High electrical conductivity of nylon 6 composites obtained with hybrid multiwalled carbon nanotube/carbon fiber fillers

The synergetic effect of multiwalled carbon nanotubes (MWNTs) and carbon fibers (CFs) in enhancing the electrical conductivity of nylon 6 (PA6) composites was investigated. To improve the compatibility between the fillers and the PA6 resin, we grafted γ‐aminopropyltriethoxy silane (KH‐550) onto the MWNTs and CFs after carboxyl groups were generated on their surface by chemical oxidation with nitric acid. Fourier transform infrared spectroscopy and thermogravimetric analysis proved that the KH‐550 molecules were successfully grafted onto the surface of the MWNTs and CFs. Scanning electron microscopy and optical microscopy showed that the obtained modified fillers reduced the aggregation of fillers and resulted in better dispersion and interfacial compatibility. We found that the electrical percolation threshold of the MWNT/PA6 and CF/PA6 composites occurred when the volume fraction of the fillers were 4 and 5%, respectively. The MWNT/CF hybrid‐filler system exhibited a remarkable synergetic effect on the electrically conductive networks. The MWNT/7% CF hybrid‐filler system appeared to show a second percolation when the MWNT volume fraction was above 4% and a volume resistivity reduction of two orders of magnitude compared with the MWNT/PA6 system. The mechanical properties of different types of PA6 composites with variation in the filler volume content were also studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40923.     

Improvement of dispersion of carbon nanotubes in epoxy resin through pyrogallol functionalization

Multiwalled carbon nanotubes (MWNTs) were functionalized with pyrogallol. The functionalized MWNTs were well‐dispersed in the epoxy/curing agent/ethanol solution, as demonstrated by UV‐vis spectra and optical micrographs. Epoxy resin/MWNTs composites were prepared via solution mixing method. The cure behavior was characterized using differential scanning calorimetry. Pyrogallol‐functionalized carbon nanotubes (CNTs) reacted with the epoxy through the mediation reaction of pyrogallol with the curing agent, leading to the interfacial bonding between the functionalized carbon nanotubes (CNTs) and the resin matrix. Due to the excellent dispersion and interfacial bonding, the mechanical strength and electrical conductivity of the epoxy resin/CNTs composites have been improved. POLYM. ENG. SCI. 56:1079–1085, 2016. © 2016 Society of Plastics Engineers     

Investigation on the multiwalled carbon nanotubes reinforced polyamide 6/polypropylene composites

Multiwalled carbon nanotubes (MWNTs) reinforced polyamide 6/polypropylene (PA6/PP = 70/30) composites were prepared by melt compounding. Maleated polypropylene (MPP) was used as a compatibilizer for the composites. The morphology, mechanical properties, thermal stability, rheological properties and crystallization behavior of the composites were investigated. It was found that the addition of MWNTs to PA6/PP blend resulted in decrease in the size of the dispersed particles. Most of MWNTs were selectively dispersed in the PA6 phase and a small amount of MWNTs were located in the interphase between PA6 matrix and PP phase as characterized by scanning electric microscopy. The strength and stiffness of the PA6/PP blend were greatly improved by the addition of MWNTs. The MPP and MWNTs had a synergistic effect on the improvement ofthe thermal stability. In addition, the complex viscosity, storage modulus and loss modulus of the composites increased with the addition of MWNTs or MPP. MWNTs could induce the formation of α crystalline form of PA6. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Pseudoreinforcement effect of multiwalled carbon nanotubes in epoxy matrix composites

The carbon nanotube possesses outstanding physical properties. Theoretically, adding carbon nanotubes into a polymer matrix can remarkably improve the mechanical properties of the polymer matrix. In the present work, a series of composites was prepared by incorporating multiwalled carbon nanotubes (MWNTs) into an epoxy resin. The influences of MWNT content and curing temperature on the flexural properties of the epoxy resin were investigated. The results showed that a very low MWNT content should be used to ensure homogeneous dispersion of MWNTs in the epoxy matrix. A higher MWNT content may lead to deteriorated mechanical properties of the composites because of the aggregation of MWNTs. A decline in the flexural properties of the neat epoxy resin with increasing curing temperature was found. However, under the same curing conditions, improvement in flexural properties was observed for the composite with the low MWNT content and a mild curing temperature. The improvement was far beyond the predictions of the traditional short‐fiber composite theory. In fact, this improvement should be attributed to the retarding effect of MWNTs on the curing reaction of epoxy matrix. Therefore, the improvement in the flexural properties was only a pseudoreinforcement effect, not a nano‐reinforcement effect of the MWNTs on the epoxy resin. Perhaps, it is better for MWNTs to be used as functional fillers, such as electrical or thermal conductive fillers, than as reinforcements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3664–3672, 2006     

