形状记忆聚偏氟乙烯/丙烯酸酯/碳纳米管纳米复合材料的导电及导热性能

利用聚偏氟乙烯(PVDF)微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物(PVDF/ACM)共混材料,为提高其导电及导热性能,于其中引入了碳纳米管(CNT),系统研究了PVDF/ACM/CNT三元体系纳米复合材料的导热及导电性能。结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,碳纳米管的加入使材料导热性能及导电性能有较大程度的提高:质量分数为4%的CNT使材料25℃的电阻值降低至5000Ω/square,导热系数提高至0.157 W/(m·K)。     

形状记忆聚偏氟乙烯/丙烯酸酯/碳纳米管纳米复合材料的导电及导热性能

利用聚偏氟乙烯（PVDF）微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物（PVDF/ACM）共混材料,为提高其导电及导热性能,于其中引入了碳纳米管（CNT）,系统研究了PVDF/ACM/CNT三元体系纳米复合材料的导热及导电性能。 结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,碳纳米管的加入使材料导热性能及导电性能有较大程度的提高：质量分数为4%的CNT使材料25 ℃的电阻值降低至5000 Ω/square,导热系数提高至0.157 W/(m·K)。     

同时添加碳纳米管及石墨烯对热致液晶聚酯形状记忆行为及拉伸性能的影响

利用溶液共混的方法将碳纳米管(CNT)及石墨烯(G)同时加入到热致液晶聚酯中制备纳米复合材料.通过透射电镜(TEM)研究纳米粒子的分散及形貌.采用荧光光谱及拉曼光谱研究碳纳米填料与热致液晶聚酯基体之间存在π-π相互作用.利用电子万能试验机(EUTM)研究了材料的拉伸性能,由于CNT与G与基材之间作用力强,且CNT与G间的协效作用能有效地实现应力转移,同时加入CNT及G有助于提升复合材料的拉伸强度.动态热机械分析(DMA)数据表明,同时添加CNT与G对于复合材料的固定率影响不大,但会降低回复率;同时复合材料的回复应力也得到显著的提升.     

聚降冰片烯/聚乳酸共混物形状记忆效应的研究

将聚降冰片烯(PNB)和聚乳酸(PLA)按照PNB/PLA(80/20)、(70/30)、(60/40)、(50/50)4种不同质量配比进行共混,采用X射线衍射(XRD)、动态力学分析(DMA)、示差扫描量热分析(DSC)等对共混物基本性能进行表征,同时采用DMA-Q800对其形状记忆效应进行探究.结果显示:4种共混物均有明显屈服现象,随着PLA含量的增加,屈服现象越明显;PNB/PLA共混物出现2个玻璃化转变温度(T_g),且不随共混物配比变化而变化;4种共混物均在2θ=18.45o附近出现特征衍射峰,且其结晶度随PNB含量的减少而降低;随PNB含量的增多4种共混物的形状记忆性能提高.对于PNB/PLA(80/20),在双重形状记忆中,其形状固定率为99.88%,形状恢复率为81.04%;在三重形状记忆中,总固定率和恢复率分别为98.83%和94.26%.     

聚偏氟乙烯/蒙脱土纳米复合材料的形态结构

采用有机改性的蒙脱土与聚偏氟乙烯熔融共混, 制备了聚偏氟乙烯/蒙脱土纳米复合材料. 利用X射线衍射分析、透射电子显微镜(TEM)和Molau实验研究了复合材料的微观结构. 通过X射线衍射、傅里叶变换红外光谱(FTIR)以及差热扫描(DSC)研究了有机改性蒙脱土对聚偏氟乙烯结晶结构的影响. 结果表明, 有机改性蒙脱土在聚偏氟乙烯中以插层、剥离和碎片的形式存在. 在X射线衍射谱中发现蒙脱土的(001)峰向低角方向移动, 在TEM中可见到剥离的片层碎 片.蒙脱土的引入改变了聚偏氟乙烯的结晶结构, 导致了具有压电性能的β相形成, 引起α相内应力的产生, 同时也导致了聚偏氟乙烯基体的结晶度下降, 球晶尺寸随蒙脱土含量明显减少. 蒙脱土引起的β相在 160℃退火表明是相当稳定的. 根据这些实验结果, 对由于蒙脱土的引入引起的聚偏氟乙烯结晶结构的变化提出了可能的解释.     

