《聚合物特征和试验》PPT课件.ppt

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1、Polymer characterization and testing聚合物特征和试验Testing and characterization(generally 3 categories)试验和特征（通常可分为三类）Production lab testing for polymer QA release为发放聚合物质量保证书而进行的生产实验室试验Mfr,solubles,additives,etc，熔体流动速率（MFR）、可溶性和添加剂等Non-routine polymer structure testing非常规的聚合物结构试验MWD,tacticity,melting behavi

2、or，分子量分布（MWD）、立构规正度、熔融特性Application testing(how does it perform post processing)应用试验（在后加工过程中表现的特性）Tensiles,HDT,flex mod,impact,etc，拉伸强度、热变形温度（HDT）、弯曲模量、抗冲击强度等Testing of molded parts(microscopy,gloss,etc)，对模塑零件进行的试验（显微镜试验、表面光泽等）Production testing生产试验Mfr，熔体流动速率（MFR)Additive content，添加剂含量Ethylene conte

3、nt，乙烯含量Hexane extractables，己烷可抽提物Decalin solubles，十氢化萘可溶物Xylene extractables，二甲苯可抽提物Volatiles，挥发份Yellowness index，黄度指数Pellet size，塑料粒子尺寸Powder particle size distribution，粉体颗粒度分布Powder metals analysis，粉体金属含量分析Dirt/contamination/pellet appearance test，杂质污染物以及粒子的外观试验Filter pressure rise/gel test，过滤器压力升

4、高凝胶试验Mfr熔体流动速率ASTM D1238美国材料实验协会ASTM D1238（试验方法的标准）Measures viscosity of PP melt(a function of Mw)测量聚丙烯熔体的粘度（是分子量的函数）Samples size from 2.5 to 6.0 grams(higher MFR requires more sample because more flows through machine during test)样品重量克（MFR较高的样品，由于在试验中流经测试仪器的流量较大，所以需要更多试样量）Cylindrical chamber filled

5、 with resin and piston set in place将被测树脂填满圆筒形的测试管，将活塞安放就位After 4 minute preheat,2.16kg weight placed on piston and piston pushed to calibration mark(6 minutes)预热4分钟后，将公斤的重锤安放在活塞的顶端，并将活塞推到校准的标记位置（6分钟）Cut extrudate start timer.At end of time period,cut extrudate切断熔体的挤出条，按动秒表计时，在定时周期结束时，再次切断熔体的挤出条Mfr c

6、ontinued熔体流动速率（MFR)（续）Mfr(gms/10 minutes)=weight of extrudate/time intervalMFR（克10分钟）挤出条的重量时间间隔Generally an automated process通常是一个自动进行的测试过程Customers often have only 1 plastometer;may not agree with our lab客户通常只有一台塑性计，有可能和我们实验室仪器的型号不同Tinius Olsen MP600=右图为Tinius Olsen MP600 型Multiple extrusions/MFR t

7、esting measures additive package effectiveness多次挤出熔体流动速率测试，测量添加剂配比的有效性Additive content添加剂含量Only one“key additive”is measured in the pellet 只测定塑料颗粒中“关键添加剂”的含量The key additive level is used as an indicator of total additive level and other additive levels.根据各项添加剂的添加比例，用这项关键添加剂的含量来表示总的添加剂含量以及其它添加剂含量Met

8、hod depends on the additive Masterbatch being correct!本方法取决于添加剂母料混合物的配方比例必须是正确的Some additives are easier to measure with precision than others(typical key additives are phenolics,phosphites,and CaSt or DHT).某些添加剂要比其它添加剂更容易精确测定（常用的关键添加剂有酚醛树脂、磷酸酯，和硬脂酸钙或二丁基羟甲苯（DHT）Specific tests used to determine addit