Synergetic effects on the mechanical and fracture properties of epoxy composites with multiscale reinforcements: Carbon nanotubes and short carbon fibers

The ball‐milling/liquid‐phase oxidation (BMLPO) method was used to fabricate surface‐modified short carbon fibers (SCFs). Multiscale epoxy composites reinforced with a combination of SCFs and multiwalled carbon nanotubes (MWNTs) were prepared. Atomic force microscopy observations and contact angle measurement were used to investigate the modification effect of the BMLPO method. Mechanical tests and scanning electron microscopy observations were used to study the effects of the SCFs, MWNTs, and their combination on tensile properties, impact strength, and fracture toughness of the epoxy composites. The results show that the surface roughness of the SCFs after BMLPO treatment increased, and the wettability of the SCFs was improved as well. The combined use of the SCFs and MWNTs had a synergetic effect on the tensile strength, fracture toughness, and impact strength of the epoxy composites. The addition of MWNTs promoted the plastic deformation of the epoxy matrix and decreased the stress‐concentration level near the SCF/matrix interface; these were considered the main causes of the synergetic effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43500.     

多壁碳纳米管／环氧树脂复合材料性能研究

采用物理机械方法与化学方法相结合的手段,制备了多壁碳纳米管（MWNTS）／环氧树脂（Epoxy）复合材料。通过力学拉伸试验测试了MWNTs/Epoxy复合材料拉伸强度和拉伸模量与MWNTS添加量的关系,利用扫描电镜（SEM）分析了MWNTS／Epoxy复合材料的拉伸断面,并用表面电阻测试仪对所制备的碳纳米管复合材料进行了电学性能测试。结果表明：经过化学酸化的方法处理后的MWNTS在复合材料中的分散得到了改善,力学性能也得到了明显的提高,但酸处理后的复合材料的电学性能明显低于未处理的复合材料。     

Crystallization and melting behavior of multi‐walled carbon nanotube‐reinforced nylon‐6 composites

The crystallization and melting behavior of neat nylon‐6 (PA6) and multi‐walled carbon nanotubes (MWNTs)/PA6 composites prepared by simple melt‐compounding was comparatively studied. Differential scanning calorimetry (DSC) results show two crystallization exotherms (T_{CC, 1} and T_{CC, 2}) for PA6/MWNTs composites instead of a single exotherm (T_{CC, 1}) for the neat matrix. The formation of the higher‐temperature exotherm T_{CC, 2} is closely related to the addition of MWNTs. X‐ray diffraction (XRD) results indicate that only the α‐phase crystalline structure is formed upon incorporating MWNTs into PA6 matrix, independently of the cooling rate and annealing conditions. These observations are significantly different from those for PA6 matrix, where the increase in cooling rate or decrease in annealing temperature results in the crystal transformation from α‐phase to γ‐phase. The crystallization behavior of PA6/MWNTs composites is also significantly different from those reported in PA6/nanoclay systems, probably due to the difference in nanofiller geometry between one‐dimensional MWNTs and two‐dimensional nanoclay platelets. The nucleation sites provided by carbon nanotubes seem to be favorable to the formation of thermodynamically stable α‐phase crystals of PA6. The dominant α‐phase crystals in PA6/MWNTs composites may play an important role in the remarkable enhancement of mechanical properties. Copyright © 2005 Society of Chemical Industry     

Effects of nanotube modification on the dielectric behaviors and mechanical properties of multiwall carbon nanotubes/epoxy composites

Multiwall carbon nanotubes (MWNTs) were modified by three methods, namely, oxidizing the tubes and opening both ends, filling the tubes with Ag, and grafting the tubes with hexamethylene diamine. Modified MWNTs/epoxy composites were prepared by melt‐mixing epoxy resin with the tubes. Transmission electron microscope images showed that the modified MWNTs can be dispersed in the epoxy matrix homogeneously. The dielectric behaviors and mechanical properties of the composites were investigated. The dielectric and mechanical properties of the modified MWNTs/epoxy composites were considerably improved compared with those of the epoxy matrix. The tensile strengths of the Ag‐filled, opened, and grafted MWNTs composites at the same filler content of 1.1 wt% were higher by ～30.5%, 35.6%, and 27.4%, respectively, than that of neat epoxy. The Izod notched impact strength of the grafted MWNTs/epoxy composite with filler content of 1.1 wt% was approximately four times higher than that of neat epoxy. A dielectric constant of ～150 of the composite with 1.1 wt% Ag‐filled nanotubes was observed in the low‐frequency range, which was ～40 times higher than that of the epoxy matrix. The proper modification of nanotubes provides a way to improve the properties of the polymer‐based composites. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Properties of anionic polymerized ε‐caprolactam in the presence of carbon nanotubes

