LLDPE／EVA／CB导电复合材料PTC效应的研究

研究了线性低密度聚乙烯（LLDPE）／乙烯-醋酸乙烯酯共聚物（EVA）／碳黑（CB）复合材料的导电性及正温度系数（PTC）特性。发现在LLDPE／CB复合材料中加入少量的EVA能增加PTC强度1．5～2个数量级。并分别用DCP交联和辐射交联等方法探讨了对LLDPE／EVA／CB复合材料PTC效应稳定性的影响。研究结果表明复合材料中加入1％DCP或经过320KGy辐射剂量处理都可以提高PTC效应的稳定性。复合材料经过辐射交联后有优良的热循环稳定性。     

掺炭黑的聚偏氟乙烯/氟橡胶导电复合材料的电热性能

以聚偏氟乙烯（ＰＶＤＦ）／氟橡胶（Ｆ２６）合金为基体;研 究了两种不同炭黑类型及用量、不同环境温度、不同热历史条件 及辐照交联对复合物ＰＴＣ（正电阻温度系数）导电特性的影响。 结果表明,掺有乙炔炭黑的聚偏氟乙烯／氟橡胶导电复合材料具 有一种强ＰＴＣ特性,可用于制作电致发热稳定性良好的、自限 温度（１２０±５）℃的、具有商业用途的自控温型伴热带。     

通过挤出-热拉伸制备CB/PET/PE导电复合材料

在前期热塑性塑料原位成纤研究基础上，尝试通过挤出-热拉伸制备原位微纤化炭黑(CB)／聚对幕二甲酸乙二醇酯(PET)／高密度聚乙烯(HDPE)导电复合材料。先将CB／PET熔融混合制成母料，再将母料和HDPE按一定的比例挤出一热拉伸。实验发现，体系成纤性能受母料的熔融粘度影响。在相对低的CB含量下，复合物能形成较好的原位微纤，从而具有较好的电性能．     

高转变温度聚合物PTC材料的研究

研究了以尼龙12（PA12）为基体树脂，炭黑（CB）为导电填料的高转变温度聚合物正温度系数（P11C）材料。采用熔融共混方法制备了PA12/CB聚合物PTC复合材料，研究了炭黑种类、炭黑含量、炭黑表面改性等因素对PA12/CB复合材料PTC性能的影响。结果表明：Vxc305炭黑填充的PA12复合材料，当炭黑含量为30％时，PTC强度可达到105；炭黑表面改性能够抑制材料的NrC效应。     

炭黑／聚丙烯／聚碳酸酯复合材料导电性能和PTC特性

以聚丙烯（PP）／聚碳酸酯（PC）共混物为基体,采用不同种类炭黑（CB）填充制备导电复合材料并对其导电性能和PTC特性进行研究。结果表明：在常温时,PP／PC共混基体中PP含量大于40wt％时,材料的电阻率急剧下降;共混比为50：50（wt％）复合材料的电阻率达到最小值。加热时,两者均未出现明显NTC现象,说明PP／PC的共混可以有效的消除NTC效应。但PTC强度仅为1个数量级,远低于PP／CB二元复合材料。CB是影响PTC效应的重要因素之一,达到逾渗值时随着体系CB含量减少PTC效应会增强;乙炔炭黑与炉法CB填充的CB／PP／PC复合材料相比较,前者的体积电阻率较低,而两者的逾渗阈值相近,均为6．6％;乙炔CB为填料的CB／PP／PC三元复合材料的阿C突变温度在140℃附近,以炉法CB为填料时,PTC效应突变点出现在150℃（PC的Tg）附近。DSC分析结果表明,复合材料中PP的结晶度随着CB含量增加呈上升趋势,CB含量为15％时,PP的结晶度为32．75％,对于整个PP／PC／CB体系而言结晶部分的含量较低,因此该体系的PTC效应强度较低。     

碳纳米管/丁苯橡胶复合材料的电学性能

采用喷雾干燥法可制备不同配比的碳纳米管（Carbon nanotubes,CNTs）/粉末丁苯橡胶复合材料,观察CNTs在橡胶基体中的分散情况,检测复合材料的导电性能及介电性能,并进行了简要的理论分析。结果表明:CNTs在橡胶基体中获得了充分均匀的分散,有利于CNTs改性补强作用的发挥。与纯胶样品及填充炭黑（Carbon black,CB）样品相比, 填充CNTs样品在8~18GHz下具有较高的介电常数及低介电损耗。随着CNTs加入量的增加,CNTs/粉末丁苯橡胶复合材料的电导率逐渐升高,当CNTs加入量为60phr（per hundred rubber）时,与纯胶样品及添加60phr CB样品相比,电导率提高近10个数量级;复合材料内部导电同时存在隧道导电机制和渗逾导电机制。采用喷雾干燥法制备的CNTs/粉末丁苯橡胶复合材料,将是一种综合性能良好的新型纳米复合材料,有望在抗静电橡胶、电磁屏蔽及介电材料等领域获得应用。      

