PET/MWNT/CB纳米复合材料制备与性能研究

采用原位聚合方法制备了聚对苯二甲酸乙二醇酯/多壁碳纳米管/炭黑(PET/MWNT/CB)纳米复合材料,研究了MWNT与CB对复合材料导电性能、结晶性能和热稳定性的影响,考察了二者的协同导电效应。结果表明,当MWNT与CB复合填料含量为0.5%(质量分数)时,复合材料的表面电阻为10~(11)Ω。CB与MWNT在PET中能形成"共支撑"网络结构和复合导电通路,具有协同导电效应。二者对PET具有诱导成核与结晶作用,但CB的诱导能力要弱于MWNT。CB的添加对复合材料的热稳定性影响不大。     

静电纺丝法制备低渗流阈值聚酰亚胺/炭黑导电复合材料

原位聚合法得到聚酰胺酸(PAA)/炭黑(CB)聚合物溶液,通过静电纺丝、热亚胺化制备了聚酰亚胺(PI)/炭黑复合纳米纤维膜,经过热压加工工艺得到以炭黑为填料的聚酰亚胺基导电复合材料。扫描电镜(SEM)和透射电镜(TEM)观察了复合材料的微观形貌,通过LCR数字电桥、拉伸测试和热重分析(TGA)研究了复合材料的电学性能、力学性能与热稳定性。实验表明,PI/CB导电复合材料的渗流阈值为6%(质量分数);在渗流阈值时,材料的拉伸强度和断裂伸长率分别为93.9 MPa和68.9%,10%热失重温度为575.8℃。聚酰亚胺/炭黑导电复合材料表现出优异的力学性能和热稳定性能。     

石墨烯/超高分子量聚乙烯复合材料的导电性能

采用氧化还原法制备了石墨烯(GNS),用X射线衍射(XRD)、红外光谱、透射电子显微镜对所得GNS进行了分析和表征。采用溶液混合、超声波分散的方法,制备了GNS/超高分子量聚乙烯(UHMWPE)导电复合材料,研究了材料的导电渗流行为和阻-温特性。结果表明,溶液混合法可使GNS较好地分散于UHMWPE基体中,复合材料表现出典型的导电渗流行为,其渗流阈值为3.6%(质量分数)。在大于渗流阈值的情况下,复合材料的正温度系数效应(PTC)强度随GNS含量的增加而提高;热循环使得复合材料的PTC强度有所降低。     

填充型聚合物基复合材料的导电和导热性能

研究了高密度聚乙烯为基体、炭黑和炭纤维为填料复合体系的导电和导热性能。发现当导电填料的含量达到渗流阈值时,复合材料的电导率急剧升高;而在渗流阈值附近,其热导率未出现突变。这表明电导渗流现象不完全是由导电粒子通过物理接触生成导电链所致。其导电机制是相当数量的导电粒子相互发生隧道效应。     

炭黑改性对炭黑/高密度聚乙烯体系电性能稳定性的影响

采用熔体共混法制备了炭黑（CB）/高密度聚乙烯（HDPE）导电复合材料。研究了硝酸氧化对CB/HDPE导电复合材料正温度系数（PTC）、负温度系数（NTC）效应和电性能稳定性的影响。结果表明,填充氧化炭黑（CB-O）提高了CB-O/HDPE体系的电性能稳定性和PTC强度,部分消除或降低了复合材料的NTC效应。而CB-O/HDPE体系的室温电阻率比CB/HDPE体系只增加了0.3个数量级,但比经过交联处理的CB/HDPE（CB/crosslinked-HDPE）体系降低了1个数量级。CB-O/HDPE复合材料性能的改善主要是由于CB经氧化后,表面羧基、羟基等极性基团含量增加,抑制了CB粒子高温时的自团聚作用,减弱了体系的NTC效应;同时CB表面微晶晶界处导电性较差区域的减少,提高了CB的导电性,,并且CB-O表面大量孔洞和裂缝的形成,增强了CB-O与HDPE的物理吸附作用,提高了复合材料的电性能稳定性。      

双组分聚合物基CB-PP/PVDF复合材料导电网络及热敏特性研究

将两种不相混容的半结晶聚合物PP和PVDF以适当体积比和合适工艺与纳米炭黑（CB）复合，所得材料的渗流阈值远远低于CB和单一聚合物复合，且具有很强的PTC效应。结合对材料显微照片的分析，研究了CB在基体中的选择性分布形成的特殊的导电网络及双渗阈结构特点，探讨了双组分聚合物基纳米复合材料渗流阈值大幅降低及PTC效应增强的内部机制。     