聚己内酯/聚酯丙烯酸酯共混物的辐射交联及其形状记忆行为

研究了聚酯丙烯酸酯 (PEA)类多官能团物质与聚己内酯 (PCL)共混物的辐射交联效应 .分别考察了多官能团PEA的用量、官能团数目、辐射交联剂量等因素对聚己内酯的辐射交联规律、动态力学性能、形状记忆行为等性能的影响 .结果表明 ,PCL PEA共混物的辐射交联规律不再遵从Charlesby Pinner关系式 ,而是符合陈欣方 刘克静 唐敖庆关系式 .多官能团PEA的加入可以显著提高PCL辐射交联的效率 ;相同剂量时 ,官能团数目越多、用量越大的样品 ,生成的凝胶含量越多 ,强化辐射交联效应越大 .DMA分析表明 ,PCL强化辐照交联后的弹性模量和耐热性能显著提高 .强化交联PCL在其熔点以上都呈现出高弹态平台 ,可以实现形状记忆 .且交联度较高 ,形状记忆恢复速率较快 .     

碳纳米管对聚偏氟乙烯膜的共混改性研究

用相转化法制备了聚偏氟乙烯/碳纳米管共混膜,研究了共混膜的表面结构、水通量、孔隙率、接触角和机械性能。结果显示碳纳米管的加入提高了聚偏氟乙烯膜的亲水性和水通量,当聚偏氟乙烯浓度为10wt.%,碳纳米管含量为1.5wt.%时,共混膜的水通量和孔隙率最高,从243 L/m2·h和86.2%提高到365 L/m2·h和91.4%;接触角也由82°减小为67°;同时,共混膜的机械性能也得到显著提高。     

相分离对聚偏氟乙烯/聚甲基丙烯酸甲酯共混物的力学与耐紫外老化性能的影响

采用熔融共混法制备聚偏氟乙烯/聚甲基丙烯酸甲酯( PVDF/PMMA)共混物,考察其力学性能、耐紫外老化性能、熔体动态流变、结晶与热分解行为.PMMA含量(wPMMA)为10 wt％时,共混物形成均相结构,力学与耐老化性能最好.wPMMA≥20 wt％时,PMMA形成球状聚集体,共混物力学性能与耐候性显著降低.PMMA的存在可提高PVDF的结晶度,降低熔融温度,但不改变PVDF晶体结构.     

形状记忆高分子材料的新型共混制备方法

形状记忆高分子材料(shape memory polymers,SMPs)作为一种特点突出、性能优良的智能材料具有极高的研究和实用价值,受到各国研究人员的广泛关注,新的制备方法和材料体系不断涌现,显示出巨大的发展潜力.本文总结了近年来出现的以共混方式为基础的多种重要制备方法,包括聚合物与聚合物直接熔融共混、溶液共混、借助增容剂或交联剂进行共混、通过新型微层共挤出技术进行交替层状共混、以及利用静电纺丝技术进行三维网络结构共混等.相较于化学合成方法,这些共混方法具有操作简单、原料易得、制备效率高、产品性能调节方便、制备过程更为环保等优点,并且能够得到与化学合成方法性能相同甚至更好的产品,优势突出,是今后制备形状记忆高分子材料的一大趋势.本文从这些新型共混材料的制备过程、微观结构、形状记忆性能等角度详细分析了不同方法的特点和优势.这些近年来出现的共混制备方法对于形状记忆高分子材料的发展和未来应用将是至关重要的.     

