in Oct.,2006).Whilst not officially released as a standard,the document is a useful guide to follow for RoHS testing.它代替了111/54/CDV(2006年10月已经被否决），同时并不作为官方标准进行发表，而是RoHS测试的指导性文件.Some change on Analysis of PBB/PBDE:PBB/PBDE分析方法的改变-extraction time:from”about 2 hours(20 extraction cycles)”to“at least 2 hours with keep each cycle as 2-3 mins.”萃取时间:从大约2个小时(20个萃取循环)到 至少2个小时(保持2至3分钟一个萃取循环)-prevent light during extraction(emphasis)再次强调了萃取过程中的避光 Analysis on Cr(VI)in plating of metal.-Main Test method,主要的检测方法 1.IEC 111/95/CDV(Project No.IEC62321),spot test,if found red,then use boiling water extraction procedure,measured by UV-Vis 擦拭实验,如果发现红色,则用水煮萃取过程,并用分光光度计而是测试,detection limit 检出限:0.02mg/kg with 50cm2 sample surface area;if detection limit,then fail;如果大于检出限,则是阳性结果,判不合格.2.EN15205:2006 boiling water extraction procedure,measured by UV-Vis,水煮萃取过程,并用分光光度计而是测试,detection limit 检出限:0.1g/cm2;if detection limit,then sample contains Cr(6+);如果大于检出限,则样品含有六价铬.,Test method standard for RoHSRoHS的测试方法,Some topic during the meeting in Tel Aviv in Mar.10/11 特拉维夫TC111会议的一些议题：-Try to put(informative)annexes into normative body(GC-MS,Cr VI methods)将六价铬测试方法和气质联用方法放入附件中。-Have the possibility to include additional test methods 加入可能的其他附加方法，如EN15205.-Try to merge PAS on sample disjointment with the IEC 62321 尝试将样品的拆解也放入标准，也有意见将另外设立方法：-62xxx 1 General Rules(including sample preparation)通用规则（包括样品准备）-62xxx 2 Method(including possible specific indication for sample preparation)方法(包括可能的对于样品准备的特殊指导）-62xxx 3 Method(including possible specific indication for sample preparation)方法(包括可能的对于样品准备的特殊指导）Have the possibility to Include new substances(e.g.the ones suggested by Norway in their draft legislation or by the(soon to be published)RoHS revision)挪威代表提出了是否有可能将新的限制物质（RoHS有可能会扩项）也加入到这个标准中。,Test method standard for RoHSRoHS的测试方法,The time frame of the publication of the standard should be the following:标准发布时间表Meeting Tel Aviv 10.&11.MarchIssue CC with observations14.MarchDraft FDIS to task leader19.MarchReviewed Draft FDIS to Markus1.AprilFDIS English 4.AprilFDIS French 30.AprilFDIS CO,official publication27.JuneVoting ends 29.AugustIS Sept./Oct.Meeting(Korea)13.(PM)/14./15.October,-The electronics industry has seen its first prosecution for noncompliance with the RoHS directive.电子工业已经有第一起由于不符合RoHS的要求而被起诉的案件。At the end of September,a U.K.company whose name was not disclosed was accused of marketing lead-containing products that violated the RoHS Lead restrictions.在2007年9月底，一家英国的公司被发现其产品中含有被RoHS禁止的铅，遭到控告。-As a lot of political consideration and pressure,new RoHS will be pushed out,由于一些政治考虑和压力,新的RoHS将被推出（2010年）-The pressure of PoHS 挪威PoHS的压力-The pressure of the implementation of ROHS RoHS执行过程不是十分顺利，需要新的推动力-The pressure of new environmental target 新的环保目标的压力-More and more TBT,to protect EU enterprises.为保护欧盟企业，也需要更多的技术性贸易壁垒 New RoHS will be pushed out,and will add a lot of new restricted items;till now about 460 substances was brought forward,but 7 items was the hot;they are:Arsenic,Beryllium,HBCDD,TBBP-A,MCCP,Phthalates,Bisphenol-A.Denmark,UK some EU countries support this.新的RoHS会增加很多新的限制项目，目前已经有超过460个物质被提出，但最有可能的是以下内容：砷、铍、六溴烷十二烷、四溴双酚-A，中链氯化石蜡、邻苯二甲酸盐类、双酚-A等。包括丹麦、英国等欧盟国家都支持这一改变。,Current situation for RoHS implementation目前RoHS执行的情况,-Cancel exemption:Deca-BDE will be restricted from Jul.1,2008.取消豁免：十溴联苯醚将在2008年7月1日起正式限制使用 The European Court of Justice(ECJ)has ruled in Apr.1,2008,that flame retardant decabromodiphenyl ether(deca-BDE)will be“banned”from electrical and electronic equipment from the end of June.The European Commission(EC)had originally granted an exemption for deca-BDE from the list of banned substances under the RoHS Directive Amended version 2005/717/EC.The current exemption will apply until the 30th of June 2008.Therefore the exemption known as 9a ends on that date.欧洲司法法庭在2008年4月1日规定：作为阻燃剂的十溴联苯醚将在六月底禁止使用在电子电器产品中。欧盟关于十溴联苯醚豁免的指令：RoHS指令的修订版2005/717/EC将十溴联苯醚豁免了，现有的豁免将被继续用到2008年6月30日，也就是说对于十溴联苯醚的第9a条豁免将在那一天终止。-New Exemption 新的豁免：2008/385/EC,issued in Jan.4,2008 2008年1月4日发布30.Cadmium alloys as electrical/mechanical solder joints to electrical conductors located directly on the voice coil in transducers used in high-powered loudspeakers with sound pressure levels of 100 dB(A)and more.音压大于100dB(A)的大功率扬声器中，直接位于转换器音圈上的连接电导体的作为电器/机械焊料的镉合金。31.Lead in soldering materials in mercury free flat fluorescent lamps(which e.g.are used for liquid crystal displays,design or industrial lighting).无汞平板荧光灯（如用于液晶显示、设计或工业照明的荧光灯）中的焊料中的铅。32.Lead oxide in seal frit used for making window assemblies for Argon and Krypton laser tubes.氩和氪激光管中，使用于视窗装配的密封玻璃中的氧化铅。,Current situation for RoHS implementation目前RoHS执行的情况,Halogen Free Solution无卤素化和解决方案,What is Halogens and its applications?什么是卤素及其应用？,Fluorine 氟,Chlorine 氯,Bromine 溴,Iodine 碘,Astatine砹,Why is there a need for Halogen-Free products?为什么需要“无卤”产品？,The term implies Halogen-Free means the product material does not contain any compounds derived from these elements.“无卤”意味着产品材料不包含由这些元素组成的任何化合物.Harmful properties of the use of Halogens 使用卤素的有害性-Carcinogenic 致癌-Release toxic gas when combusion:Dioxin/Furan 燃烧时释放有毒气体,二恶因和呋喃-Toxic for immunity system,and effect incretion system,toxic for reproduction 免疫系统毒性、内分泌系统影响、对生殖系统的毒害-Mutagenic 诱导有机体突变-Most of halogen su