Review of the mechanical properties of carbon nanofiber/polymer composites

In this paper, the mechanical properties of vapor grown carbon nanofiber (VGCNF)/polymer composites are reviewed. The paper starts with the structural and intrinsic mechanical properties of VGCNFs. Then the major factors (filler dispersion and distribution, filler aspect ratio, adhesion and interface between filler and polymer matrix) affecting the mechanical properties of VGCNF/polymer composites are presented. After that, VGCNF/polymer composite mechanical properties are discussed in terms of nanofibers dispersion and alignment, adhesion between the nanofiber and polymer matrix, and other factors. The influence of processing methods and processing conditions on the properties of VGCNF/polymer composite is also considered. At the end, the possible future challenges for VGCNF and VGCNF/polymer composites are highlighted.     

Study on morphology and characterization of poly(mphenylene isophtalamide)/multi-walled carbon nanotubes composite nanofibers by electrospinning

Electrospinning technique is the main method of preparing polymer nanofiber simply, directly and continuously at present. In this work, electrospinning blend solution was prepared by in-situ polymerization using acid-modified multi-walled carbon nanotubes (MWNTs), m-phenylenediamine (MPD) and isophthaloyl chloride (IPC). And then composite nanofibers were prepared by electrospinning. MWNTs played an important role in nanofiber's properties. The effects of MWNTs on the morphology and characterization of the MWNTs/PMIA composite nanofibers were investigated. Scanning electron microscopy (SEM), thermal gravimetric analyzer (TGA), and X-ray diffraction (XRD) were utilized to characterize the MWNTs/PMIA nanofibers morphology and properties. The experimental results indicated that the nanofibers diameter decreased and solution dynamic viscosity increased with increasing MWNTs contents. XRD data demonstrated that PMIA composite nanofibers had the same crystal type as the pure PMIA nanofiber, and crystallinity was improved with increasing MWNTs loading. Transmission electron microscopy (TEM) was used to confirm MWNTs aligned along the axis of composite nanofibers.     

Fire retardancy of clay/carbon nanofiber hybrid sheet in fiber reinforced polymer composites

In this paper, two kinds of clay/carbon nanofiber hybrid sheets containing 0.05 wt% and 0.20 wt% of Cloisite Na⁺ clay, were fabricated through a high-pressure filtration system. These sheets were integrated onto the surface of laminated composites like traditional continuous fiber mats through vacuum-assisted resin transfer molding process. The fire performance of the laminated composites was evaluated with cone calorimeter tests under an external radiant heat flux of 50 kW/m². Their residues were analyzed with scanning electron microscopy and thermal gravimetric analyses. It was found that the clay/nanofiber hybrid sheets survived on the combustion surface of composites and significantly reduced the heat release rate by 60.5%. The protective clay layer reduces the heat release rates and the nanofiber network reinforces the clay layer against the air bubbling and melt flow of the products degraded from the polymer resin. The clay/carbon nanofiber hybrid sheet combines the barrier and insulator effects of the clays with the re-emitting heat effect of carbon nanofibers on the combustion surface of composites.     

Electrically Conductive Carbon Nanofiber Composites with High-Density Polyethylene and Glass Fibers

Carbon nanofibers are being investigated for incorporation into composites to improve mechanical, thermal, and electrical properties. The difficulties in making such composites are issues of dispersion of the nanofiber and wetting of the nanofibers by the matrix. The processing methods developed to date tend to be complex, involving multiple steps. This paper reports on a study to make electrically conductive composites with small volume fraction of vapor-grown carbon nanofibers (VGCF). The matrix is a high-density polyethylene (HDPE); the effect of adding glass fibers to this composite is also studied. Certain types of the VGCF fibers did not produce conductive composites with standard mixing techniques; however, VGCF nanofibers heat treated with a post-processing surface treatment produced conductive composites without extensive or vigorous dispersion techniques. The results indicate that surface treatments and dispersion methods are important factors in producing conductive composites. It is demonstrated that small volume fractions of nanofiber can be used to produce conductive composites without extensive processing steps.     

