多壁碳纳米管对聚甲醛性能的影响

将多壁碳纳米管(MWCNTs)和聚甲醛(POM)在转矩流变仪中熔融混合得到POM/MWCNT复合材料.研究了复合材料的形态,导热性能,导电性能,流变性能和结晶性能.结果表明,MWCNTs在没有经过处理的情况下能够均匀地分散在POM基体中;当向POM中添加1.0 wt%含量MWCNTs时,复合材料的导热系数上升到0.5289 W/(K m),比纯POM的导热系数0.198 W/(K m)提高1.5倍,通过有效介质方法(EMA)验证了体系导热系数提高幅度不大的原因是MWCNTs与POM之间形成了很高的界面热阻;当MWCNTs的含量为1.0 wt%时,体系产生了导电逾渗效应,逾渗值在0.5 wt%~1.0 wt%之间;MWCNTs对POM有显著的成核作用,当向POM中添加0.5 wt%含量的MWCNTs时,POM的结晶温度提高6℃左右,但当MWCNTs的添加量进一步增加时,结晶温度几乎不再变化,成核效果呈现"饱和"状态.另外,材料的复数黏度,储能模量和损耗模量随MWCNTs含量的增加而增加.     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

Effect of oxyfluorination on electromagnetic interference shielding of polyaniline-coated multi-walled carbon nanotubes

Highly conducting polyaniline (PANi)-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ polymerization method for electromagnetic interference shielding. The thickness of the PANi coatings was controlled by the oxyfluorination treatment on the multi-walled carbon nanotubes and analyzed with both SEM and TEM. The oxyfluorination with higher oxygen content produced more hydrophilic functional groups on the surface of multi-walled carbon nanotubes. The functional groups led to the well distribution and coating of PANi on the multi-walled carbon nanotubes resulting in the higher interfacial affinity between them. The uniform coating of PANi on MWCNTs by controlling the oxyfluorination conditions also played a crucial role in increasing the electrical conductivity of nanocomposites. The improved interfacial affinity resulted in the higher electromagnetic interference (EMI) SE of 47.03?dB based on the synergistic combination of the conductive components. The EMI shielding mechanism of PANi on MWCNTs suggested that EMI was mainly shielded by adsorption to avoid secondary EMI.     

Fabrication and electroactive responsive behavior of shape–memory nanocomposite incorporated with self‐assembled multiwalled carbon nanotube nanopaper

A novel shape–memory nanocomposite that exhibits electrical actuation capabilities was fabricated by incorporating a conductive multiwalled carbon nanotube (MWCNT) nanopaper into shape–memory polymer matrix. The self‐assembled MWCNT nanopaper was made on hydrophilic polycarbonate membrane. This process was based on well‐defined dispersion of the nanosized individual MWCNT and controlled traditional pressure vacuum deposition procedure. The self‐assembled MWCNTs in the nanopaper provided a percolating conductive network with a large interfacial area. It not only offered a high electrical conductivity but also simultaneously enhanced recovery speed by electrically resistive heating, with increasing the content of MWCNT nanopaper in nanocomposite. Copyright © 2011 John Wiley & Sons, Ltd.     

The transfer of carbon nanotubes in an immiscible high density polyethylene and polyamide 6 blend

The transfer process of multi‐walled carbon nanotubes (MWCNTs) from the high density polyethylene (HDPE) phase to the polyamide 6 (PA6) phase has been observed in the study. In this paper, the transfer is divided into six steps according to the level of mixing energy during the blending process. The MWCNTs could be extracted from HDPE phases and transfer into PA phases due to a stronger adhesion between MWCNTs and PA than HDPE. Additionally, the morphology change observed by optical microscope (OPM) is also thought to be crucial for the transfer. The PA phase version from disperse phase to continuous phase was obvious during the transfer process. Furthermore, the changes of electrical conductivity, yield strength and rheology have also been studied in this paper. The electrical conductivity changes with the transfer of MWCNTs and variation of phase morphology. Yield strength got the highest peak about 25.6 MPa and lowest peak about 22.3 MPa, respectively, at different mixing energies. The complex viscosity got the lowest value when the MWCNTs located in the interface. Copyright © 2014 John Wiley & Sons, Ltd.     

