新型碳纤维用原丝——高强高模Lyocell纤维纺丝工艺研究

采用天然高相对分子质量纤维素脱脂棉为原料 ,制备了高强高模纤维素纤维 ( L yocell纤维 ) ,并用此作为碳纤维原丝 ,成功制得了强度优于粘胶基碳纤维的 L yocell基碳纤维。考察了高相对分子质量纤维素的溶解特点 ,纺丝工艺对 L yocell纤维聚集态及性能的影响 ,比较了 L yocell纤维和粘胶原丝的表面及截面形态。实验表明 :高相对分子质量纤维素溶解的静溶胀时间和温度对其溶解有明显的影响 ;纺丝过程中 ,大的气隙长度对提高纤维的性能有利 ;随着凝固浴中 N -甲基吗啉 N -氧化物( NMMO )的浓度增加 ,纤维的强度和模量增加 ,当其在凝固浴中的质量分数达到 10 %时 ,强度模量最大 ,浓度继续增加 ,纤维的力学性能开始下降 ;拉伸比增加 ,L yocell纤维的强度模量增加 ,当拉伸比大于 3.0时 ,纤维的性能略有下降     

Mechanical and viscoelastic properties of soybean oil thermoset reinforced with jute fabrics and carded lyocell fiber

Composites and hybrid composites were manufactured from renewable materials based on jute fibers, regenerated cellulose fibers (Lyocell), and thermosetting polymer from soybean oil. Three different types of jute fabrics with biaxial weave architecture but different surface weights, and carded Lyocell fiber were used as reinforcements. Hybrid composites were also manufactured by combining the jute reinforcements with the Lyocell. The Lyocell composite was found to have better mechanical properties than other composites. It has tensile strength and modulus of about 144 MPa and 18 GPa, respectively. The jute composites also have relatively good mechanical properties, as their tensile strengths and moduli were found to be between 65 and 84 MPa, and between 14 and 19 GPa, respectively. The Lyocell‐reinforced composite showed the highest flexural strength and modulus, of about 217 MPa and 13 GPa, respectively. In all cases, the hybrid composites in this study showed improved mechanical properties but lower storage modulus. The Lyocell fiber gave the highest impact strength of about 35 kJ/m², which could be a result of its morphology. Dynamic mechanical analysis showed that the Lyocell reinforced composite has the best viscoelastic properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nano‐carbon black filled Lyocell fiber as a precursor for carbon fiber

In this work, Lyocell fibers filled with various amounts of carbon black were prepared. Wide angle X‐ray diffraction (WAXD) results showed that carbon black filled Lyocell fibers still had a cellulose II crystal structure and kept the characteristic peak of carbon black at the same time. The results of mechanical properties showed a slight reduction in the carbon black filled Lyocell fiber. Moreover, the heat stabilities of the carbon black filled Lyocell fibers showed no obvious change. The residue of carbon black filled Lyocell fiber at 1000°C was higher than that of Lyocell fiber, implying higher carbon yield could be obtained for the carbon black filled Lyocell precursor. Scanning electron microscopy (SEM) experiments showed that the surface and the cross section of carbon black filled Lyocell fiber were smooth and round, which are consistent with the carbon fiber precursor. The WAXD pattern of carbon black filled Lyocell‐based carbon fiber was different from that of Lyocell‐based carbon fiber. The addition of carbon black transfers the diffraction peak of carbon fiber while keeping the characteristic structure of carbon black. The results of mechanical properties of carbon fibers show that, if an appropriate amount of carbon black was chosen, carbon fiber with better properties than Lyocell‐based carbon fiber could be obtained by using the carbon black filled Lyocell fibers as the precursor. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 65–74, 2006     

Lyocell fibers as the precursor of carbon fibers

In this work, Lyocell fibers, used as carbon fiber precursors, were investigated. Lyocell fibers used for the carbon precursors and the carbon fibers themselves were produced in our laboratory. The mechanical properties morphology and structure of the precursors and the obtained carbon fibers were studied and compared to those of rayon. The results show that Lyocell fibers have higher tenacity and modulus, and better thermal stability than rayon fibers. Scanning electron microscopy (SEM) experiments show that Lyocell precursors have round cross‐sections and fewer defects in the fibers, while rayon fiber has an oval cross‐section and many defects. Wide angle X‐ray diffraction (WAXD) results for the Lyocell precursors indicate that the degree of crystallinity of the Lyocell precursor is higher than that of a rayon precursor. They also show that Lyocell based carbon fibers have better mechanical properties than those that are rayon‐based. WAXD data of the obtained carbon fibers show that the crystallinity of Lyocell‐based carbon fiber is higher than that of rayon‐based carbon fiber. It is concluded that the Lyocell fibers are better precursors for carbon fibers than rayon. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1941–1947, 2003     

