聚合物纳米复合材料

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1、CollegeofPolymerScience&Engineering聚合物纳米复合材料聚合物纳米复合材料聚合物共混改性原理聚合物共混改性原理复合体系组合分散相的尺度大小1000nm(1m)1001000nm(0.11 m)1100nm(0.0010.1 m, 101000)0.510nm(5100 ) （1）聚合物/低分子物低分子作增容剂低分子流变改性剂外部热塑性聚合物（2）聚合物/聚合物宏观相分离型聚合物掺混物微观相分离型聚合物合金（1）分子复合物；（2）完全相容型 聚合物合金（3）聚合物/填充物聚合物/填充物复合体系聚合物/填充物复合体系聚合物/超细粒子填充复合体系聚合物纳米复合体系聚合

2、物复合体系的分类第一节第一节 概述概述聚合物共混改性原理聚合物共混改性原理纳米概念的形成n早期，石墨、炭黑中的颗粒n1959年，美国物理学家Richard Feynman提出“what would happen if we could arrange the atoms one by one the way we want them?”n20世纪70年代康乃尔大学C.G.Granqvist & R.A.Buhrman 小组气相沉积制备纳米n20世纪80年代，原西德Gleiter首次制备金属纳米，提出纳米材料及其应用n1981年，IBM发明AFM和STM，推动纳米技术发展n20世纪80年代末期，

3、日本丰田研究中心制得PA6/粘土纳米复合材料聚合物共混改性原理聚合物共混改性原理What nanocomposites areA nanocomposite is defined as a composite material where at least one of the dimensions of one of its constituents is on the nanometre size scale.1.纳米复合材料(nanocomposite)定义:聚合物共混改性原理聚合物共混改性原理纳米复合材料非聚合物纳米复合材料金属/金属金属/陶瓷陶瓷/陶瓷聚合物纳米复合材料有机/无机纳米

4、复合材料聚合物/聚合物纳米复合材料聚合物基聚合物基无机物基分子复合原位复合微纤/基体Classification of nanocomposite 聚合物共混改性原理聚合物共混改性原理Polymer/inorganic nanocomposites Polymer nanocomposites are generally defined as the combination of a polymer matrix resin and inorganic particles (particles, layers or fibres) which have at least one dimensi

5、on (i.e. length, width, or thickness) in the nanometer size range. 2.聚合物聚合物/无机纳米复合材料定义无机纳米复合材料定义聚合物共混改性原理聚合物共混改性原理 纳米纤维 (碳纳米管、纤维素晶须、凹凸棒土 ) 层状无机物层状无机物 ( layered silicates)纳米粒子(CaCO3 、SiO2 、 TiO2、ZnO、Al2O3、Cr2O3 )Schematic of nanoscale fillers第二节第二节.制备聚合物纳米复合材料的无机物的种类制备聚合物纳米复合材料的无机物的种类聚合物共混改性原理聚合物共混改性

6、原理碳纳米管 碳纳米管是由多个碳原子六方点阵的同轴圆柱面套构而成的空心小管，其中石墨层可以因碳纳米管是由多个碳原子六方点阵的同轴圆柱面套构而成的空心小管，其中石墨层可以因卷曲方式不同而具有手性。碳纳米管的直径一般为几纳米至几十纳米，长度为几至几十微米。卷曲方式不同而具有手性。碳纳米管的直径一般为几纳米至几十纳米，长度为几至几十微米。 碳纳米管可以因直径或手性的不同而呈现很好的金属导电性或半导体性。碳纳米管可以因直径或手性的不同而呈现很好的金属导电性或半导体性。 (Iijima 1991)聚合物共混改性原理聚合物共混改性原理 Derived from expandable 2:1 layered

7、 smectite family of clays Isomorphous substitution of atoms creates a charge imbalanceSodium Montmorillonite Platelet StructureNa+Si OxideAl/Mg/Fe Oxide/HydroxideSi OxideNa+ 50nm - 300nm 1 nm 聚合物共混改性原理聚合物共混改性原理Layered silicates Advantages over conventional fillersExpandable structures Individual sil

8、icate layers have at least one dimension in nanoscopic size rangeLayers have high aspect ratios (length/thickness), extremely large surface areas, and high moduliLarge property benefits achievable at very low filler levels as compared to conventional reinforcing additivesWeight saving (2.5 wt% nanoc