9、ive level include FTIR and XRF用于测定添加剂含量的特殊试验方法包括富利埃变换红外光谱法（FTIR)和X射线荧光分析法（XRF）FTIR富利埃变换红外光谱“Fourier Transform InfraRed”Spectroscopy“富利埃变换红外”光谱Good for Phenolics,Hindered Phenols(Primary stabilizers and UV Stabilizers),and similar molecules适合于酚醛树脂、受阻酚(主要的稳定剂和紫外光稳定剂)以及类似分子的检测Common Key additives inclu

10、de Irganox 1010/3114,DGMS,and Tinuvin 622,and Sodium Benzoate常用的关键添加剂包括 Irganox 1010/3114、DGMS 以及 Tinuvin 622 和苯甲酸钠Pellets are compression molded into sheet,which is inserted into machine先将样品塑料粒子压制成薄片，然后将样片插入到检测仪器中Calibration curve needed to calculate additive level需要用校正曲线来计算添加剂的含量XRF:X-Ray Fluoresc

11、ence SpectrometerXRF:X-射线荧光光谱仪Good for additives containing Calcium,Phosphorus,Sodium,Sulfur,Zinc适合于检测含有钙、磷、钠、硫、锌的添加剂Pellets pressed into plaque and inserted into machine先将试样塑料粒子压制成型为样板，然后将样板插入检测仪器Need to have a calibration curve for additive必须先建立一条添加剂含量的校正曲线 添加剂元素硬脂酸钙钙，CaDHT镁，Mg磷，P磷，P磷，P磷，P磷，P磷，P柠檬

12、酸二氢钾钾，K钠，Na苯甲酸钠钠，NaDSTDP，硫代二丙酸二硬脂醇酯 硫，SDMTDP，硫代二丙酸二甲酯硫，SBZ，二丁基二硫代氨基甲酸锌 锌，ZnEthylene Content乙烯含量Uses FTIR(pressed plaques,etc)采用富利埃变换红外光谱（试样压片等）Calculates计算Total weight percent ethylene乙烯的总重量百分比含量Weight Percent ethylene in the random copolymer segment无规共聚物片断中的乙烯重量百分比含量Calculates the percentage of the

13、 impact copolymer composed of ethylene-propylene random copolymer计算由乙烯-丙烯无规共聚物组成的高抗冲共聚物的百分比含量Used for QC control and product release用于QC控制以及发放产品质量证书Hexane Extractables己烷可抽提物Pellets are ground into a powder 先将塑料粒子磨成粉末Refluxed in boiling hexane for 3 hours in a thimble放在套管内用沸腾的己烷回流三小时Weight lost in ex

14、traction is reported as%hexane extractables称重计算抽提失重，计作己烷可抽提物百分比 In plant environment,%HE is also measured by NMR在工厂环境中，己烷可抽提物百分比也可以用核磁共振法（NMR）进行测定Same sample prep准备相同的样品NMR must be calibrated based on numerous known samplesNMR必须用各种已知的样品进行校正Decalin and Xylene Solubles十氢萘和二甲苯可溶物Xylene extracts more fr

15、om the resin than hexane二甲苯可以比己烷从树脂中抽提出更多的提取物Decalin extracts more from the resin that Xylene十氢化萘可以比二甲苯从树脂中抽提出更多的提取物Decalin test procedure:十氢化萘试验步骤：powder sample is dissolved in heated decalin将粉状样品溶解在加热的十氢化萘中the solution is chilled at 0C,and then filtered将溶液在0C下冷冻，然后进行过滤The resulting solution is pla

16、ced in a weighed pan,and heated at 120C for 2 hours.Material in pan is decalin solubles.将过滤所得的溶液放置在一个称量盘中，在120C下加热两小时，称重盘中的剩余物料计作十氢化萘可溶物Xylene typically not used by BP NA,though other suppliers use itBP 北美通常不采用二甲苯可溶物指标，虽然其它供应商采用这个指标NMR is also used to test DS and XS也可以用核磁共振法(NMR)进行十氢化萘可溶物(DS)和二甲苯可溶物