The results of the investigations of the relations between structure, physical and usage properties of polyamide 6 (PA6) reinforced with multiwall carbon nanotubes (MWNTs) are presented. A method of in situ anionic bulk polymerization of ε‐caprolactam in the presence of MWNTs was used for the preparation of reinforced PA6. The polymerization product was crushed, and the pellets of PA6 and PA6/MWNTs composites were injection molded to produce the standard test specimens for various measurements. The surface morphology (SEM), thermal (DSC, TGA, DMTA), and mechanical properties (tensile strength, Charpy's notched impact strength) of these materials were examined. Some differences between our specimens and those obtained by hydrolytic polymerization of ε‐caprolactam (CL) were found. It was found that a small amount of carbon nanotube decreases the crystallinity degree of PA6 matrix in the composites. The thermal stability was higher than that for neat PA6. DMTA results showed that the magnitudes of the storage modulus are higher for the PA6/MWNTs composites than for the unmodified PA6 in the temperature range between ?90 and 200°C. The tensile strength and tensile modulus are higher compared with the neat PA6. The elongation at break showed no noticeable change in the range of MWNTs loading considered, while the Charpy's notched impact strength slightly decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

High performance polyamide 6 composites prepared by reactive extrusion

To improve the properties of polyamide 6 (PA6) composites, a series of modified PA6 composites was prepared by reaction extrusion. An amorphous PA6 was first obtained by the complexing reaction of Li⁺ in lithium chloride with amino groups, and then epoxy resins, nano‐SiO₂ as well as POE‐g‐MAH were in turn added into the PA6/LiCl system. The effect of different additives on the crystallization behavior and mechanical properties of PA6 composites was well‐studied by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and mechanical properties tests. The results demonstrated that PA6 was amorphous at 6 phr lithium chloride and a network structure was formed in PA6 matrix in the presence of epoxy resins, thus the mechanical properties of composites greatly were enhanced. However too many nano‐SiO₂ particles might impair the tensile strength of PA6 composites. Additionally, a PA6 composite with excellent properties was obtained in the presence of POE‐g‐MAH due to the crystal form change in PA6 matrix and the strong interaction between PA6 and POE‐g‐MAH. POLYM. COMPOS., 35:985–992, 2014. © 2013 Society of Plastics Engineers     

PP-g-MAH对尼龙6/炭黑复合材料性能和形貌的影响

以炭黑(CB)为导电填料,马来酸酐接枝聚丙烯(PP-g-MAH)为增韧剂,通过双螺杆挤出机和注射成型机制备了尼龙(PA)6/PP-g-MAH/CB复合材料,研究了PP-g-MAH含量对7.5%CB填充PA6力学性能、抗静电性能、热稳定性能和形貌的影响。结果表明,添加质量分数20%的PP-g-MAH可提高PA6/CB复合材料的拉伸强度、韧性、抗静电性能和热稳定性。PA6/PP-g-MAH/CB复合材料力学强度和热稳定性的提高源于PP-g-MAH产生的能量耗散以及CB,PP-g-MAH与PA6之间较好的界面粘附和PP-g-MAH均匀细化分散在PA6/CB中。PP-g-MAH改变了CB在共混物中的选择性分布,使PA6/CB的表面电阻率和体积电阻率分别下降5个和3个数量级。     

Electrical and thermal properties of silicone rubber composites filled with Cu-coated carbon fibres and functional carbon nanotubes

ABSTRACT

The thermal and electrical conductivities of SR composites containing Cu-CFs and f-MWNTs were studied. The Cu-CFs and f-MWNTs were prepared by chemical deposition and the coupling method, respectively. Both the fillers were characterised by FT-IR, XRD and SEM and the results showed that the Cu layers were deposited on the surface of the CFs and the MWNTs were successfully modified. In addition, the results of thermal and electrical conductivities for SR composites showed that the hybrid fillers system exhibited a better enhancement on thermal and electrical conductivities for SR composites than the single filler system. The maximum thermal conductivity and the least volume resistivity of SR/Cu-CFs/f-MWNTs composites could reach 3.86?W (m?K)^?1 and 3.5?×?10³?Ω?cm, respectively. Based on the experimental results, we recognised the improvement of intrinsical thermal and electrical conductivities of CFs and the good dispersion of MWNTs contributed to the formation of densified 3D conducting networks. Thus, the hybrid fillers system could synergistically enhance the thermal and electrical conductivities of SR composites. We believe, this study could provide an effective way for the design of high conductive polymer composites.     