Thin and high conductive multi-walled carbon nanotubes/polydimethylsiloxane composite film prepared via solvent method as strain sensors

Flexible strain sensors based on conductive fillers and flexible polymers possessed significant advantages in human motion detection. Preparing a strain sensing layer with high electrical conductivity and excellent mechanical property under high content of conductive filler contributed to the stability of flexible strain sensors. In this study, MWCNTs/PDMS composite film was prepared by the organic solvent method. The microstructure, electrical conductivity, mechanical property, and piezoresistive characteristics of the composite film at different MWCNTs contents were characterized and discussed. When the mass fraction of MWCNTs in the composite film was 5%, the composite film exhibited a high electrical conductivity of 9.56 S/m while maintaining ideal mechanical properties, and the film thickness was just about 180 μm. The relationship between electrical signals and film strain was performed. The piezoresistive characteristic results demonstrated that the prepared composite film could be used as flexible strain sensor for human motion detection. The prepared thin MWCNTs/PDMS composite film in this paper illustrated high conductive and desired flexibility, and was an alternative material for human motion detection.     

碳纳米管/炭黑混杂填充聚甲醛复合材料导电性能研究

采用在转矩流变仪中熔融混合的方法制备了多壁碳纳米管(MWCNTs)和导电炭黑(CB)共同填充的聚甲醛(POM)导电复合材料,研究了材料的体积电阻率和导电填料用量之间的关系.用该体系的实验数据点对已发表的混合导电填料体系的定量关系式进行了验证,结果表明实验数据点和理论预测略有偏差.为方便实际应用,把混合导电填料体系的定量关系式加以发展,推导出逾渗值和两种导电填料质量比之间的关系式,并绘出了工作曲线.设计实验对工作曲线进行了验证,结果表明工作曲线对实践具有指导意义.     

Influence of maleic anhydride-grafted EPDM and flame retardant on interfacial interaction of glass fiber reinforced PA-66

In this paper, the effects of melamine polyphosphate flame retardant (MPP-FR) and maleic anhydride-grafted EPDM (MA-EPDM) on the interfacial interaction of PA66/GF were investigated by means of scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), rheological behavior and mechanical properties. The experimental results demonstrate that MPP-FR and MA-EPDM could effectively improve interfacial interactions between the PA66 and GF. Based on SEM, good interfacial adhesion between PA66 and GF in PA66/GF/FR and PA66/GF/FR/MA-EPDM composites was observed, however, MPP-FR destroyed the PA66 matrix. DMA results show that MPP-FR increased glass transition temperature (T_g) and storage modulus, and lower tan δ, while MA-EPDM showed a little effect on them in PA66/GF/FR/MA-EPDM composite compared with PA66/GF/FR. MPP-FR made PA66 crystallization temperature and the activation energy of the macromolecular segments transport increase clearly, and enhanced crystallization degree of PA66 according to DSC results. These results demonstrate MPP-FR presented the nucleate effect for the crystallization of PA66. At the low shear rate, MPP-FR and MA-EPDM obviously enhanced apparent viscosities of the composites. This is attributed that MPP-FR improved the interfacial interaction of the composites, and MA-EPDM promoted the formation of high molecular weight structures by the reactions between MA and amine groups. All results in this paper were consistent, and showed the good interaction among PA66, GF, MPP and MA-EPDM, which were proved by the mechanical properties of the composites.     

玻璃纤维对聚甲醛基导电复合材料性能的影响

采用在转矩流变仪中熔融混合的方法制备了聚甲醛(POM)/多壁碳纳米管(MWCNTs)/玻璃纤维(GF)和POM/炭黑(CB)/GF复合材料,研究了GF的加入对复合材料的导电性能、结晶行为和动态力学性能的影响.采用场发射扫描电镜(FESEM)观察了复合材料中导电填料的分散状态,发现GF的加入对MWCNTs和CB的分散状态没有明显影响.虽然GF为导电惰性填料,但因其加入起到了占位作用,明显提高了导电填料的有效浓度,从而使复合材料的体积电阻率明显降低.采用示差扫描量热仪(DSC)研究了复合材料中POM的结晶行为,发现GF的加入对POM的结晶温度、熔点和结晶度均无明显影响.采用动态机械分析仪(DMA)对复合材料的动态力学性能进行了研究,表明GF的加入能够明显地提高复合材料的储能模量.     