Morphology and mechanical and electrical properties of oriented PVA-VGCF and PVA-MWNT composites

The composites poly(vinyl alcohol) (PVA) and vapor growth carbon fiber (VGCFs) and multi wall carbon nanotubes (MWNTs) were prepared by gelation/crystallization from the mixture of dimethyl sulfoxide (DMSO) and water (H₂O). The composite films were elongated to 5-10-fold uniaxially. The mechanical properties of PVA composites were improved significantly by introduction of VGCFs and MWNTs and also by the orientation of fillers. Compared to VGCFs, MWNTs was more effective to improve the electric conductivity of the composites because of its network structure. The change in the electrical conductivity for the PVA/MWNT composites containing 5 wt% MWNT was independent of the draw ratio up to eight-fold indicating no disruption of the network formation. A certain high level of filler content was proved to be necessary for the promotion of both mechanical and electrical properties in oriented composite.     

Influence of the spinning conditions on the structure and properties of polyamide 12/carbon nanotube composite fibers

The inclusion of nanoparticles in polymer fibers is potentially useful for improving or bringing new properties such as mechanical strength, electrical conductivity, piezoresistivity, and flame retardancy. In this study, composite fibers made of polyamide 12 and multiwall carbon nanotubes were investigated. The fibers were spun via a melt‐spinning process and stretched at different draw ratios. The influence of several spinning factors, including spinning speed, extrusion rate, and draw ratio were investigated and correlated to the structure and properties of the fibers. X‐ray diffraction analyses and mechanical tests indicated that the spinning speed barely affected the structure and mechanical properties of the fibers under tension. The spinning speed, however, is critical for future industrial applications because it determines the possible production rates. By contrast, drawing during spinning or after spinning strongly affected the polymer chain alignment and fiber mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of hemicelluloses on the structure and properties of Lyocell fibers

In the present paper the difference in the structure and properties of Lyocell fibers with different hemicelluloses content was investigated. The supermolecular structure and the morphological characterization were compared. The fibril aggregation size was estimated by the cross‐polarization magic‐angle spinning carbon‐13 nuclear magnetic resonance (CP/MAS¹³C‐NMR) spectroscopy. Meanwhile, the difference in the mechanical, the fibrillation resistance and the dyeing properties of Lyocell fiber with different hemicelluloses content was also analyzed. POLYM. ENG. SCI., 47:702–706, 2007. © 2007 Society of Plastics Engineers.     

Extension‐induced mechanical reinforcement in melt‐spun fibers of polyamide 66/multiwalled carbon nanotube composites

In this work, polyamide 66 (PA66) and its composites with multiwalled carbon nanotubes (MWNTs) were melt spun into fibers at different draw ratios. PA66 fibers at high draw ratio demonstrate a 40% increase in tensile strength, 66% increase in modulus and a considerable increase in toughness. It is demonstrated that this reinforcement can be mainly attributed to high‐draw‐ratio‐induced good dispersion and orientation of MWNTs, particularly the enhanced interfacial adhesion between MWNT and matrix thanks to interfacial crystallization. Our work provides a simple but efficient method to achieve good dispersion and strong interfacial interaction through melt spinning. Copyright © 2011 Society of Chemical Industry     

纳米炭黑添加剂对纤维素/NMMO纺丝原液流变行为及其纤维结构性能的影响

研究了纳米炭黑添加剂对纤维素/NMMO·H2O溶液流变行为及Lyocell纤维结构与性能的影响。研究结果表明:添加了纳米炭黑的纤维素/NMMO·H2O溶液属典型的切力变稀型流体。纳米炭黑的加入使溶液的流动活化能有所增大,并且少量纳米炭黑的加入使体系的黏度有明显的降低,但随着炭黑含量的进一步增加,溶液黏度又逐渐增大。添加了适量纳米炭黑的Lyocell纤维的结构致密,其强度和模量虽略有降低,但结晶结构和热稳定性不变,由此制得的碳纤维不仅得率可有效提高,且强度和模量大大改善。     

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     

Impact damage sensing in glass fiber reinforced composites based on carbon nanotubes by electrical resistance measurements