9、lay vs. 25 wt% talc)Better processibility ( faster cycling times and quicker fill)Dont need new lines of tools1 nm聚合物共混改性原理聚合物共混改性原理Cationic Exchange of Sodium Montmorillonite+Sodium MMT*Swollen “Organoclay”R1*R2R3CH3N+Cl-+NaClCationic Surfactant (e.g., alkyl-ammonium chloride)= Na= Alkylammonium 蒙脱

10、土族矿物具有离子交换性、吸水性、膨胀性、触变性、黏结性、吸附性等特性。聚合物共混改性原理聚合物共混改性原理插层剂的作用插层剂的作用n利用离子交换的原理进入蒙脱土片层之间；n扩张片层间距；n改善层间的微环境；n使蒙脱土的内外表面由亲水性转化为疏水性；n增强蒙脱土片层与聚合物分子链之间的亲和性；n降低硅酸盐材料的表面能。常用的插层剂有烷基铵盐、季铵盐、吡啶类衍生物和常用的插层剂有烷基铵盐、季铵盐、吡啶类衍生物和其他阳离子型表面活性剂其他阳离子型表面活性剂聚合物共混改性原理聚合物共混改性原理第三节第三节.聚合物纳米复合材料主要制备方法聚合物纳米复合材料主要制备方法 n溶胶溶胶-凝胶法凝胶法(Sol-

11、Gel):烷氧基金属或金属盐等前驱物（水溶烷氧基金属或金属盐等前驱物（水溶性盐或油溶性醇盐）溶于水或有机溶剂中形成均质溶液，溶性盐或油溶性醇盐）溶于水或有机溶剂中形成均质溶液，溶质发生水解反应生成纳米级粒子并形成溶胶，溶胶经蒸发干质发生水解反应生成纳米级粒子并形成溶胶，溶胶经蒸发干燥转变为凝胶。燥转变为凝胶。 n原位聚合法原位聚合法(in-situ polymerization):分散有纳米粒子的单分散有纳米粒子的单体聚合后形成复合体系体聚合后形成复合体系n共混法共混法:聚合物与纳米粒子共混聚合物与纳米粒子共混n插层法插层法:将单体或聚合物插入层状无机物层间形成纳米复合结将单体或聚合物插入层状

12、无机物层间形成纳米复合结构构 聚合物共混改性原理聚合物共混改性原理Preparation Methods原位插层(In-situ intercalation polymerization ) 溶液插层(Polymer intercalation from solution) 熔体插层(Polymer melt intercalation ) Polymer/Layered silicate nanpcomposites聚合物聚合物/层状硅酸盐纳米复合材料制备方法层状硅酸盐纳米复合材料制备方法(插层法插层法)聚合物共混改性原理聚合物共混改性原理Morphology of layered sili

13、cate聚合物共混改性原理聚合物共混改性原理1.In situ Polymerization聚合物共混改性原理聚合物共混改性原理2.Polymer intercalation from solution聚合物共混改性原理聚合物共混改性原理3.melt intercalation聚合物共混改性原理聚合物共混改性原理Mechanically blend polymerorganoclay mixtures above the polymers Tm (i.e., high shear twin screw extrusion)Nanocomposite Formation Technique- M

14、elt Processing (常规做法)hp聚合物共混改性原理聚合物共混改性原理Naoki Hasegawa, et al, Polymer 44 (2003) 29332937a novel compounding process using Namontmorillonite water slurry for preparing novel nylon 6/Namontmorillonite nanocompositesSchematic figure depicting the compounding process for preparing the NCH-CS using the

15、 clay slurryNew method(加入层状无机材料的悬浮液)聚合物共混改性原理聚合物共混改性原理Naoki Hasegawa, et al, Polymer 44 (2003) 29332937Schematic figures depicting dispersion of the Namontmorillonite silicate layers of the slurry into nylon 6 during compounding聚合物共混改性原理聚合物共混改性原理Kinetics of polymer melt intercalationTwo steps for na

16、nocomposite formation:nPolymer transported from the agglomerate-polymer melt interface to the primary particlesnPolymer melt penetrate to the edges of the crystallites The first step is limiting step for polymer nanocomposites formation聚合物共混改性原理聚合物共混改性原理Thermodynamic analysis F = F(h) - F(h0) = E -

17、TS F 0 indicate layer separation is favorable F 0 implies the initial unintercalated state is favorable S S chain + S polymer聚合物共混改性原理聚合物共混改性原理第四节层状纳米复合材料结构与性能第四节层状纳米复合材料结构与性能1.结构结构Layered Nanocomposite structure聚合物共混改性原理聚合物共混改性原理Schematic illustration of two different types of thermodynamically ach