聚吡咯/多壁碳纳米管及其聚氨酯导电复合材料的制备和性能

以羧基化多壁碳纳米管(MWCNTs)做模版剂,采用化学氧化法将吡咯(Py)在羧基化MWCNTs表面聚合制备PPy/MWCNTs导电材料,将其添加到溶剂型聚氨酯(PU)溶液中制备了PPy/MWCNTs/PU导电复合材料,研究了Py用量对PPy/MWCNTs及其PU复合材料性能的影响.研究表明,随Py用量的增加,PPy/MWCNTs的长度不变,管径增大,sp~2和sp~3杂化C含量先提高后减少,N的掺杂梯度降低,PPy/MWCNTs的导电率高于羧基化MWCNTs和PPy.当Py用量为羧基化MWCNTs的20%时,其导电率最大.PPy/MWCNTs中N元素的掺杂程度及其管径变化是引起PPy/MWCNTs/PU复合材料的性能不同的主要原因.增加Py用量,MWCNTs中亲水的羧基因对PPy掺杂而消耗,相同导电材料用量时纳米导电粒子数目相对减少,PPy/MWCNTs/PU复合材料的耐水性能提高,定向应力、储能模量和玻璃化温度降低,导电率先增加后减小.当Py用量为羧基化MWCNTs的15%时,导电率最大.     

Electrically conductive transparent papers using multiwalled carbon nanotubes

We describe a novel class of electrically conductive transparent materials based on multiwalled carbon nanotubes (MWCNTs). Transparent nanocomposites were fabricated by incorporating an aqueous silk fibroin solution into bacterial cellulose membranes. The transparent nanocomposites had a high transmittance in the visible and infrared regions, regardless of the bacterial cellulose fiber content, due to the nanosize effect of the bacterial cellulose nanofibrils. This phenomenon allowed the preparation of a novel electrically conductive transparent paper. The high dispersity of the MWCNTs was realized by utilizing a bacterial cellulose membrane as a template to deposit them uniformly, thereby achieving electrically conductive transparent papers with outstanding optical transparency. The light transmittance and electrical conductivity varied according to the concentration of the MWCNT dispersion. Good optimal transparency and electrical properties were obtained with a light transmittance of 70.3% at 550 nm and electrical conductivity of 2.1 × 10^?3 S/cm when the electrically conductive transparent paper was fabricated from a 0.02 wt % aqueous MWCNT dispersion. In addition, the electrically conductive transparent papers showed remarkable flexibility without any loss of their initial properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1235–1242, 2008     

Mechanical Properties and Morphology of Melt-mixed PA6/SWNT Composites: Effect of Reactive Coupling

An interfacial reaction during melt mixing of maleic anhydride copolymer (SMA) encapsulated single wall carbon nanotubes (SWNT) and polyamide 6 (PA6) was used in order to disperse SWNT homogeneously and to enhance interfacial adhesion. The intended reactive coupling between PA6 and SMA was evident from IR spectroscopy. Nanocomposites with SMA encapsulated SWNT showed increased elongation at break as compared to PA6/SWNT composites. SEM investigation of tensile fractured surfaces of PA6/SWNT+SMA composites indicated enhanced interfacial adhesion between PA6 and SMA modified SWNT.     

Flory-huggins interaction parameters of LCP/thermoplastic blends measured by DSC analysis

Liquid crystalline polymer/polyamide 66 (LCP/PA66) and LCP/poly(butyl terephthalate) (LCP/PBT) blends were compounded using a Brabender Plasticorder equipped with a mixing chamber. The LCP employed was a semi-flexible liquid crystalline copolyesteramide based on 30 mol% of p-amino benzoic acid (ABA) and 70 mol% of poly(ethylene terephthalate) (PET). The Flory-Huggins interaction parameters (χ12) of the LCP/ PA66 and LCP/PBT blends are estimated by melting point depression from DSC measurement. The results indicate that c12 values all are negative for LCP/PA66 and LCP/PBT blends, and when the LCP content in these blends is more than 10 mass%, the absolute value of χ₁₂ decreases. Thereby, we can conclude that LCP/PA66 and LCP/PBT blends are fully miscible in the molten state, the molecular interaction between the LCP and PA66 is stronger than that between LCP and PBT. As the LCP content in LCP/PA66 and LCP/PBT blends is more than 10 mass%, the molecular interaction between LCP and matrix polymer decreases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Isotactic polypropylene/carbon nanotube composites prepared by latex technology: Electrical conductivity study