导电炭黑填充硅橡胶的电阻温度系数

以炭黑(CB3100)为导电相,硅橡胶为基质制备导电复合材料。研究导电橡胶中炭黑质量分数对电阻温度系数的影响,并用填料对电阻温度系数的影响。以隧道效应理论为基础,给出了导电炭黑填充橡胶的电阻温度系数计算模型,结合实验得到温度对导电炭黑/硅橡胶电阻温度系数的影响主要体现在对其电阻率的影响;基体的体积热膨胀提高复合材料的电阻率,提高了正电阻温度系数;炭黑粒子间的隧道效应降低复合材料的电阻率,增强了负电阻温度系数;在炭黑/硅橡胶中加入少量碳纳米管,利用碳纳米管和炭黑的协同补强效应,使复合材料的导电性和稳定性提高。     

特殊形态结构导电高分子复合材料的电学性能

先使聚丙烯接枝马来酸酐(PP-g-MAH)与炭黑(CB)反应,再与聚丙烯/尼龙6(PP/PA6)共混制备出CB位于两相界面处的PP/PA6/PP-g-MAH/CB导电高分子复合材料,研究了材料的特殊结构和电学性能。结果表明,在PP/PA6/CB体系中CB粒子分布在PA6相,体系的逾渗阈值为2%;而在PP/PA6/PP-g-MAH/CB体系中,CB被PP-g-MAH诱导分布在两相界面处。PP/PA6两相为海岛结构时,PP/PA6/PP-g-MAH/CB体系仍可导电。PP/PA6/PP-g-MAH/CB体系的逾渗阈值降至1.6%,低于PP/PA6/CB体系。体系的正温度效应(PTC)强度远高于PP/PA6/CB体系,在90-135℃范围内不出现负温度效应(NTC)。PP/PA6/PP-g-MAH/CB体系的电学性能归结于其特殊的界面形态结构:导电通道由位于共混物界面处的PP-g-MAH和CB构建而成。     

ABS/不锈钢纤维/石墨导电复合材料的导电特性?

以丙烯腈/丁二烯/苯乙烯共聚物(ABS)为基体,不锈钢纤维(SSF)和石墨为混杂导电介质制备了ABS/不锈钢纤维/石墨0-1-3复合体系。采用动态机械分析(DMA)、数字万用表和旋转流变仪等研究了复合材料的导电渗流行为、流变渗流特性的关联性及在DMA多频应变模式-动态微力场下的阻温特性与导电机理。结果表明,石墨的加入可明显提高复合体系的渗流导电能力;复合体系的导电渗流与流变渗流的渗滤阀值相近,均约为15％;在动态交变微载荷下,电阻率强烈的依赖于振动频率和温度,随着温度的升高,出现电阻正温度效应(PTC)和电阻负温度效应(NTC);且频率越高,SSF含量越低,复合体系的 PTC转变温度越高。     

熔融酯交换法原位合成炭黑/聚碳酸酯导电复合材料

利用原位聚合法合成具有导电性能的炭黑(CB)/聚碳酸酯(PC)复合材料。在聚合反应过程中, CB与PC在较低黏度下更好地混融, 而且通过负载催化剂连接CB和PC分子, 使CB参与PC链增长过程, 从而使CB有效分散。与传统的熔融共混法相比, 利用原位聚合法制备的CB/PC导电复合材料的渗滤阈值低, 当复合材料的体积电阻率为1.56×10⁶ Ω·mm时, CB的质量分数仅为4.32%。通过SEM观察发现, 原位法得到的样品中CB与PC充分混融, 形成导电网络更充分有效。利用原位聚合法得到的样品的正温度系数(PTC)的对数值达到4.69, 具有作为自控温材料的潜力。     

抗静电PET/ATO纤维的制备及材料的性能

采用原位聚合的方法制备了抗静电涤纶(PET)/锑掺杂二氧化锡(ATO)纳米复合材料。结果显示,ATO在PET中分散良好,团聚体尺寸小于200 nm;加入ATO没有影响PET的流动曲线类型,随着ATO含量的增加,在相同的剪切频率下,熔体黏度均呈先增加后减小的趋势;加入ATO提高了材料的热性能,利于熔融纺丝。采用熔融纺丝法制备了抗静电纳米复合纤维。ATO含量为1.0%(质量分数,下同)时纤维的比电阻由2.7×1013Ω.cm下降到4.9×108Ω.cm。抗静电纤维的渗滤阈值为1.05%,低于传统抗静电填料。     

Electrical properties of hybrid carbon black/carbon fiber polypropylene composites