18、ievable polymer/layered silicate nanocomposites.聚合物共混改性原理聚合物共混改性原理Schematic depicting the XRD patterns for various types of structures不同插层结构的表征(X射线衍射法)层状有序结构完全消失完全未解离插层结构插层结构(层间距层间距明显增大明显增大)插层结构均一插层结构无序聚合物共混改性原理聚合物共混改性原理X-ray diffraction pattern of PEO/Na+-MMT hybrid heatedto 80 for 0, 2, and 6 hVai

19、a RA, et al, Macromolecules 1995, 28: 8080MMT片层结构衍射峰聚合物共混改性原理聚合物共混改性原理Temporal series of X-ray diffraction patterns for a PS30/F18 pellet annealed in situ at 160 in vacuumVaia RA, et al, Adv Mater 1995,7,154156聚合物共混改性原理聚合物共混改性原理 2.性能Properties of polymer layered silicate nanocompositesEfficient rein

20、forcement with minimal loss of ductility and impact strengthIncrease thermal stabilityIncrease flame retardant Improved gas barrier properties Improved ionic conductivityReduced thermal expansion coefficientAltered electronic and optical properties聚合物共混改性原理聚合物共混改性原理Properties of Nylon-6 layered sili

21、cate nanocompositesPropertyNanocompositesNylon-6Tensile Modulus (GPa)Tensile Strength (MPa)Heat Distortion Temp ()Impact Strength (KJ/m2)Water Adsorption (%)Coefficient Thermal Expansion ( x,y )2.11071602.80.516.310-51.169652.30.871310-5最有价值的性能变化聚合物共混改性原理聚合物共混改性原理Comparison of the Youngs modulus of

22、clay/nylon-6 nanocomposites and glass fiber reinforced nylon-6 composites with low filler loadingFengge Gao, materials today,2004,50-55In the low filler loading range, clay/polymer nanocomposites have the potential to replace traditional fiber reinforced composites.聚合物共混改性原理聚合物共混改性原理Modulus increase

23、 by layered silicate reinforcement of PA66L. A. GOETTLER, Polymer Reviews, 47:291317, 2007普通层状填料玻纤增强聚合物共混改性原理聚合物共混改性原理(a) Organoclay (OMSFM) (wt %) dependence of HDT of neat PLA and various PLACNs. (b) Load dependence of HDT of neat PLA and PLACN7Thermal propertiesSuprakas Sinha Ray, et al, Chem. Ma

24、ter. 2003, 15, 1456-1465聚合物共混改性原理聚合物共混改性原理TGA analysis of PDMS(solid line).and PDMS nanocomposite(dashed line)(mass fraction 10% mica-type-silicate, MTS). Lines were added to indicate 50% mass loss.Burnside, S.D., Giannelis, E.P., Chem. Mater. 1995. 7, 1597聚合物共混改性原理聚合物共混改性原理Comparison of the Heat Re

25、lease RateHRR. plot for nylon-6, nylon-6 silicate-nanocomposite(mass fraction 5%)at 35 kW/m2 heat flux, showing a 63% reduction in HRR for the nanocomposite.flame retardantJeffrey W. Gilman, Applied Clay Science, 15, 1999.3149放热速率显著下降聚合物共混改性原理聚合物共混改性原理PP及其纳米复合材料的热释放速率对比（热通量=35kW/m2)聚合物共混改性原理聚合物共混改性原

26、理Flammability performance for nylon-6 nanocompositesnanocomposite works with other flame retardants in a synergistic or cooperative manner to lower the polymer flammability (heat release rate)Comparison between nanocomposites and conventional flame retardantsAlexander B. Morgan, Polym. Adv. Technol.

27、 2006; 17: 206217工业上评价材料阻燃性能的检测标准聚合物共混改性原理聚合物共混改性原理Beyer, G., 2002Nanocomposite Power Cable Kabelwerk Eupen聚合物共混改性原理聚合物共混改性原理Selected video images at 100, 200, and 400 s in nitrogen at 50 kW/m2.Takashi Kashiwagi, Polymer 45 (2004) 881891Mechanism:The silicate-rich char acts as an excellent insulator

28、 and mass transport barrier,thereby reducingthe heat release ratemand slowing down the escape of volatile products released as the polymer decomposes.阻燃机理:硅酸盐作为隔绝火焰,热量和物质的材料减缓了聚合物分解时挥发份的释出聚合物共混改性原理聚合物共混改性原理Proposed model for the torturous zigzag diffusion path in an exfoliated polymer-clay nanocompo