聚醚砜和溶剂对聚偏氟乙烯膜结晶性能的影响

研究了非相容性聚合物及不同溶剂对聚偏氟乙烯相转化膜结晶性能的影响。采用红外光谱和DSC方法测定了膜的晶型及结晶度。结果显示,与非相容性材料以适当的比例共混和采用溶度参数较低的溶剂可以降低膜β晶型的含量。     

Poly（vinylidene fluoride）/Clay Nanocomposites by Melt Compounding

The crystalline structures, morphologies, and mechanical properties of poly（vinylidene fluoride）/clay nanocomposites were studied using X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Fourier transform infrared spectroscopy（FTIR）, polarized optical microscopy（POM）, and tensile tests. The results of XRD and TEM show that organoclays are dispersed in the poly（vinylidene fluoride）（PVDF） matrix. A clay-induced crystal transformation from α-phase to β-phase of PVFD was confirmed by XRD and FTIR. Clay layers restricted the growth of spherulite. The tensile tests indicate that the tensile modulus and yield strength as well as the elongation at break decrease when clay is loaded.     

Non-Isothermal Crystallization of Poly (vinylidene fluoride)/Poly (methyl methacrylate)/Cellulose Nanocrystal Nanocomposites

Poly (vinylidiene fluoride) (PVDF)/poly (methyl methacrylate) (PMMA)/cellulose nanocrystal (CNC) nanocomposites were prepared by solution blending. Non-isothermal crystallization of PVDF/PMMA (70/30) blend and its composites was investigated using differential scanning calorimetry. It was found that the addition of CNCs played a positive role in both the crystallization rate and crystallization percentage. The addition of CNCs increased the initial crystallization temperature, peak crystallization temperature, and crystalline enthalpy. The Avrami index indicated that CNCs did not change the crystallization mechanism; while other parameters derived from Jeziorny theory and Mo's method, including Z _c , F(t), and α, further verified the positive role played by CNCs.     

基于聚乳酸的可降解形状记忆高分子的研究进展

综述了基于聚乳酸的可生物降解的形状记忆高分子材料的研究情况。首先介绍了形状记忆高分子材料的记忆效应、记忆机理,然后讨论了基于聚乳酸的三种类型的形状记忆高分子材料：单组份的聚乳酸类、聚乳酸共聚物类以及聚乳酸与无机物的复合材料,分别介绍了各种类型的形状记忆高分子材料的形状记忆性能和生物降解性能。最后,讨论了聚乳酸类记忆材料的应用情况,并对其研究前景和发展趋势进行了展望。     

碳纳米管结构对碳纳米管载Pt催化剂电催化性能的影响

在制备单、双壁及不同管径的多壁碳纳米管(CNTs)的基础上, 用液相还原法把Pt沉积到单、双壁和管径不同的多壁CNTs上. 发现制得的CNTs载Pt(Pt/CNTs)催化剂对甲醇氧化的电催化活性随CNTs管径减小而增加. 这归结于管径小的CNTs的比表面积较大, 含氧基团多, 有利于提高Pt粒子分散度, 加上管径小的单壁CNTs具有更高的导电性, 这些因素都有利于提高Pt/CNTs催化剂对甲醇氧化的电催化活性.     

Crystallization Behavior and Mechanical Properties of Poly(vinylidene fluoride)/multi-walled Carbon Nanotube Nanocomposites

Poly(vinylidene fluoride)(PVDF)/multi-walled carbon nanotube(MWCNT) nanocomposites were prepared by means of ultrasonic dispersion method. X-ray diffraction(XRD) results indicate that incorporating MWCNTs into PVDF caused the formation of β phase. A thermal annealing at 130 °C confirmed that the β phase was stable in the nanocomposites. Differential scanning calorimetry(DSC) results indicate that the melting temperature slightly increased while the heat of fusion markedly decreased with increasing MWCNT content. The tensile strength and modulus of PVDF were improved by loading the MWCNTs. The scanning electron microscopy(SEM) observations showed that MWCNTs were uniformly dispersed in the PVDF matrix and an interfacial adhesion between MWCNT and PVDF was achieved, which was responsible for the enhancement in the tensile strength and modulus of PVDF.     