单晶PZT-CFO铁电-铁磁复合纳米纤维的制备与磁学性能研究

以不同锆掺杂量的前钙钛矿结构钛酸铅和铁酸钴为原料,采用原位固相烧结法合成了一系列单晶锆钛酸铅-铁酸钴(PZT-CFO)复合纳米纤维。X射线衍射、扫描电子显微镜和能谱分析结果表明,一维单晶PZT-CFO复合纳米纤维同时存在钙钛矿相的锆钛酸铅和尖晶石相的铁酸钴。高分辨透射电子显微镜研究证实锆钛酸铅和铁酸钴之间存在外延生长关系。采用振动样品磁强计对PZT-CFO复合纳米纤维的磁学性能进行测试,发现该复合纳米纤维具有明显的铁磁性能,其剩余磁化强度和矫顽力随着锆掺杂量的增加而增加。     

High performance polyimide composite films prepared by homogeneity reinforcement of electrospun nanofibers

Highly aligned polyimide (PI) and PI nanocomposite fibers containing carbon nanotubes (CNTs) were produced by electrospinning. Scanning electron microscopy showed the electrospun nanofibers were uniform and almost free of defects. Transmission electron microscopy indicated that the CNTs were finely dispersed and highly oriented along the CNT/PI nanofiber axis at a relatively low concentration. The as-prepared well-aligned electrospun nanofibers were then directly used as homogeneity reinforcement to enhance the tensile strength and toughness of PI films. The neat PI nanofiber reinforced PI films showed good transparency, decreased bulk density and significantly improved mechanical properties. Compared with neat PI film prepared by solution casting, the tensile strength and elongation at break for the PI film reinforced with 2 wt.% CNT/PI nanofibers were remarkably increased by 138% and 104%, respectively. The significant increases in the overall mechanical properties of the nanofibers reinforced polyimide films can be ascribed to good compatibility between the electrospun nanofibers and the matrix as well as high nanofiber orientation in the matrix. Our study demonstrates a good example for fabricating high performance and high toughness polyimide nanocomposites by using this facile homogeneity self-reinforcement method.     

Stretching-induced crystallinity and orientation to improve the mechanical properties of electrospun PAN nanocomposites

Polyacrylonitrile-based carbon fibers, embedded with single-walled carbon nanotubes have been prepared by the electrospinning technique. The as-spun nanofibers were hot-stretched in an oven to enhance the orientation and crystallinity which has been confirmed by X-ray diffraction and DSC etc. With the hot-stretched process and the introduction of SWNTs, the mechanical properties of PAN nanofibers such as the modulus and tensile strength will be enhanced correspondingly. In addition, the electrical conductivities of the PAN/SWNTs nanofiber composites were also enhanced. It was concluded that the hot-stretched nanofibers and the PAN/SWNTs nanofiber composites can be used as a potential precursor to produce high-performance carbon nanocomposites.     

The effect of flow type and chemical functionalization on the dispersion of carbon nanofiber agglomerates in polypropylene

Two melt mixing methods generating flow with different characteristics are compared to study the dispersion of 5% w/w carbon nanofibers in polypropylene, namely conventional twin-screw extrusion and the simple application of a converging/diverging flow sequence to the composite melt. The effect of nanofiber surface modification and compatibilization with polypropylene modified with maleic anhydride is also studied. The dispersion of the nanofiber agglomerates through the polymer, the electrical properties of the resulting composites and nanofiber/polymer interface achieved under the different mixing conditions are analyzed. The converging/diverging flow sequence generated a better dispersion as compared with the twin-screw extruder.     

Experimental study of mechanical and electrical properties of carbon nanofiber/epoxy composites

Epoxy nanocomposites of different content of carbon nanofibers up to 1 wt.% have been fabricated under room temperature and refrigerated curing conditions. The composites were studied in terms of mechanical and electrical properties. Flexural modulus and hardness were found to increase significantly in refrigerated samples due to prevention of aggregates of nanofibers during cure condition. Increase and shifting in G-band by Raman spectra of these samples confirmed stress transfer and reinforcement between epoxy matrix and carbon nanofiber. Electrical conductivity improved by 3–6 orders after infusing carbon nanofibers in insulating epoxy. Room temperature samples acquired higher conductivity that was attributed to network formation by aggregates of nanofibers along the fiber alignment direction as revealed by electron microscopic studies.     

聚偏氟乙烯电纺纤维膜的制备及其热释电性能研究

β晶相的聚偏氟乙烯(PVDF)由于具有强压电和热释电特性,被广泛应用在能量收集、红外探测等领域。采用静电纺丝技术制备PVDF纤维,通过SEM以及XRD表征,研究了溶剂组成、溶液浓度和纺丝液供给速度等纺丝参数对PVDF纤维膜形貌和β晶相含量的影响,制备出连续、均匀、直径约600nm的PVDF纤维。另外,测试了PVDF纤维膜对不同调制频率的3.4μm波长红外光的热释电响应特性。     

Characterization and mechanical performance comparison of multiwalled carbon nanotube/polyurethane composites fabricated by electrospinning and solution casting

Multiwalled carbon nanotube/polyurethane (MWNT/PU) composites were prepared by electrospinning and solution casting. The morphological and thermal properties, and mechanical performance of the nanofiber and film composites were characterized and compared. The tensile strength of neat PU film was 9-fold higher than that of neat PU nanofibrous mat. The incorporation of MWNTs increased the tensile strength and modulus of the composite nanofibers by 69% and 140%, respectively, and 62% and 78%, respectively for composite films. The MWNT/PU composites showed an improved thermal degradation behavior, with the incorporation of low MWNT content in the composites.     

