《聚合物特征和试验》PPT课件.ppt

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 behavior， 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 content，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2.5-6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 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2.16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 continued 熔体流动速率（MFR)（续）,Mfr (gms/10 minutes) = weight of extrudate / time interval MFR（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 testing 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 Method 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 additive 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 include 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 Fluorescence Spectrometer XRF: 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,Ethylene 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 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 extraction 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 samples NMR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 from 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 placed 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 it BP 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(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 For 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, 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 dish, these are placed in seed counter, and the number of pellets are counted. 在称量盘中称重大约0.96-1.04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 suppliers 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 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 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 Park Chocolate 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 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: 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 conditions, 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, 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 RCP 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 Calorimetry DSC-差示扫描量热法,Thermal properties 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 2004 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: 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 parts, 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/purge 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 Procedure 美国材料协会（ASTM）模塑成型步骤,Mold Temp 60 +/- 3C，模具温度603C Cycle 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0.7MPa Constant part 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 (small 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 anymore: 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 load/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 MPa,General 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 on 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0.25mm（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（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 sample (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 i