29、site when used as a gas barriergas barrier properties聚合物共混改性原理聚合物共混改性原理Montmorillonite content dependence of permeability coefficient of water vapor in polyimide-clay hybrid.Montmorillonite content dependence of permeability coefficient of O2 in polyimide-clay hybridKAZUHISA YANO,et al, Journal of P

30、olymer Science: Part A Polymer Chemistry, Vol. 31,2493-2498 (1993)应用价值:食品保鲜聚合物共混改性原理聚合物共混改性原理Starch-clay nanocomposite bag made by film blowing technology. This bag has been stored filled with water did not show any release nor failure after 3 weeks聚合物共混改性原理聚合物共混改性原理(a)Real picture of biodegradabili

31、ty of neat PLA and PLACN4 recovered from compost with time. Initial shape of the crystallized samples was 3 *10 *0.1 cm3.Suprakas Sinha Ray,et al, Nano Letters, 2002,2(10),1093-1096 biodegradability可降解性提高聚合物共混改性原理聚合物共混改性原理(b) Time dependence of residual weight, Rw (%) and change of matrix Mw of neat

32、 PLA and PLACN4.Suprakas Sinha Ray,et al, Nano Letters, 2002,2(10),1093-1096 残留率由60%几乎下降为0聚合物共混改性原理聚合物共混改性原理(a)Degree of biodegradation (i.e., CO2 evolution) of neat PLA and PLACN4 under compost at 58 2 . (b)(b) Time dependence change of matrix Mw of neat PLA and PLACN4 under compost at 58 2 Supraka

33、s Sinha Ray, et al, Chem. Mater. 2003, 15, 1456-1465降解速度加快聚合物共混改性原理聚合物共混改性原理Montmorillonite content dependence of thermal expansion coefficient ofpolyimide-clay hybrid at: (a) 150, (b) 200, (c) 250, and (d) 295.KAZUHISA YANO,et al, Journal of Polymer Science: Part A Polymer Chemistry, Vol. 31,2493-2

34、498 (1993)thermal expansion coefficient热膨胀系数降低聚合物共混改性原理聚合物共混改性原理制备聚合物制备聚合物/层状硅酸盐纳米复合层状硅酸盐纳米复合材料遇到的主要问题材料遇到的主要问题n无机相分布不规则；无机相分布不规则；n无机相形态难控制；无机相形态难控制；n存在界面问题；存在界面问题；n分散方法需改进分散方法需改进。聚合物共混改性原理聚合物共混改性原理Influence factors of polymer intercalationOriginal properties of silicate Polymer architectureinteract

35、ion between surface and polymer a. Organically modified layered silicates surface b. Adding a fraction of functionalized polymersProcess condition第五节影响聚合物插层效果的主要因素聚合物共混改性原理聚合物共混改性原理WAXD patterns of organically modified clay: (a) smectite clay modified with C8, C12, and C16 phosphonium salt; (b) smec

36、tite, MMT, and mica clay modified with C16 phosphonium saltOriginal properties of silicate聚合物共混改性原理聚合物共混改性原理Comparison of PC and Nylon 6 NanocompositesWide Angle X-Ray Scattering (HE)2M1T1T (C18)N+CH3CH2CH2OHCH2CH2OHPolymer architecturePA6可以充分剥离层状结构,PC不能聚合物共混改性原理聚合物共混改性原理Schematic illustration of OM

37、LS dispersion process in PP-g-MA matrixinteraction between surface and polymer聚烯烃接枝上极性基团有助于MMT的解离和插层聚合物共混改性原理聚合物共混改性原理 LLDPE M2(HT)2 LLDPE-g-MA接枝上极性基团后MMT在LLDPE中得以充分解离和分散聚合物共混改性原理聚合物共混改性原理Effect of maleation on structure of nanocomposite随接枝率上升,LLDPE插层后的MMT层间结构趋于消失聚合物共混改性原理聚合物共混改性原理8 m Particle 3000

38、PlateletsChemistry Chemistry/Processing ProcessingDispersionDispersionTactoids/IntercalantsPartial DispersionTactoids/IntercalantsTactoids/IntercalantsTactoids/IntercalantsPaul分散机理分散机理Process conditionThree cases involving the interplay during melt processing聚合物共混改性原理聚合物共混改性原理Platelet Exfoliation Me

39、chanism During ExtrusionPlatelets peel apart by combined diffusion/shear processShearOrganoclay particle( 8 m)Stacks of silicate platelets or tactoidsShearing of platelet stacks leads to smaller tactoidsShearStress = ShearDiffusion聚合物共混改性原理聚合物共混改性原理 The key of the formation of nanocomposites is: the