Fabrication and evaluation of polyamide 6 composites with electrospun polyimide nanofibers as skeletal framework

In this study, two types of polyimide (PI) nanofiber mats, including (1) the mats consisting of (almost) randomly overlaid PI nanofibers and (2) the mats consisting of highly aligned PI nanofibers, were prepared by the materials-processing technique of electrospinning. The nanofiber mats were subsequently used to develop composites with polyamide 6 (PA6) via the composites – fabrication method of polymer melt infiltration lamination (PMIL). Owing to superior mechanical properties (i.e., the tensile strength and modulus were 1.7 GPa and 37.0 GPa, respectively) and large specific surface area of electrospun PI nanofibers, the PI/PA6 composites with PI nanofiber mats as skeletal framework demonstrated excellent mechanical properties. In particular, the PI/PA6 composite containing 50 wt.% of aligned PI nanofibers had the tensile strength and modulus of 447 MPa and 3.0 GPa along the longitudinal direction, representing ～700% and ～500% improvements as compared to neat PA6.     

Improving the interlaminar properties of polymer composites using a situ accumulation method to construct the multi-scale reinforcement of carbon nanofibers/carbon fibers

A novel method was developed to realize the situ accumulation of carbon nanofibers (CNFs) in the carbon fiber reinforced polymer composites (CFRPs) to construct the multi-scale reinforcement for improving the interlaminar properties. In this method, the prepreg was sealed by the nanomicroporous nylon membrane, and the excess resin was extracted from the prepreg by the vacuum-assisted method. It was found that the use of nylon membrane resulted in effective CNFs accumulation, especially in the interlayer by scanning electron microscopy. Short-beam strength tests and the end-notched flexure tests were conducted respectively to evaluate the interlaminar properties of CFRPs under shear loading. The results indicated that the interlaminar shear strength (ILSS) and the Mode II interlaminar fracture toughness (G_IIC) of CFRPs made by the filtering membrane-assisted method remarkably increased compared with those prepared without using filtering membrane.     

Improved fire retardancy of thermoset composites modified with carbon nanofibers

Multifunctional thermoset composites were made from polyester resin, glass fiber mats and carbon nanofiber sheets (CNS). Their flaming behavior was investigated with cone calorimeter under well-controlled combustion conditions. The heat release rate was lowered by pre-planting carbon nanofiber sheets on the sample surface with the total fiber content of only 0.38 wt.%. Electron microscopy showed that carbon nanofiber sheet was partly burned and charred materials were formed on the combusting surface. Both the nanofibers and charred materials acted as an excellent insulator and/or mass transport barrier, improving the fire retardancy of the composite. This behavior agrees well with the general mechanism of fire retardancy in various nanoparticle-thermoplastic composites.     

BaTiO3纳米线的制备及其复合物介电和储能性能研究

采用两步水热法合成钛酸钡(BaTiO₃)纳米线, 并以此为填充物, 聚偏氟乙烯六氟丙烯(P(VDF-HFP))为聚合物基体制备介电复合物, 研究不同含量BaTiO₃纳米线对复合物的介电及储能性能的影响。采用X射线衍射仪、扫描电镜、透射电镜、阻抗分析仪和铁电工作站等表征BaTiO₃纳米线及其复合物的物相、微观结构、介电和储能性能。结果表明: BaTiO₃纳米线具有典型的四方相, 且在聚合物基体中具有良好的分散性与相容性。相同频率下, 复合物的介电常数随着BaTiO₃纳米线含量的增加而增加。含量为20vol%的复合物, 在1 kHz频率下其介电常数取得最 大值30.69。含量为5vol%的复合物, 在场强为240 kV/mm时, 获得了最大的储能密度与放电能量密度, 分别为4.89和2.58 J/cm³。     

Electrospun poly(l-lactide)/zein nanofiber mats loaded with <Emphasis Type="Italic">Rana chensinensis</Emphasis> skin peptides for wound dressing