Several series of nanocomposites were prepared using a latex-based process, the main step of which consisted of mixing an aqueous suspension of exfoliated carbon nanotubes (CNTs) and a polymer latex. In the present work, a systematic study on the electrical properties of fully amorphous (polystyrene - PS) as well as semi-crystalline (isotactic polypropylene - iPP) nanocomposites containing either single-wall (SWCNTs) or multi-wall carbon nanotubes (MWCNTs) has been conducted. Percolation thresholds as low as 0.05 wt.% or 0.1 wt.% were observed for SWCNT/iPP and MWCNT/iPP nanocomposites, respectively. The formation of a conductive percolating network at such a low CNT concentration is favored by the high intrinsic conductivity and the low viscosity of the polymer matrix. The electrical percolation threshold of the iPP-based system was found to be lower than its rheological percolation threshold. Beyond the percolation threshold, MWCNT-based nanocomposites generally exhibited higher conductivity levels than those based on SWCNTs, most probably due to the higher intrinsic conductivity of the MWCNTs as compared to that of the SWCNTs. These excellent electrical properties, associated with the strong nucleating effect of the CNTs reported earlier [1] and [2], render this type of nanocomposites extremely attractive from a technological point of view.     

PA66/PA12/clay based nanocomposites: structure and thermal properties

In a previous paper the structure and the physical properties of melt mixed polyamide 66 (PA66)/polyamide 12 (PA12) blends characterized by different compositions have been investigated by means of morphological and physical analyses. A low amount of organically‐modified layered silicate (OMLS, 4 wt%) was introduced in order to evaluate its effect on blends structure and components miscibility. This paper completes the characterization of these materials investigating their thermal properties by means of standard and modulated differential scanning calorimetry (DSC, MDSC), dynamic‐mechanical analysis (DMA), and thermogravimetric analysis (TGA). The partial miscibility of PA66 and PA12, with phase separation depending on blend composition, has been confirmed by analyzing the glass transition temperature (T_g) dependence on composition as well as the existence of strong segmental interactions between polymer components. A compatibilizing action of OMLS has been observed because of a lowering of interfacial tension avoiding coalescence phenomena between particles during melt mixing process. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of dispersion and selective localization of carbon nanotubes on rheology and electrical conductivity of polyamide 6 (PA6), Polypropylene (PP), and PA6/PP nanocomposites

Nanocomposites were prepared by adding 1–3 vol % multiwalled carbon nanotubes (MWCNTs) to polyamide 6 (PA6), polypropylene (PP), and their co‐continuous blends of 60/40 and 50/50 volume compositions. Because of the good interaction and interfacial adhesion to the PA6, nanotubes were disentangled and distributed evenly through nanocomposites containing PA6. In contrast, lack of active interactions between the matrix and the CNTs resulted in poor tube dispersion in PP. These observations were then verified by studying the rheology and electrical conductivity of their respective nanocomposites. Absence of percolated CNT clusters and possible wrapping of the tubes by PA6 resulted in low electrical conductivity of PA6/CNT nanocomposites. On the other hand, despite the weak dispersion of the tubes, electrical conductivities of PP/CNT nanocomposites were much higher than all other counterparts. This could be the result of good three‐dimensional distribution of the agglomerated bundles and secondary aggregation of tubes in PP. Adding CNTs to blends of PA6/PP (60/40 and 50/50) resulted in almost full localization of carbon nanotubes in PA6, leading to their higher effective concentration. At the same CNT loadings, the blend nanocomposites had three to seven orders of magnitude higher electrical conductivity than pure PA6. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 368–378     

Investigation on properties of V<Subscript>2</Subscript>O<Subscript>5</Subscript>–MWCNTs composites as cathode materials

