碳纳米管填充不相容共混物的双PTC效应*

将碳纳米管(CNTs)、苯乙烯马来酸酐无规共聚物(SMA)改性后的CNTs分别与PS/PA6不相容共混体系熔融共混, 制备出PS/PA6/CNTs及PS/PA6/SMA-CNTs导电高分子复合材料, 并研究其PTC效应。结果表明, 对于PS/PA6/CNTs体系, CNTs选择性分布于PA6相, 体系的逾渗阈值为5%(质量分数), 且PTC效应不明显。对于PS/PA6/SMA-CNTs体系, 由于SMA的诱导作用, 使得CNTs分布于PS/PA6共混物相界面及PA6相, 导致体系的逾渗阈值降低至0.112%。PS/PA6/SMA-CNTs体系具有独特的“双PTC效应”, 且其形态结构影响PTC效应的形成机制。对于PA6相为分散相的体系, 其PTC效应是由于PS相的玻璃化转变及PA6相的熔融造成的。对于PS相为分散相及PS/PA6形成双连续相的体系, 其PTC效应是由于PA6相的熔融造成的。     

预制炭黑/尼龙6纤维网络在导电高分子复合材料中的逾渗行为

通过超声法将炭黑(CB)粒子固定在静电纺丝尼龙6(PA6)纤维膜表面,制备出一系列具有不同CB含量的CB/PA6导电纤维薄膜。利用热压成型法将制备的导电纤维膜与高密度聚乙烯(HDPE)粉末热压复合,制备出CB/PA6/HDPE导电高分子复合材料(CPC)。扫描电子显微镜图片显示,CB粒子均匀地锚固在PA6纤维表面,且CB/PA6导电纤维膜在HDPE基体中形成连续的导电网络结构。研究了材料的导电逾渗行为,发现CB/PA6/HDPE复合材料的逾渗值仅为2.5%,显著低于传统的CB/HDPE复合材料的逾渗值(8.5%)。同时,由于CB/PA6/HDPE复合材料具有特殊的预制CB/PA6导电纤维网络状结构,PA6电纺纤维膜的含量在复合材料体系中也呈现出有趣的逾渗行为。     

多级拉伸PP/PA1010/CB导电复合材料的结构与性能

利用自主设计的多级拉伸挤出设备,制备了含不同长径比的聚酰胺/炭黑（PA1010/CB）纤维的原位微纤聚丙烯/聚酰胺/炭黑（PP/PA1010/CB）导电复合材料,炭黑仅选择性分散在PA1010中,形成一种特殊的双逾渗现象。扫描电子显微镜观察、电学性能测试结果表明,随着分割叠加单元个数的增加,（PA1010＋CB）导电相...     

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。     

交替微层结构PPCB/PP导电复合材料的结构与性能EI

利用自主设计的微层共挤出设备,制备了具有交替微层结构的炭黑填充聚丙烯/聚丙烯(PPCB/PP)导电复合材料。PPCB层和PP层均为连续相,炭黑仅选择性分散在PPCB层内,形成一种特殊的双逾渗现象。电性能测试表明,微层共挤出技术可显著降低微层PPCB/PP复合材料的逾渗阈值和电阻率,其导电性能与材料层数相关。此外,微层共挤出方法能明显改善材料的韧性。     

交替微层结构PPCB/PP导电复合材料的结构与性能

利用自主设计的微层共挤出设备,制备了具有交替微层结构的炭黑填充聚丙烯/聚丙烯(PPCB/PP)导电复合材料。PPCB层和PP层均为连续相,炭黑仅选择性分散在PPCB层内,形成一种特殊的双逾渗现象。电性能测试表明,微层共挤出技术可显著降低微层PPCB/PP复合材料的逾渗阈值和电阻率,其导电性能与材料层数相关。此外,微层共挤出方法能明显改善材料的韧性。     

多壁碳纳米管增强炭黑/聚丙烯导电复合材料导电行为

为了充分利用不同导电粒子的导电作用,在炭黑(CB)/聚丙烯(PP)导电复合体系中引入了多壁碳纳米管(CNTs)。研究发现：引入的CNTs分散在CB粒子间起到“桥梁”作用,使体系的导电性能得到明显改善,并且CB∶CNTs为19∶1时其协同导电效果最好,该复合体系出现逾渗现象,对应的导电填料体积分数明显降低。在导电填料总体积分数为4.76%时,少量CNTs的引入就可使复合体系的体积电阻率从109Ω·cm下降到105Ω·cm;同时少量的CNTs能明显抑制炭黑/聚丙烯导电复合材料的正温度效应(PTC),使PTC强度从6.10降低到1.48,PTC转变峰温度从166℃升高到174℃。少量的 CNTs可以使PP的结晶温度提高12℃,对PP结晶的成核作用比CB更加明显。复合体系力学性能随导电填料体积分数增加而明显降低,但因为体积电阻率一定时CB-CNTs/PP体系所需导电填料体积分数较CB/PP体系明显降低,因此少量CNTs的引入能够使复合体系的力学性能得到更大程度的保持。     