17、(XS)试验Oven Volatiles烘箱挥发份试验Sample is sealed in metal container when taken from unit 将从生产装置上取来的样品放置在密封的金属容器中For powder,20 g is placed into a pre-weighed disposable aluminum dish and heated at 105C for one hour.The weight lost is the%volatiles.对于粉状样品，取20克样品放置在预先称重的一次性铝盘中，然后在105C下加热一小时，称重计算失重，计作挥发份百分比F

18、or pellets,5 g is place in a dish,heated for one hour at 165C.Weight lost is%volatiles.对于颗粒状样品，取5克样品放置在预先称重的一次性铝盘中，然后在165C下加热一小时，称重计算失重，计作挥发份百分比Reminder:weight lost could be oligomers,additives,water,or anything else that happened to be on or in the sample!注意：失重的物质中可包括低聚物、添加剂、水以及任何偶然沾染到样品表面或进入样品中的其它

19、物质Yellowness Index黄度指数Hunter Lab colorimeter used for test试验用Hunter试验室色度仪进行Pellet YI measured by placing pellets into sample cup and measuring with device将颗粒料放置在样杯中，然后用色度仪进行颗粒料的黄度指数测定B color sometimes used by film customers有些时候薄膜制造商采用B色度Old method included pressing a film from the powder or pellets,

20、and then measuring the film老的测试方法还包括将粉料或颗粒料压制成薄膜，然后用薄膜样进行色度测试Additional thermal history makes this a less repeatable,more variable test由于制样过程中承受的热经历，老方法的重现性较差，测试结果的变化也较大Pellet size颗粒料的粒度Reported in#of pellets/g以颗粒数克计Seed counter used采用种子计数器进行测试Roughly 0.96 to 1.04 grams of pellets are weighed into a

21、 dish,these are placed in seed counter,and the number of pellets are counted.在称量盘中称重大约克的样品颗粒，然后放入种子计数器进行颗粒数计数Many ways to test/report:有许多测试报告的方式：Some customers count by hand(this can lead to debates over what is considered a pellet vs a chip or chafe）有些客户采用手工计数法（这种方法在决定哪些颗粒算作碎片或磨屑时会导致争议）Some supplie

22、rs report g per 100 pellets or a similar measure有些供应商报告为每100颗塑料粒子的重量（克），或类似的计量方法Powder particle size distribution粉料的颗粒度分布Malvern Matersizer measures the size of particles falling from a powder feeder using a laser light source and multiple detectors采用Malvern Matersizer 激光粒度仪作颗粒度测定，被测粉料的样品从加料器中加入，使用激

23、光光源和多通道检测器进行颗粒度计数Software reports result使用专用的软件来报告测定的结果Sieve test often used(more labor intensive)经常采用筛分试验（但需耗费较多的人力）Powder Residual Metals Analysis粉料残余金属含量分析Uses XRF instrument and procedure采用X-射线荧光光度计和测试步骤进行测试Typically track aluminum,titanium,and chlorine通常追踪铝、钛和氯的残余量Can be used to help determine

24、catalyst activity(how much catalyst is needed to produce X kg of PP)测试结果可以用于决定催化剂的活性（生产X公斤聚丙烯需要多少催化剂）Dirt/Contamination/Appearance杂物污染物外观For dirt and contamination,a 4”X 4”X 1/8”plaque is compression molded.压制一个4”X 4”X 1/8”的样板，用于杂物和污染物测定Plaque visually inspected for dirt&contamination对样板进行杂物和污染物的目视检

25、测Pellet appearance 45 g of pellets poured into square tray 1 pellet deep塑料粒子的外观将45克塑料粒子倒入一个颗粒深度的方型盘中，检查Fines are small particles 10 mesh(usually tails from poor cut)粒度小于10目的为细料（通常为粒料切割不当而产生的尾料）Snake skins:thin streamers/films formed from abrasion/buildup of resin in transfer pipes蛇皮料：由于树脂颗粒在输料管道中摩擦和