An effective method to prepare the composites of multi-wall carbon nanotubes (MWCNTs) and vanadium pentoxide (V₂O₅) was presented. Vanadyl-triisopropoxide (VO(OC₃H₇)₃) was used as the starting material, MWCNTs pretreated with acids by a two-step process was used as the conductive ingredient. V₂O₅–MWCNTs composites were synthesized via a sol–gel method with solvent exchange and an ambient pressure drying technique. The samples were characterized by SEM, TEM, XRD, BET, Raman spectra and electrical resistivity measurement respectively. The experimental results indicate that the V₂O₅–MWCNTs nanocomposite has a fiber-like and tri-dimensional network structure. Its surface area is up to 189.7 m²/g when the MWCNTs’ content is 15 wt%. And MWCNTs are dispersed homogeneously in the composites. The electrical resistivity of the composites decreases from 1,239 to 765 Ω·cm when the MWCNTs’ content increases from 0 to 10 wt%. Thus MWCNTs can improve properties of V₂O₅ aerogels as the cathode material in lithium batteries.     

One-step process to make electrically conductive thermoplastic vulcanizates filled with MWCNTs

Electrically conductive thermoplastic vulcanizates(TPVs) filled by multi-walled carbon nanotubes(MWCNTs) are prepared by a simple one-step melt mixing process,based on linear low density polyethylene(LLDPE) and ultrafme full-vulcanized rubber particles(UFRP).An ideal morphology with controlled localization of MWCNTs in continuous LLDPE matrix and appropriate size of finely-dispersed UFRP can be achieved at the same time.The controlled localization of MWCNTs in the continuous phase facilitates the formation of conductive pathway,and thus the volume resistivity of the as-prepared LLDPE/UFRP/MWCNTs thermoplastic vulcanizates is significantly decreased.The results show that both the blend ratio of LLDPE/UFRP and the loading of MWCNTs have remarkable effect on the volume resistivity.Significantly, the electrically conductive TPVs exhibit good mechanical properties duo to the fine dispersion of UFRP in LLDPE.The added MWCNTs are capable of imparting reinforcement effects to thermoplastic vulcanizates with just a slight loss of stretchability and elasticity.     

磺化聚苯乙炔/多壁碳纳米管复合材料导电特性和机理的研究

将磺化聚苯乙炔(SPPA)与多壁碳纳米管(MWCNTs)超声共混制备得到SPPA/MWCNTs复合材料. 用X光电子能谱仪、固体紫外-可见分光光度计、X射线衍射仪、四探针、场发射扫描电镜等对复合材料导电特性及机理进行研究. 结果表明: SPPA/MWCNTs 复合材料中SPPA与MWCNTs发生电荷转移而被掺杂, 并且由于SPPA与MWCNTs间的电荷转移, 彼此间存在一定的相互作用力; 复合材料电阻呈负温度系数效应; SPPA/MWCNTs复合材料电导率发生两次突跃. 可能的导电机理为, 复合材料中SPPA不仅被MWCNTs物理填充, 同时还被MWCNTs掺杂, 复合材料中存在两种导电通路, 一是SPPA与MWCNTs的碳原子发生电荷转移而被掺杂, 彼此之间存在一定的相互作用力, 导致SPPA包裹MWCNTs形成独立导体单元, 这种独立单元相互接触形成导电通路; 二是MWCNTs彼此之间相互接触形成导电通路, 并建立了该导电机理的理论模型.     

Annealing induced electrical conductivity jump of multi‐walled carbon nanotube/polypropylene composites and influence of molecular weight of polypropylene

Multi‐walled carbon nanotube (MWCNT)/polypropylene (PP) composites were prepared by a micro melt mixing process. As‐prepared composites had relatively low electrical conductivity due to the disruption of MWCNT network by strong shear. The electrical conductivity jumped to high values throughout an annealing process above the melting temperature of PP. The significant enhancement of electrical conductivity was influenced by annealing time, temperature, and content of MWCNTs. In particular, molecular weight of PP played an important role in affecting the conductivity enhancement. The molecular weight of PP was varied from 190,000 to 340,000 to examine its effect on the electrical conductivity. By comparing the conductivity enhancement behavior of composites with different molecular weight PPs and observing the morphology evolution during annealing, it was found that reaggregation of MWCNTs and the subsequent formation of MWCNT network during annealing are the main reasons for the jump of electrical conductivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010