基于空间限域强制组装法制备短切碳纤维/乙烯-醋酸乙烯导电复合材料性能

采用空间限域强制组装法（SCFNA）制备短切碳纤维/乙烯-醋酸乙烯共聚物（SCF/EVA）导电复合材料,研究SCFNA方法制备SCF/EVA复合材料中导电填料分布形态的演变规律及该方法对复合材料导电性能和力学性能的影响。与传统共混方法相比,采用SCFNA方法制备的SCF/EVA复合材料,导电网络上SCF的间距变小,网络密实度显著提高,导电性能得到大幅度提升并具有良好的力学性能。实验表明:通过SCFNA方法制备的SCF/EVA复合材料的逾渗阈值为6.5 wt%,低于共混自组装法的8.2 wt%。相同SCF质量分数下,SCF/EVA复合材料的电导率比共混法自组装最高提高4个数量级。随着SCF质量分数的增加,SCF/EVA复合材料的力学性能呈先提高后降低的趋势,其中10 wt%SCF/EVA复合材料的力学性能最优,拉伸强度达到19.86 MPa。      

多元碳纳米材料协同改性玻璃微珠/环氧树脂复合材料

采用静电自组装法制备了还原氧化石墨烯表面修饰中空玻璃微珠（rGO@HGB）,与导电炭黑（CB）、石墨烯纳米片（GNPs）一起与环氧树脂（EP）共混,制备了CB-GNPs-rGO@HGB/EP复合材料,并系统研究了复合材料的微观结构、导电性能和介电性能。结果表明,rGO@HGB的加入能够显著提高rGO@HGB/EP复合材料的导电性能和介电常数,进一步引入CB和GNPs后,形成了被rGO@HGB隔离的导电逾渗网络,rGO、CB和GNPs三者对提高CB-GNPs-rGO@HGB/EP复合材料性能具有协同作用。在CB与GNPs的总含量固定为0.2vol%,且二者的体积比为10:1时,CB-GNPs-rGO@HGB/EP复合材料的导电与介电性能最优,对应的体积电阻率为1.88×104 Ωcm,在1 kHz下的介电常数高达454.5,分别比CB-rGO@HGB/EP和GNPs-rGO@HGB/EP复合材料提高了11.3%和10.7%,而其介电损耗仅为0.065。      

HDPE/EVA/CB复合导电材料的研究

研究了HDPE/EVA/CB(炭黑)复合材料的导电性及正温度系数(PTC)特性,包括电阻-温度特性和电流-时间特性.发现在HDPE/CB复合材料中加入少量的EVA能降低室温电阻率、改善炭黑粒子的分散、增强PTC效应以及缩短材料的响应时间,并从基体的结晶性及炭黑在共混基体中分布的角度探讨了EVA组分对复合材料电性能影响的作用机理.     

TLCP/GF/PP复合材料中纤维的主承载与微纤的作用

本文对热致液晶聚合物（TLCP）／玻璃纤维（GF）／聚丙烯（PP）原位混杂复合材料的形态结构，破坏过程，力学性能进行了研究，显微镜的观察结果表明，TLCP的加入使得加工过程中玻纤的破断减弱，TLCP／GF／PP原位混合复合材料中GF的平均长度是GF／PP复合材料的2．36倍。这使其主承载作用更显著，使用带拉伸实验台的扫描电镜观察到了TLCP微纤或微球对微裂纹扩展的阻滞及延缓作用。TLCP／GF／PP（5／15／85）样品拉伸强度度及断裂伸长度分别比GF／PP（15／85）样品提高了22．6％和321％，PP-g-MAH的加入使得原位混杂复合材料的拉伸强度进一步得到提高。     

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。     

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.     

Crystallization of partially miscible linear low-density polyethylene/poly(ethylene-co-vinylacetate) blends

Miscibility and crystallization of linear low-density polyethylene (LLDPE)/poly(ethylene-co-vinylacetate) (EVA) blends were investigated by optical microscopy (OM) and differential scanning calorimetry (DSC). It was found that there existed liquid–liquid phase separation (LLPS) below 220 °C over the whole composition. However, the depression in the crystallization temperature, melting temperature and equilibrium melting temperature of LLDPE all indicated that this polymer pair was partially miscible. The crystallization and melting behavior of LLDPE were determined by the dilute effect of non-crystalline EVA and the probable co-crystallization of parts of EVA chains with LLDPE chains. The crystallization and melting behavior of EVA was determined by the competence between a nucleation effect of LLDPE crystals and partial miscibility between this polymer pair, which was different from that of LLDPE.     