Reinforced thermal conductivity and mechanical properties of in situ microfibrillar composites through multistage stretching extrusion

To surmount difficulty of the melt processing and deterioration of mechanical properties of polymer composites induced by high fraction of the reinforced fibers and thermal conductive fillers, polyethylene (PE)/boron nitride (BN)/polyamide 6 (PA6) and PE/BN/poly(‐hydroxybenzate‐co‐DOPO‐benzenediol dihydrodiphenyl ether terephthalate) (PHDDT) in situ microfibrillar composites were prepared through multistage stretching extrusion. The experimental results showed that both the tensile and impact strength of the PE/BN/PA6 and PE/BN/PHDDT composites were improved. Meanwhile, the thermal conductivities of the PE/BN, PE/BN/PA6, and PE/BN/PHDDT composites were also reinforced. Based on the equation proposed by Y. Agari, the new modified equations can well predict the thermal conductivity of the composites prepared through multistage stretching extrusion with different number of laminating‐multiplying elements. In addition, it was found that PHDDT can act as a “processing aid” to reduce the viscosity of the PE/BN composites. POLYM. COMPOS., 38:2663–2669, 2017. © 2015 Society of Plastics Engineers     

Polyamide‐6 composites reinforced with cellulose fibers and fabricated by extrusion: Effect of fiber bleaching on mechanical properties and stability

We prepared polyamide‐6 (PA‐6) composites using bleached and semibleached cellulose fibers from Eucalyptus species by processing in a corotating interpenetrating twin‐screw extruder. PA‐6 is a challenging matrix because of its high processing temperature, which overlaps the thermodegradation temperature of the fibers. The selection of the processing conditions for extrusion and the use of the lubricant ethylene bis (stearamide) permitted the production of composites with 20, 30, and 40 wt% of bleached fibers, which are lighter than the corresponding glass fiber composites. Composites with 30 wt% of bleached fibers yield the best mechanical properties and good fiber/matrix interaction, as demonstrated by mechanical tests and scanning electron microscopy. X‐ray photoelectron spectroscopy studies showed that the natural moisture in the fibers promotes the fiber/matrix interaction through the formation of ester bonds. We assessed the effect caused by the presence of lignin in the fibers. Composites containing 30 wt% of semibleached fibers maintained the flexural properties and showed small improvements in thermal stability when compared with bleached fiber composites; however, there is a slight decrease in the tensile properties. Through accelerated aging tests, we observed that increased lignin concentration in the fibers reduced the formation of carbonyl compounds on sample surfaces, indicating a stabilization effect. POLYM. COMPOS., 38:299–308, 2017. © 2015 Society of Plastics Engineers     

Improving thermal conductivity while retaining high electrical resistivity of epoxy composites by incorporating silica-coated multi-walled carbon nanotubes

Silica-coated multi-walled carbon nanotubes (MWCNT@SiO₂) were synthesized by a sol–gel method and then incorporated into an epoxy matrix. The less stiff silica intermediate shell on the MWCNTs not only alleviates the modulus mismatch between the stiff MWCNTs and the soft epoxy, but also improves the interaction between them. The thermal conductivities of the epoxy/MWCNT@SiO₂ composites increase by 51% and 67% at low filler loadings of 0.5 wt.% and 1 wt.%, respectively. At the same time, the silica shell retains the high electrical resistivity of these composites.     

Synthesis of polyamide 6/11 copolymers and their use as matrix polymer in wood‐plastic composites

The goal of this study was to investigate the synthesis and the resulting thermal, rheological, and mechanical properties of polyamide 6/11 copolymers (PA 6/11) as a function of their composition and to further investigate their usability as matrix polymers for wood‐plastic composites (WPC). A significant composition dependency of the melting temperature was found due to the hindered crystallization of the PA 6/11 copolymers with increasing content of the minor component. In result, the lowest melting temperature of the copolymers was measured at 120 °C for 40 wt % of ?‐caprolactam (PA 6/11‐40/60) by DSC analysis. Due to its low melting point and feasible mechanical properties, a copolyamide with 70 wt % of ?‐caprolactam (PA 6/11‐70/30) was chosen as matrix material for the processing of WPC. Incorporation of 30 wt % of wood fibers into PA 6/11‐70/30 caused a significant increase in tensile modulus and a decrease in tensile strength and strain at break. However, the processed WPC still showed an exceptional ductility with a strain at break of 15 to 20%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44155.     