The electrical conductivity and morphology of injection molded polypropylene based composites containing two conductive fillers, carbon black (CB) and carbon fibers (CF) were studied. Injection moldings containing both, CB and CF, where the content of each filler was above its own percolation threshold, resulted in similar or lower values of overall composite volume resistivity compared with the resistivity of systems filled only with CB at the corresponding content. However, the resistivity of two-filler systems is always higher than the resistivity of systems filled only with CF at the corresponding content. The morphology and fiber length analysis of the injection molded composites are quite intriguing. Fiber orientation in the injection molded two-filler systems was found to be almost perpendicular to the melt flow direction, with no significant skin-core fiber orientation patterns, contrary to the typically observed fiber orientation in injection molded fiber filled composites. Moreover, the CF breakage in the presence of the CB was found more intense than when just CF is used, resulting in shorter fibers with narrower length distributions. This unexpected fiber behavior is responsible for the unexpected electrical behavior. However, the coexistence of CB and CF electrically conductive networks, supporting each other, was confirmed, in spite of the mechanical disturbances caused by the presence of fibrilar and particulate fillers.     

玻璃纤维增强PET工程塑料性能及界面研究

用红外光谱分析，扫描电镜，粘弹谱仪，差示扫描量热法及力学性能测试方法，考察了玻璃纤维增强聚对苯二甲酸乙二醇酯的界面情况及力学性能等，并分析了玻璃纤维表面处理剂对ＰＥＴ树脂及其界面粘结性的影响，结果表明，经偶联剂表面处理的玻璃纤维对ＰＥＴ树脂有明显的增强效应能显著提高ＰＥＴ工程塑料的力学性能及界面粘结强度。     

Lower electrical conductive percolation threshold of multiwall carbon nanotube reinforced poly(vinylidene fluoride) induced by nano-clay and coupling agent

The multiwall carbon nanotube/poly(vinylidene fluoride) nanocomposites with a series of nano-clay and coupling agent were prepared. The effect of nano-clay and coupling agent on the electrical and mechanical properties of nanocomposites were studied and compared. The results showed that nano-clay and coupling agent could not only enhance the electrical conductivity and storage modulus but also reduce the percolation threshold of such nanocomposites. The dispersion of fillers, interaction between fillers and matrix, were studied as main factors.     

Effect of hybridization on the physical and mechanical properties of high density polyethylene–(pine/agave) composites

This work reports on the properties of high density polyethylene based hybrid composites made with two natural fibers: agave and pine. The composites were produced by a combination of extrusion and injection molding. The effect of hybridization was analyzed via morphological, mechanical and water immersion tests for two total fiber contents, 20 and 30 wt.%, and different pine-agave fiber ratios (100–0, 80–20, 60–40, 40–60 and 0–100). Moreover, the effect of coupling agent (maleated polyethylene) in the hybrid composite formulation was evaluated. The results showed that addition of agave fibers improves tensile, flexural and impact strength, while pine fibers decreases water uptake. As expected, the addition of a coupling agent improves substantially the quality of the polymer–fiber interface as well as the mechanical properties, but this effect was more important for composites produced with higher agave fibers content due to the their chemical composition.     

氧化石墨烯改性玄武岩纤维及其增强环氧树脂复合材料性能

为了改善玄武岩纤维/环氧树脂复合材料的界面性能,通过偶联剂对氧化石墨烯进行改性,并将改性后的氧化石墨烯引入到上浆剂中对玄武岩纤维进行表面涂覆改性,同时制备了氧化石墨烯-玄武岩纤维/环氧树脂复合材料.采用FTIR表征了氧化石墨烯的改性效果;运用SEM分析了改性上浆剂处理对玄武岩纤维表面及复合材料断口形貌的影响和作用机制.结果表明:偶联剂成功接枝到氧化石墨烯表面;玄武岩纤维经氧化石墨烯改性的上浆剂处理后,表面粗糙度及活性官能团含量增加,氧化石墨烯-玄武岩纤维/环氧树脂界面处的机械齿合作用及化学键合作用增强,界面黏结强度得到改善,玄武岩纤维的断裂强力提高了30.8%,氧化石墨烯-玄武岩纤维/环氧树脂复合材料的层间剪切强度提高了10.6%.     

Percolation threshold and morphology of composites of conducting carbon black/polypropylene/EVA

Conducting carbon black (CB), one of the intrinsic semi-conductors, was added into matrix polypropylene (PP) to prepare conducting composites by means of the melt processing method. Another component EVA was mixed into the composites in order to lower the percolation threshold. The percolation threshold of the ternary CB/PP/EVA composites was merely 3.8 vol%, while it was up to 7.8 vol% for the binary CB/PP composites without EVA. The conductivity of the ternary CB/PP/EVA composites was up to 10^–2 S/cm when the CB percentage was 5 vol%, while that of the binary CB/PP was lower than 10^–2 S/cm when the CB percentage was up to 10 vol%. DSC thermograms of the CB/PP/EVA composites showed that the melting peak shifted to low temperature with increasing CB content. The addition of CB and EVA resulted in the decrease of the crystallinity of PP in the ternary composites. The mechanical properties are also discussed. SEM and TEM were employed to study the morphology of the blend system. The results indicated that CB existed in the form of aggregations in the blend system. The smallest unit that formed a percolation network was grape-like aggregates with some small branches, which consisted of some CB particles, rather than the individual particles. This distribution was very valuable for forming conducting paths and for lowering the percolation value.     