26、积聚而形成的薄的条带薄膜Angel hair:thin,small strands of fiber/film similar to snake skin(frequently ball together in clumps)毛边料：类似于蛇皮料的薄的、小纤维条薄膜束（常常团聚成为块状）Chips:fragment of pellets片状料：塑料粒子的碎片Smears:flattened pellets not cut cleanly扁平料；没有完全切割好的扁平的塑料粒子Tails:pellets with small strands attached knives not cutting

27、well尾料：连有细小的料束的塑料粒子切割刀片没有切割好Doubles:two pellets joined by film knives not cutting cleanly双联料：由薄膜连接的两颗塑料颗粒切割刀片没有切割干净Filter Pressure Rise/Gel Test过滤器压力升高凝胶试验Neither used at Chocolate Bayou,both run at Deer ParkChocolate Bayou两种试验均不进行，Deer Park两种试验都采用In filter pressure rise test,resin is extruded long

28、enough to flush extruder,a new filter disk is inserted,and a specific amount of resin(or time)is run and the pressure rise measured.This is an indication of resin cleanliness normally not a problem with 4th generation catalysts在过滤器压力升高试验中，先用树脂样进行足够长时间的挤出以便将挤出机冲洗干净，然后插入一张新的过滤盘，挤出规定量的树脂（或运行规定的时间），测定压力

29、的升高。压力升高值可以代表树脂的清洁程度对于第四代催化剂通常不会存在树脂清洁度问题In gel test,the resin is extruded into a film and the film is examined for gels(often an automated process).Generally not an issue with 4th generation catalyst,can be an issue with ICPs.在凝胶试验中将树脂挤出成一张薄膜，然后测定薄膜上的凝胶点（通常采用一种自动的测试过程）。对于用第四代催化剂生产的树脂通常不会出现问题，对于抗冲共聚

30、物（ICPs）会有问题Non-Routine Polymer Testing非常规聚合物试验 GPC MWD气体渗透色谱法测定分子量分布NMR Tacticity核磁共振法测定立构规正度DSC Melting Behavior差示扫描量热法测定熔融特性GPC MWD气体渗透色谱法测定分子量分布Gas Permeation Chromatography气体渗透色谱法Measures molecule length(bigger molecules take longer to go through the column)测定分子的长度（大分子需要花费更多的时间透过色谱柱）Reported as:

31、报告为：Number average molecular weight(Mn)，数均分子量（Mn)Weight average molecular weight(Mw)，重均分子量（Mw)Z average MW(Mz)，Z平均分子量（Mz)Mz+1(the really long chains)，Mz+1（真正的长分子链）Typically used to reverse engineer competitive resins,benchmark a resin,or for experimental purposes(evaluate new catalysts,reactor condi

32、tions,etc).通常用于对工程竞争树脂进行逆向研究，建立树脂的基准样，或用于实验研究的目的（评价新型催化剂、反应器条件等）NMR Tacticity核磁共振法测定立构规正度Nuclear Magnetic Resonance Spectroscopy核磁共振光谱法Expensive，昂贵Determines how carbons are bonded，检测碳原子是如何连接的Tells you how“perfect”or isotactic a resin samples is.可以告诉您，一种树脂样品是如何“结构完美”或全同立规的The higher the isotacticity

33、,the more perfect the molecules,the higher the strength and stiffness全同立规的程度越高，分子的结构就越完美，强度和刚性就越大Lower tacticity desirable for film grades(to help in the film stretching process)and for applications that need lower stiffness对于薄膜级产品以及需要较低刚度的应用，就需要立构规正度低一些的树脂（有助于薄膜的拉伸过程）For homopolymers only ICP and R