40、re are enough interaction between polymer and layer silicates so that the intercalation and exfoliation can occur聚合物共混改性原理聚合物共混改性原理Co Rotating, Low Shear 15A/PA6Single ScrewCo Rotating, Medium Shear剪切场对改性剪切场对改性clayclay分散状态的影响分散状态的影响聚合物共混改性原理聚合物共混改性原理Network in iPP/clay nanocompositesRheology behavio

41、r聚合物共混改性原理聚合物共混改性原理Selected ApplicationsAutomotive (Enhanced Modulus and Dimensional Stability，Higher Heat-Distortion Temperature，Improved Scratch and Mar Resistance)Packaging (Permeation Barrier)Flame Retardancy聚合物/层状硅酸盐复合材料的应用聚合物共混改性原理聚合物共混改性原理上世纪80年代，日本丰田中央研究院在最早用于丰田车内部件的尼龙6纳米复合材料，但是由于价格的原因很快被放弃了

42、。 通用汽车公司在其2002年的两款新车GMC Safari和Chevrolet Astro 上采用了一种全新的材料聚丙烯/膨润土纳米复合材料制备的脚踏板（step-assist），这项技术创新获得了国际塑料工程师协会的大奖，对整个高分子纳米复合材料的发展有里程碑的意义。汽车的应用聚合物共混改性原理聚合物共混改性原理Toyoto Nylon 6-Clay Hybrid (NCH) 1986In situ polymerization processInjection molded timing belt cover see M. Kawasumi, J. Polym. Sci. Part A:

43、 Polym. Chem., 42, 819 (2004)聚合物共混改性原理聚合物共混改性原理1st Commercial LaunchStep Assist on Astro and Safari Van聚合物共混改性原理聚合物共混改性原理HUMMER H2 SUT: Most Recent Nanocomposite Application聚合物共混改性原理聚合物共混改性原理包装材料包装材料 nHoneywell公司：公司：含2%和4%纳米膨润土的尼龙6，作为中等阻隔材料对氧气敏感产品的包装，其对氧气的阻隔性与尼龙6相比分别提高了3倍和6倍，同时还增加了膜的刚度、耐热性和透明度。 nHon

44、eywell公司：公司：以纳米膨润土作为透过层，以特定尼龙作为氧气捕捉活性层的纳米复合材料。纳米膨润土的作用是保护氧气捕捉层以免其过早耗尽。用于三层结构的PET瓶。nNanocor公司与三菱瓦斯：公司与三菱瓦斯：纳米膨润土加入到无定形的MDX6尼龙中，纳米复合材料的的氧气阻隔性为PET的100倍，作为三层PET瓶中的中间层，据称作为啤酒瓶的货架期可达到200天。nBayer公司：公司：Nanocor的纳米膨润土用于尼龙6的浇注膜，用于多层包装、保护膜和药品的包装等。 nUbe公司：公司：纳米膨润土加入到尼龙6/66的共混物中，作为汽车的燃油系统，2%纳米膨润土含量的尼龙6与未改性的尼龙6相比，

45、对甲醇的阻隔性提高了5倍 。 聚合物共混改性原理聚合物共混改性原理Insert that fits into the shoeNanocomposite Pouch filled with HeliumConverse Basketball ShoePouch by Triton Systems Inc.聚合物共混改性原理聚合物共混改性原理Wilson Double Core Tennis BallCoating Air Defense by InMatTMButyl Rubber Nanocomposite Core聚合物共混改性原理聚合物共混改性原理部分高分子纳米复合材料的提供厂商部分高分

46、子纳米复合材料的提供厂商聚合物共混改性原理聚合物共混改性原理n1.简述双螺杆挤出机生产玻纤增强简述双螺杆挤出机生产玻纤增强PP时的螺杆各时的螺杆各段结构特点和功能段结构特点和功能n2.为什么制备玻纤增强热塑性塑料时要控制玻纤为什么制备玻纤增强热塑性塑料时要控制玻纤长度长度?n3.填料填充聚合物后流动性和力学性能填料填充聚合物后流动性和力学性能(拉伸强度拉伸强度,模量模量,硬度硬度,抗冲击韧性抗冲击韧性,断裂伸长率断裂伸长率)一般会有什一般会有什么变化么变化?填料的表面处理有何作用填料的表面处理有何作用?n4.制备纳米复合材料主要有哪些方法制备纳米复合材料主要有哪些方法?n5.简述任何用插层法制备聚合物简述任何用插层法制备聚合物/层状硅酸盐纳米层状硅酸盐纳米复合材料复合材料