Effect of a novel coupling agent,alkyl ketene dimer,on the mechanical properties of wood–plastic composites

The objective of this study was to investigate the incorporation of poplar wood fibers both with and without a novel coupling agent, alkyl ketene dimer (AKD), on the mechanical properties of wood fiber/polypropylene (PP) composites. The resulting properties were compared to those obtained with the most commonly used coupling agent, maleic anhydride grafted PP (MAPP). Tensile and impact strengths of the composites decreased with increasing poplar wood fibers content. Tensile modulus of the composites increased by the incorporation of the wood fibers content up to 70 wt% but further increment in the wood fibers decreased the tensile modulus. At the constant content of poplar wood fibers (70 wt%), the tensile strength determined for the coupled composites with 5% AKD increased by 41% in comparison with the non-coupled composites while the tensile modulus increased by 45%, the impact strength of the coupled composites increased by 38%. The performance of 5% AKD on the mechanical properties of the composites is a little better than 3% MAPP. The good performance of 5% AKD is attributed to the enhanced compatibility between the poplar wood fibers and the polymer matrix. The increase in mechanical properties of the composites demonstrated that AKD is an effective coupling agent for wood fiber/PP composites.     

A study of the mechanical properties of short natural-fiber reinforced composites

The degree of fiber–matrix adhesion and its effect on the mechanical reinforcement of short henequen fibers and a polyethylene matrix was studied. The surface treatments were: an alkali treatment, a silane coupling agent and the pre-impregnation process of the HDPE/xylene solution. The presence of Si–O–cellulose and Si–O–Si bonds on the lignocellulosic surface confirmed that the silane coupling agent was efficiently held on the fibres surface through both condensation with cellulose hydroxyl groups and self-condensation between silanol groups.

The fiber–matrix interface shear strength (IFSS) was used as an indicator of the fiber–matrix adhesion improvement, and also to determine a suitable value of fiber length in order to process the composite with relative ease. It was noticed that the IFSS observed for the different fiber surface treatments increased and such interface strength almost doubled only by changing the mechanical interaction and the chemical interactions between fiber and matrix.

HDPE-henequen fiber composite materials were prepared with a 20% v/v fiber content and the tensile, flexural and shear properties were studied. The comparison of tensile properties of the composites showed that the silane treatment and the matrix-resin pre-impregnation process of the fiber produced a significant increase in tensile strength, while the tensile modulus remained relatively unaffected. The increase in tensile strength was only possible when the henequen fibers were treated first with an alkaline solution. It was also shown that the silane treatment produced a significant increase in flexural strength while the flexural modulus also remained relatively unaffected. The shear properties of the composites also increased significantly, but, only when the henequen fibers were treated with the silane coupling agent. Scanning electron microscopy (SEM) studies of the composites failure surfaces also indicated that there is an improved adhesion between fiber and matrix. Examination of the failure surfaces also indicated differences in the interfacial failure mode. With increasing fiber–matrix adhesion the failure mode changed from interfacial failure and considerable fiber pull-out from the matrix for the untreated fiber to matrix yielding and fiber and matrix tearing for the alkaline, matrix-resin pre-impregnation and silane treated fibers.     

Lowering the percolation threshold of polymer matrix composite by using raspberry-like carbon black/polystyrene composite particles

Our previous studies of raspberry-like carbon black/polystyrene (CB/PS) composite particles suggested that their morphologies could be tailored as the coverage degree of CB on PS microspheres. Morphologies of these composite particles were investigated by scanning electron microscope. The CB/PS composites prepared by using raspberry-like CB/PS particles had lower percolation threshold than that of general CB/PS composites. Optical microscopy photographs indicated that hierarchical structure of composite particles enabled CB particles to form more effective networks within the matrix. Raspberry-like structure dispersed CB particles in the interfaces between polycarbonate (PC) and PS when CB/PS particles were introduced into PC as additives. The effects of concentration of PS, coverage degree of CB, and concentration of CB on electrical properties of CB/PS/PC composite were investigated. The results showed that the percolation threshold of CB/PS/PC composite was improved when PS concentration was at the range of 20–80% and coverage degree of CB was more than 5% simultaneously.