Electrospun nanofiber mats can display impressive performance as an ideal wound dressing. In this study, poly(l-lactide)(PLLA)/zein nanofiber mats loaded with Rana chensinensis skin peptides (RCSPs) were successfully produced by two different electrospinning techniques, blend and coaxial, with the goal of developing a wound dressing material. The nanofiber mats were investigated by environmental scanning electron microscope (ESEM), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), water contact angle, mechanical tests and cell viability. The resulting nanofiber mats exhibited smooth surfaces, tiny diameters and different cross-sectional shapes from pure PLLA and zein nanofibers. The FTIR result showed that PLLA, zein and RCSPs were well dispersed, without chemical interactions. Compared with coaxial nanofiber mats, blending zein-RCSPs with PLLA enhanced hydrophilicity but decreased mechanical properties. Adding RCSPs into the electrospun nanofibers significantly improved the mechanical properties of the mats. Cell viability studies with human foreskin fibroblasts demonstrated that cell growth on PLLA/zein-RCSPs nanofiber mats was significantly higher than that on PLLA/zein nanofiber mats. The results indicate that nanofiber mats containing RCSPs are potential candidates for wound dressing.     

再生丝素/聚乙烯醇共混纳米纤维的制备及表征

以三氟乙酸、二氯甲烷和水为溶剂,采用静电纺丝的方法制备再生丝素/聚乙烯醇共混纳米纤维。分析了共混配比对相容性及静电纺丝的影响,采用扫描电镜、X射线衍射仪、红外光谱仪等对所得纤维的形态与结构进行了表征,测试了纳米纤维的力学性能,结果表明:丝素分子和聚乙烯醇分子间发生了某种程度的相互作用,相容性得到改善,添加聚乙烯醇的丝素纳米纤维的力学性能有明显改善。     

Improved fire retardancy of thermoset composites modified with carbon nanofibers

Abstract

Multifunctional thermoset composites were made from polyester resin, glass fiber mats and carbon nanofiber sheets (CNS). Their flaming behavior was investigated with cone calorimeter under well-controlled combustion conditions. The heat release rate was lowered by pre-planting carbon nanofiber sheets on the sample surface with the total fiber content of only 0.38 wt.%. Electron microscopy showed that carbon nanofiber sheet was partly burned and charred materials were formed on the combusting surface. Both the nanofibers and charred materials acted as an excellent insulator and/or mass transport barrier, improving the fire retardancy of the composite. This behavior agrees well with the general mechanism of fire retardancy in various nanoparticle-thermoplastic composites.     

Reusing recycled fibers in high-value fiber-reinforced polymer composites: Improving bending strength by surface cleaning

Glass fiber-reinforced polymer (GFRP) composites and carbon fiber-reinforced polymer (CFRP) composites were recycled using superheated steam. Recycled glass fibers (R-GFs) and recycled carbon fibers (R-CFs) were surface treated for reuse as fiber-reinforced polymer (FRP) composites. Treated R-GFs (TR-GFs) and treated R-CFs (TR-CFs) were characterized by scanning electron microscopy (SEM) and remanufactured by vacuum-assisted resin transfer molding (VARTM). Most residual resin impurities were removed by surface treatment. Analysis indicated no adverse effect of surface treatment on bending strength. The mechanical properties of the TR-GF reinforced polymer (TR-GFRP) and TR-CF reinforced polymer (TR-CFRP) composites were determined and compared with those of R-GF reinforced polymer (R-GFRP) and R-CF reinforced polymer (R-CFRP). The bending strengths of R-GFRP (26%) and R-CFRP (49%) were very low, compared to that of virgin glass fiber-reinforced polymer (V-GFRP) and that of virgin carbon fiber-reinforced polymer (V-CFRP). The bending strength of TR-GFRP composites was improved to about 90% of that of V-GFRP, and the bending strength of TR-CFRP composites was improved to about 80% of that of V-CFRP.     

A comparative study of EMI shielding properties of carbon nanofiber and multi-walled carbon nanotube filled polymer composites

Electromagnetic interference shielding properties of carbon nanofiber- and multi-walled carbon nanotube-filled polystyrene composites were investigated in the frequency range of 8.2-12.4 GHz (X-band). It was observed that the shielding effectiveness of composites was frequency independent, and increased with the increase of carbon nanofiber or nanotube loading. At the same filler loading, multi-walled carbon nanotube-filled polystyrene composites exhibited higher shielding effectiveness compared to those filled with carbon nanofibers. In particular, carbon nanotubes were more effective than nanofibers in providing high EMI shielding at low filler loadings. The experimental data showed that the shielding effectiveness of the composite containing 7 wt% carbon nanotubes could reach more than 26 dB, implying that such a composite can be used as a potential electromagnetic interference shielding material. The dominant shielding mechanism of carbon nanotube-filled polystyrene composites was also discussed.