Mechanical properties of carbon fiber composites modified with graphene oxide in the interphase

The surface topographies of carbon fibers treated by sizing agents with different graphene oxide (GO) content were investigated by scanning electron microscopy. The surface elements compositions of carbon fibers were determined by X‐ray photoelectron spectrometer. The interfacial properties of composites were studied by interfacial shear strength. The thermo‐mechanical properties of two typical specimens (CF‐G0 and CF‐G1 composites) were investigated by dynamic mechanical thermal analysis. The results showed the introduction of GO sheets on carbon fibers surfaces effectively improved the mechanical properties of carbon fibers/epoxy composites. POLYM. COMPOS., 38:2425–2432, 2017. © 2016 Society of Plastics Engineers     

Processing and characterization of epoxy nanocomposites reinforced by cup-stacked carbon nanotubes

The effect of the dispersion, ozone treatment and concentration of cup-stacked carbon nanotubes on mechanical, electrical and thermal properties of the epoxy/CSCNT nanocomposites were investigated. Ozone treatment of carbon fibers was found to increase the surface oxygen concentration, thereby causing the contact angle between water, epoxy resin and carbon fiber to be decreased. Thus, the tensile strength, modulus and the coefficient friction of carbon fiber reinforced epoxy resin were improved. Moreover, the dispersion of fibers in polymer was increased and the electrical resistivity was decreased with the addition of filler content. The dynamic mechanical behavior of the nanocomposite sheets was studied. The storage modulus of the polymer was increased by the incorporation of CSCNTs. But the glass transition temperature decreased with increasing fiber loading for the ozone treated fiber composites. The ozone treatment did affect the morphology, mechanical and physical properties of the CSCNT.     

Synthesis of glass fiber‐multiwall carbon nanotube hybrid structures for high‐performance conductive composites

The conductive polyamide 66 (PA66)/carbon nanotube (CNT) composites reinforced with glass fiber‐multiwall CNT (GF‐MWCNT) hybrids were prepared by melt mixing. Electrostactic adsorption was utilized for the deposition of MWCNTs on the surfaces of glass fibers (GFs) to construct hybrid reinforcement with high‐electrical conductivity. The fabricated PA66/CNT composites reinforced with GF‐MWCNT hybrids showed enhanced electrical conductivity and mechanical properties as compared to those of PA66/CNT or PA66/GF/CNT composites. A significant reduction in percolation threshold was found for PA66/GF‐MWCNT/CNT composite (only 0.70 vol%). The morphological investigation demonstrated that MWCNT coating on the surfaces of the GFs improved load transfer between the GFs and the matrix. The presence of MWCNTs in the matrix‐rich interfacial regions enhanced the tensile modulus of the composite by about 10% than that of PA66/GF/CNT composite at the same CNT loading, which shows a promising route to build up high‐performance conductive composites. POLYM. COMPOS. 34:1313–1320, 2013. © 2013 Society of Plastics Engineers     

Piezoresistive behavior of epoxy matrix‐carbon fiber composites with different reinforcement arrangements

In this work, the self‐monitoring capability of epoxy matrix‐carbon fiber composites has been studied. Different concentrations and arrangements of reinforcements were used, including random chopped, unidirectional and bi‐directional continuous carbon fibers, weaved and nonweaved. Mechanical properties were determined by uniaxial tensile tests. The composite electric to mechanical behavior was established by determining its electrical resistivity variation as a function of the stress‐strain curve. It was observed that the composites electrical resistance increased during tensile tests, a trend that indicates piezoresistive behavior. The increase was linear for the chopped reinforced composites, while it exhibits different slopes in the continuous reinforced composites. The initial smaller slope corresponds mainly to separation of the 90° oriented fibers and/or transversal cracking of the matrix, whereas the latter higher slope is caused by fiber fracture. The results demonstrated how each reinforcement configuration exhibited a unique and typical electrical response depending on the specific reinforcement, which might be appropriate either for strain‐monitoring or damage‐monitoring. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009