34、CP give strange results because of high ethylene content本测定方法只适用于均聚物由于乙烯基含量高，抗冲共聚物（ICP）和无规共聚物（RCP）会给出奇怪的测定结果DSC Differential Scanning CalorimetryDSC-差示扫描量热法Thermal properties 热性能热性能Melting point熔点温度Melting enthalpy熔融焓Crystallization point结晶温度Crystallization enthalpy结晶焓 From GHO,Secco Training June 2

35、004 取自于GHO，赛科培训，2004年6月Application Testing应用性试验Used to compare resins 用于进行树脂的比较Tests suitability for an end-use application对某一项终端应用进行适用性试验Typically test a part made under controlled conditions,such as a tensile bar or cast film常用于对在某一规定条件下制造的部件进行测试，例如，拉伸试条或流延薄膜Most common tests used on PP Datasheets

36、:用于聚丙烯特性数据表的最常用的试验Tensiles,elongation,modulus，抗拉强度、伸长率、模量Flexural modulus，弯曲模量Heat deflection temperature，热变形温度 Impact testing，冲击试验Visual characteristics gloss,blush,haze,etc.，目视特性光泽度、泛红光、浑浊度等Tensile Testing Sample Prep拉伸强度试验准备样品Typically PP,RCP,or ICP pellets典型的聚丙烯、无规共聚物、抗冲共聚物塑料粒子Can use chopped pa

37、rts,reclaim,etc if pellets not available.如果无法获得塑料粒子，可以使用破碎的塑料件、回收料等Tensile bars are molded under standard conditions into a standard mold(ISO,ASTM,etc).Complete Lab Injection Molding machines are sold for this application.拉伸试条是在标准的模具中（ISO，ASTM等）标准的条件下模塑成型的，市场有售用于这项应用的成套实验室注塑成型机Important to flush/pur

38、ge older polymer from extruder.将陈旧的聚合物从挤出机中冲洗清除干净是十分重要的Important to have enough resin(Naperville typically uses 25 lbs per test,most for purging)拥有足够数量的树脂进行试验是十分重要的（在Naperville通常每次试验使用25磅树脂，其中大部分用于挤出机内的物料清除）Important to let molded bars cool(do not stack)使拉伸样条得到充分的冷却是十分重要的（不要将样条堆积存放）ASTM Molding Proc

39、edure美国材料协会（ASTM）模塑成型步骤Mold Temp 60+/-3C，模具温度603CCycle Time:45 sec total，周期：总计45秒20 sec injection，20秒注塑20 sec cooling，20秒冷却5 sec ejection，5秒样条取出Melt Temp varies with MFR(higher mfr=lower temp because of viscosity difference)熔融温度根据MFR而不同（由于粘度的不同，较高MFR的试验采用较低的熔融温度）Back Pressure 0.7 MPa背压Constant part

40、weight is targeted指标是恒定的样条重量Molded Bar Tensiles模塑样条的拉伸试验Sample is inserted into a tensile load tester,which clamps both ends of the bar and pulls until break.Load is measured by a load cell;elongation by the rate of extension(speed of the test).将样条插入一台拉伸载荷试验机，试样两端被夹住并拉伸至断裂。通过一个测力传感器测量载荷，通过延伸的速率（测试的速

41、度）测量伸长率Typically report load and elongation at yield,and load and elongation at break通常报告试样在屈服和断裂时的载荷以及伸长率Modulus(the ratio of stress to strain)is also sometimes reported(load/elongation,typically at low elongations)有时也报告模量（应力应变之比）（载荷伸长率，特别是在低伸长率）Measurement of the tensile behaviour of a specimen(sm

42、all injected piece):tensile modulus,tensile strength at yield and at break样条（小型的注塑件）拉伸特性的测量：在屈服和断裂时的拉伸模量、拉伸强度In Europe,we use:ISO 527，在欧洲，我们采用：ISO 527标准In NA,we use:ASTM D638，在北美，我们采用：ASTM D638标准Units:Modulus MPa(psi in NA)，单位：模量 MPa（北美用psi)Strength at yield and at break MPa(psi in NA)屈服和断裂强度 MPa(北美