力化学方法制备PP-g-HMA增容PA6/PP/硅灰石复合材料的形态和力学性能

以力化学方法制备的N-羟甲基丙烯酰胺接枝聚丙烯(PP-g-HMA)作尼龙6(PA6)/聚丙烯(PP)共混体系的增容剂,将增容尼龙6/聚丙烯共混体系与硅灰石复合.研究了复合材料的形态结构、硅灰石用量、偶联剂种类和用量以及增容剂等对复合材料的力学性能的影响.结果表明,PP-g-HMA能提高PA6/PP/硅灰石复合材料的力学性能,而KH-550和ON-330两种偶联剂复配使用则可以显著提高PP-g-HMA增容PA6/硅灰石复合材料的力学性能.     

聚丙烯/尼龙6共混物熔体的松弛时间

用扫描电镜对聚丙烯(PP)/尼龙6(PA6)共混物断面形貌进行了表征,用旋转流变仪小振幅剪切模式测试了PP/PA6共混物的动态模量,并采用广义Maxwell模型对于损耗模量-角频率曲线进行了拟合。扫描电镜结果表明,聚丙烯接枝马来酸酐(PP-g-MAH)有效提高了PP和PA6之间的相容性,使得分散相PA6粒径尺寸减小。广义Maxwell模型中,当松弛模数为N=5和6时,拟合曲线与实验数据在低频下存在明显的偏差,而松弛模数为N=7时,广义Maxwell模型能够较好地拟合实验曲线。固定PP/PP-g-MAH质量比为90/6时,随着PA6含量的增加,共混物PP/PP-g-MAH/PA6的松弛时间延长,松弛时间谱曲线以短时区为轴心逆时针旋转,向长时区偏移。     

聚丙烯/碳纳米管复合材料的结晶和介电行为

采用熔融共混制备了聚丙烯/碳纳米管复合材料(PP/MWCNTs)。利用场发射扫描电镜(FESEM)、差示扫描量热仪(DSC)、偏光显微镜(POM)、X射线衍射仪(XRD)及宽频介电仪(BDS)对复合体系的形态、非等温结晶行为、结晶结构以及介电行为进行了研究。结果表明,碳纳米管均匀分散于聚丙烯基体中,二者界面结合紧密;极少量碳纳米管的加入即对聚丙烯的结晶起显著的异相成核作用,促进聚丙烯α晶型的形成;此外,复合体系在导电逾渗阀值附近介电松弛行为显著加强。     

In situ microfibrillar morphology and properties of polypropylene/polyamide/carbon black composites prepared through multistage stretching extrusion

Isotactic polypropylene/polyamide/carbon black (PP/PA/CB) composites with microfibrillar morphology were designed and prepared using a multistage stretching extruder with an assembly of laminating-multiplying elements (LMEs). CB was selectively located in PA. With the increase of LME number from zero to seven, the conductive PA/CB phase was found to experience an elongating-breaking-elongating process. This morphological development resulted in the strong dependence of electrical resistivity on the LME number. When no LME was used, PP/PA/CB materials with 2.0, 3.0, or 4.0 wt% (1.0, 1.6, and 2.1 vol%) CB employed were insulators (resistivity: 10¹⁰ Ω cm) due to their droplet morphology. With the introduction of LMEs, a conductive network was formed because of the microfibrillation of the conductive PA/CB phase; these materials became conductors (resistivity: 10⁴–10⁶ Ω cm). The percolation threshold can lower to 1.5 wt% (0.9 vol%). The low resisticity and percolation threshold cannot be obtained through the conventional method.     

Compatibilizing effect of maleated polypropylene on the mechanical properties of injection molded polypropylene/polyamide 6/functionalized-TiO2 nanocomposites