基体分子运动对聚偏氟乙烯/碳纤维复合材料的聚合物基正温度系数性能的影响

聚合物基正温度系数(PTC)材料中,基体分子在熔体状态下的运动能力可显著影响填料分布、PTC强度及稳定重复性等,明确其机理有利于高灵敏性且稳定可重复的PTC复合材料的设计与制备.通过探究基体熔体黏度不同的聚偏氟乙烯(PVDF)/碳纤维(CF)的电阻-温度响应行为,可以发现复合材料PTC转变温度区间仅取决于基体化学结构与结晶性,而PTC循环稳定性却受到基体分子运动能力的显著影响.当基体分子运动能力较强时,分子链极易黏附填料在CF表面形成包覆层,导致局部填料间距增大到隧穿距离以上,不利于复合材料导电网络的重建,导致随热循环次数增加,复合材料的室温电阻率有所升高,PTC可重复性略微降低.而对基体分子链缠结明显的PVDF/CF复合材料中,运动能力较弱的分子链不会包覆CF粒子,在多次升温-降温循环后导电通路能恢复到初始状态,复合材料呈现良好的PTC可重复性,将其应用于电路过热保护装置时,复合材料表现出灵敏的温度响应特性及可多次循环的开关特性.     

Non-Isothermal Crystallization of Poly(vinylidene Fluoride)/Multiwalled Carbon Nanotube Composites

Poly(vinylidene fluoride)/multiwalled carbon nanotube (PVDF/MWCNT) composites were prepared by the method of solution blending. The non-isothermal crystallization of PVDF and its composites was investigated by differential scanning calorimetry (DSC). The results showed that the crystallization peaks shifted to lower temperature and the exothermic trace became wider when cooling rate increased for PVDF and its composites. The MWCNTs caused an increase in crystallization temperature and initial crystallization temperature. In addition, the Jeziorny and Mo methods were used to analyze the non-isothermal crystallization kinetics. The results showed that the crystallization rate rose with an increase in cooling rate, however, the MWCNTs decreased the crystallization rates of PVDF.     

Polymorphism Control of Poly(vinylidene fluoride) through Electrospinning

Polymorphism control of PVDF has been realized through electrospinning. PVDF fibrous membranes with fiber diameter in the range of 100 nm to several micrometers were produced by electrospinning and the crystal phase of electrospun PVDF fibers can be adjusted at the same time. Through the control of electrospinning parameters such as the solvent, electrospinning temperature, feeding rate, and tip‐to‐collector distance, PVDF fibrous membranes containing mainly α‐ or β‐ or γ‐phase could be fabricated successfully.

     

Poly(vinylidene fluoride)/clay nanocomposites prepared by melt intercalation: Crystallization and dynamic mechanical behavior studies

The preparation and properties of poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported for the first time. PVDF/clay nanocomposites were prepared by melt intercalation with organophilic clay. The composites were characterized with X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical analysis. X‐ray diffraction results indicated intercalation of the polymer into the interlayer spacing. PVDF in the nanocomposites crystallized in the β form. Differential scanning calorimetry nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity, as evidenced by the melting and crystallization peaks. Isothermal crystallization studies showed an enhanced rate of crystallization with the addition of clay, as evidenced by a reduction in the crystallization time. Dynamic mechanical analysis indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. The tan δ peak signifying the glass‐transition temperature of PVDF shifted to higher temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1682–1689, 2002     

Poly(methyl methacrylate)-induced Microstructure and Hydrolysis Behavior Changes of Poly(L-lactic acid)/Carbon Nanotubes Composites

Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.