43、用psi)Elongation at break and at yield(%)，屈服和断裂伸长率（）Elongation at break断裂伸长率Strength at break断裂强度Elongation at yield屈服伸长率Strength at yield屈服强度Tensile Test Continued拉伸试验 续 yield point beyond which the material deforms irreversibly屈服点：超过该点后材料的变形是不可逆转的 break point where the material can not stretch anym

44、ore:it breaks.断裂点：材料发生断裂，再也无法伸长From G.Hallot presentation摘自G.Hallot 的演示General Rules for Tensiles拉伸试验的通用规律Lower MFR=Lower Tensile Strength较低的MFR=较低的抗拉强度Higher Tacticity=Higher Tensile Strength较高的规正度=较高的抗拉强度Lower Solubles=Higher Tensile Strength较低的可溶物=较高的抗拉强度Narrower MWD=Higher Tensile Strength较窄分子量分

45、布=较高的抗拉强度Nucleation=Higher Tensile Strength晶核形成=较高的抗拉强度Ethylene Content=Lower Tensile strength较高的乙烯含量=较低的抗拉强度Flexural Modulus弯曲模量Measures stiffness测量刚度ASTM D790A-Tests bar molded bar stiffness in a three point test:bar is supported at ends,and a standard tip presses against the middle and measures l

46、oad/resistance.ASTM D790A 在一个三点试验中测试模塑样条的刚度：样条的两端受到支撑，用一个测试尖端压在样条的中部，测试载荷冲击强度，Typically reported as kpsi or MPa通常报告的单位为kpsi 或 MPaGeneral Rules for Flex Mod弯曲模量的通用规律Lower MFR=Higher Flexural Modulus较低的MFR=较高的弯曲模量Higher Tacticity=Higher Flex Mod较高的立构规整度=较高的弯曲模量Lower Solubles=Higher Flex Mod较低的可溶物=较高的弯

47、曲模量Narrower MWD=Higher Flex Mod较窄的分子量分布=较高的弯曲模量Nucleation=Higher Flex Mod晶核形成=较高的弯曲模量Higher Ethylene Content=Lower Flex Mod较高的乙烯含量=较低的弯曲模量Heat Deflection Temperature热变形温度Measures stiffness/heat resistance测量刚度耐热性能Bar is supported at the ends in an oven with a tip under a standard load pressing down o

48、n it.The temperature is increased at a steady rate until the bar deflects by 0.25mm(ASTM D648)将样条两端支撑起来，置于烘箱内，在标准的载荷下用一个测量尖端向下施压。以一个稳定的升温速率升高温度直至样条变形达到（ASTM D648）Typically has same trends as flex mod.通常和弯曲模量有相同的趋势Fillers and nucleation will increase stiffness 填充料和晶核形成会增加刚度Notched Izod Impact Test缺口（

49、艾氏）冲击试验Measures the ability of the polymer to absorb an impact.测定聚合物吸收冲击的能力ASTM D256 uses 1/8”thick bar.NA typically runs notched bar test.ASTM D256采用1/8”厚的样条。北美常采用缺口样条冲击试验Un-notched side is impacted with a pendulum the height to which the pendulum rebounds indicates the energy absorbed by the sampl

50、e(or it breaks)用摆锤冲击样条不开缺口的一侧，摆锤回弹的高度表明了样条吸收的能量（或完全断裂）HPP typically has very poor impact(brittle),especially cold impact均聚聚丙烯通常具有较差的抗冲击强度（脆性的），特别在冷态冲击试验中RCP slightly better无规共聚物的抗冲击强度略好ICP very good;cold impact good enough for bumpers and frozen food containers等规共聚物有极好的抗冲击强度：冷态下的抗冲击强度极好可以制作保险杠和冷冻食品的