TiO₂ nanoparticles were pretreated with excessive toluene-2,4-diisocyanate to synthesize TDI-functionalized TiO₂ (TiO₂-NCO), and then the polypropylene/polyamide 6/(PP/PA6, 70/30 wt%) blends containing 3 phr of the TDI-functionalized TiO₂ were prepared using twin-screw extruder followed by injection molding. Maleated polypropylene (PP-g-MAH) was used to compatibilize the blends. The mechanical properties of PP/PA6 blends based nanocomposites were studied through tensile and flexural tests. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the fracture surface morphology and the dispersion of the TDI-functionalized TiO₂, respectively. The dynamic mechanical properties of PP/PA6 based nanocomposites were analyzed by using dynamic mechanical thermal analyzer (DMTA). The strength and stiffness of the PP/PA6 compounds were improved significantly in the presence of PP-g-MAH. This has been attributed to the synergistic effect of TDI-functionalized TiO₂ and PP-g-MAH. The PP-g-MAH compatibilized PP/PA6 compounds showed a homogeneous morphology supporting the compatibility improvement between PP, PA6 and TDI-functionalized TiO₂. TEM results revealed that the TDI-functionalized TiO₂ nanoparticles were exfoliated and uniformly dispersed in blends matrix. Possible chemical interactions between PP, PA6, TDI-functionalized TiO₂ and PP-g-MAH were proposed based on the experimental work.     

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.     

聚丙烯/尼龙1010的失效强度预报

在定义了聚丙烯最小体积分数基础上由聚丙烯(PP)和尼龙1010(PA1010)性能预报了共混物的极限失效强度。试验结果表明,V(PP)／V(PA1010)=40／60时材料强度最低,利用简化力学模型计算的PP最小体积分数约为32％,接近于由共混物微观形貌观察到的发生相转接区域体积分数值,说明材料在相反转区力学性能也有相应的转变。在PP／PA1010中添加增容剂PP—g—MAH使转折点位置发生了变化,失效强度较未加增容剂有所提高．在PA1010含量＞40％时与预报结果符合更好。     

Electrical properties and morphology of carbon black filled PP/EPDM blends: effect of selective distribution of fillers induced by dynamic vulcanization

The roles of dynamic vulcanization process in the electrical properties, morphology, and rheology of carbon black (CB)-filled polypropylene (PP)/ethylene–propylene-diene rubber (EPDM) blends have been investigated. With the addition of CB, the uncross-linked (TPE) and dynamically vulcanized (TPV) composites showed a notable difference in the electrical properties, which is mainly caused by different distributions of CB particles resulting from the dynamic vulcanization process. Particularly, it was found that the CB particles in the TPE composites tended to distribute in EPDM phase, whereas the CB particles in the TPV composites were almost located in the PP matrix. The rheological behavior of the TPE and TPV composites was significantly changed with the incorporation of CB particles. Due to the selective distribution caused by the dynamic vulcanization process, the formation of the conductive network for the TPE composites is caused by the double percolation effect, while for the TPV composite, the formation of the conductive network is caused by the excluded volume effect.     

Morphology and electrical properties of polyamide 6/polypropylene/multi-walled carbon nanotubes composites

Morphology, electrical properties and conductive mechanisms of polyamide 6/polypropylene/muti-walled carbon nanotubes (PA6/PP/MWNTs) composites with varied compositions and different blending sequences were investigated. The MWNTs were found to be located preferentially in the PA6 phase in the composites, whatever the PA6 was continuous or dispersed phase. While the incorporation of MWNTs changed the dispersed PA6 phase from spherical to elongated or irregular shape. The PA6/PP/MWNTs (20/80/4) composite with a dispersed PA6 phase exhibited a higher electrical conductivity in comparison with the PA6/PP/MWNTs (50/50/4) composite which has a co-continuous phase and exhibits double percolation. This was due to the formation of a conductive MWNTs networks in the PA6/PP/MWNTs (20/80/4) composite as proved by means of field emission scanning electron microscopy and rheological measurements. The morphology and electrical properties of the PA6/PP/MWNTs (20/80/4) composites were significantly influenced by blending sequences. When blending 3.9 phr MWNTs with a pre-mixed PA6/PP/MWNTs (20/80/0.1) composite, the dispersed PA6 phase formed an elongated structure, which was beneficial to the electrical properties.     

蒙脱土/聚丙烯复合材料结晶形态及耐电树枝化特性

为了改善聚丙烯(PP)的耐电树枝性能,以有机化蒙脱土(MMT)作为纳米填充相,马来酸酐接枝聚丙烯(PP-g-MAH)作为相容剂,采用熔融插层一步法和二步法制备了MMT/PP复合材料。分别利用偏光显微镜(PLM)及差示扫描量热(DSC)曲线观测了PP及MMT/PP复合材料的结晶形态及结晶过程,采用SEM考察了MMT在复合材料中的分散状态。通过电树枝引发实验,探究了制备方法及结晶形态对复合材料耐电树枝化性能的影响。实验结果表明:采用熔融插层二步法制备的MMT/PP复合材料,其无机相分散较均匀,结晶尺寸减小,结晶结构由球晶转变为片晶的堆叠,结晶度提高了约2.7%;在PP试样中,电树枝长度较长且分枝较少,而MMT/PP试样中电树枝转变为长度较小且分枝较多的稠密结构。