Positive temperature coefficient characteristic and structure of graphite nanofibers reinforced high density polyethylene/carbon black nanocomposites

Graphite nanofibers (GNF) and carbon black (CB) filled high density polyethylene (HDPE) hybrid composites were fabricated using a melt mixing method. The effects of the CB and GNF content on the room temperature resistivity and positive temperature coefficient (PTC) behavior of the nanocomposites were examined. The room temperature resistivity of the composites decreased significantly with increasing GNF content, but this was not always the case with the PTC intensity. The incorporation of a small amount of GNF into the HDPE/CB composites significantly improved the PTC intensity and reproducibility of the hybrid nanocomposites. The maximum PTC effect, whose log intensity was approximately 7.2, was observed in the HDPE/CB/GNF (80/20/0.25 wt%) nanocomposite with relatively low room temperature resistivity. The mechanism for the effects of GNF in HDPE/CB/GNF hybrid composites were examined using differential scanning calorimetry, transmission scanning electron microscopy and X-ray diffraction.     

Thermal Analysis Studies of (Bi,?Pb)-2223/Linear Low Density Polyethylene Composite Materials

Series of superconductor/polymer composites were prepared using high-temperature superconductor Bi_1.8Pb_0.4Sr₂Ca_2.1Cu_3.2O_10+?? phase and linear low density polyethylene (LLDPE). The LLDPE concentration varied from 0.0 to 100 wt. % of the sample??s total mass. The composite materials were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM), whereas the crystallization point of LLDPE and its composites were determined using differential scanning calorimetery (DSC). Furthermore, the thermal expansion measurements for composite materials were taken from room temperature up to 160?°C. The results showed that the thermal expansion coefficient increased with increasing of the percentage of LLDPE content.     

热塑性塑料的电阻焊焊接工艺

采用导电炭黑(CB)填充的高密度聚乙烯(HDPE)复合材料加热单元来焊接HDPE样条。研究发现,炭黑填充量高于12%(质量分数,下同)时,复合材料的电阻率降到3Ω.cm以下;用炭黑含量为12%、16%及20%的加热单元来焊接HDPE时,合适的焊接电压分别为33 V、23 V和20 V。通过搭接焊和对焊,从剪切破坏强度和拉伸破坏强度两个方面来评价焊接性能。结果表明,当焊接时间在6 min左右时,三种不同炭黑含量的加热单元的焊接系数均超过0.9,焊接时间10 min左右时,焊接系数可以达到1,焊接性能优良。     

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。     

双交联体系互穿聚合物网络对石墨烯/乙烯-醋酸乙烯酯共聚物/高密度聚乙烯复合材料抗静电性能的影响

以高密度聚乙烯(HDPE)、乙烯-醋酸乙烯酯共聚物(EVA)为基体材料,石墨烯为导电填料,2,5-二甲基-2,5-双(叔丁基过氧基)己烷(DBPH)、三烯丙基异氰脲酸酯(TAIC)为交联剂,通过物理-化学方法在2种交联剂的协同作用下制备了具有互穿聚合物网络(IPN)结构的石墨烯/EVA/HDPE复合材料。实验结果表明,所用2种交联剂的协同作用能使复合材料的交联度达到54.3%。扫描电镜图中可以观察到EVA和HDPE形成的IPN结构可以促使石墨烯在复合材料基体中形成较完善的网络结构。实验结果还表明网络结构能在复合材料达到抗静电性能标准的情况下,很大程度上减少了石墨烯在EVA/HDPE基体中的添加量。当复合材料的交联度为40%~50%时,会出现类渗流阈现象,石墨烯的质量分数为2%时,复合材料的拉伸强度达到28.1 MPa,体积电阻率达到10~8Ω·cm。     

增容剂EVA-g-MAH对乙烯-醋酸乙烯共聚物/聚酰胺6阻燃合金性能的影响

采用熔融共混法,以聚磷酸铵(APP)、季戊四醇(PER)为原料组成的膨胀阻燃剂(IFR),制备了乙烯-醋酸乙烯共聚物/聚酰胺6/IFR(EVA/PA6/IFR)阻燃复合材料,并研究了增容剂EVA-g-MAH对EVA/PA6阻燃合金阻燃性和力学性能的影响。通过极限氧指数、垂直燃烧、熔融指数、力学性能、热重分析和扫描电子显微镜等手段对EVA/PA6阻燃合金进行了性能测试与表征。结果表明:随着EVA-g-MAH用量的增加,EVA/PA6阻燃合金的极限氧指数稍有降低,但当EVA-g-MAH质量分数为10%时,垂直燃烧可达UL 94V-0级;拉伸强度和断裂伸长率随着增容剂含量的增加而逐渐升高。热重分析结果表明,增容剂可提高EVA/PA6阻燃合金的热稳定性。