In this article, we report an interesting employment of multi‐walled carbon nanotubes as a filler in the epoxy matrix of a glass fiber reinforced composite (FRP). The intrinsic electrical conductivity of carbon nanotubes made the development of a nanocomposite with enhanced electrical properties possible. The manufactured nanocomposite was subsequently employed in the production of a glass FRP. Due to the high aspect ratio of carbon nanotubes, very small amounts of these particles were sufficient to modify the electrical properties of the obtained glass fiber composites. Basically, a three‐phases material was developed, in which two phases were electrically insulating—epoxy matrix and glass fiber—and one phase highly conductive, the carbon nanotubes. The main goal of this study was to investigate the possibility of developing a glass fiber reinforced nanocomposite (GFRN), which is able to provide measurable electrical signals when subjected to a low‐velocity impact on its surface. Following this goal, the drop in the mechanical performance of the composite was evaluated before and after the impact. At the same time, the variation in its electrical resistance was measured. The results have shown that it is possible to associate the increase in electrical resistance of the composite with the formation of damages caused by impact. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Carbon‐Polymer Composite Bipolar Plate for HT‐PEMFC

Graphene reinforced carbon‐polymer composite bipolar plate is developed using resole phenol formaldehyde resin, and conductive reinforcements (natural graphite, carbon black, and carbon fiber) using compression molding technique. Graphene is reinforced into the composite to alter various properties of the composite bipolar plate. The developed composite bipolar plate is characterized and the effect of temperature on mechanical and electrical properties is investigated with an overall aim to achieve benchmark given by US‐DOE and Plug Power Inc. The flexural strength and electrical conductivity of the composites was almost stable with the increase in temperature upto 175 °C. The composite bipolar plate maintained high in‐plane and through‐plane electrical conductivities, which is about 409.23 and 98 S cm^–1, respectively, at 175 °C. The flexural strength and shore hardness of the developed composite was around 56.42 MPa and 60, respectively, at 175 °C, and on further increase in the temperature the mechanical strengths deceases sharply. The electrical and mechanical properties of the composite bipolar plates are within the US‐DoE target. However, the various properties of the composite bipolar plate could not be sustained above 175 °C.     

Comparison of the structures and properties of Lyocell fibers from high hemicellulose pulp and high α‐cellulose pulp

Lyocell fibers were produced from a cheap pulp with a high hemicellulose content and from a conventional pulp with a high α‐cellulose content. The mechanical properties, supermolecular structure, fibrillation resistance, and dyeing properties as well as the fibril aggregation size of the high hemicellulose Lyocell fiber and high α‐cellulose Lyocell fiber were compared. The results showed that the high hemicellulose spinning solution could be processed at a higher concentration, which improved the mechanical properties and the efficiency of the fiber process. Compared with the high α‐cellulose Lyocell fiber, the high hemicellulose Lyocell fiber had better fibrillation resistance and dyeing properties. Therefore, it is feasible that this cheap pulp with a high hemicellulose content can be used as a raw material for producing Lyocell fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of novel epoxy composites containing electrospun PA6/F‐MWNTs fibers

The Nylon 6 (PA6)/the functionalized multiwalled carbon nanotubes (F‐MWNTs) fibrous membranes were fabricated by electrospinning, and then incorporated into an epoxy matrix. Their morphology, thermal stability, mechanical properties, thermal conductivities, and electrical resistivity were investigated. The electrospun PA6/F‐MWNTs fibers performed as a skeleton in the epoxy matrix, and the well interfacial adhesion between the epoxy matrix and the PA6/F‐MWNTs fibers leads to high mechanical properties of composites. The PA6 serves as an intermediate layer and alleviates the modulus mismatch between the stiff MWNTs and the soft epoxy matrix. The thermal conductivities of the epoxy composites increase by 27.3, 35.0, and 36.1%, respectively, with 0.5, 1 and 1.5 wt% F‐MWNTs loading in the PA6/F‐MWNTs fibers. At the same time, the PA6 simultaneously retains the high electrical resistivity of these epoxy composites. POLYM. ENG. SCI., 56:1259–1266, 2016. © 2016 Society of Plastics Engineers     

Study on the preparation and properties of aligned carbon nanotubes/polylactide composite fibers

The oriented carbon nanotubes (CNTs)/polylactic acid (PLA) composite fibers was prepared by the modified electrospinning technology, and characterized by Raman, X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and thermogravimetric (TG)/differential scanning calorimetric (DSC) analyses, respectively. Results showed that functionalized MWNTs have obvious orientation along the fiber axial in the interior of the electrospun PLA fibers, and improved the crystallization degree of PLA in the composite fibers due to the heterogeneous nucleation effect. The influences of polycaprolactone‐functionalized multiwalled carbon nanotubes (MWNTs‐PCL) on the performances of PLA fibers were studied. The crystallization region inside the MWNTs–PCL/PLA composite fibers was enlarged by increasing the MWNTs‐PCL content. As a result, enhanced crystallization temperature was obtained. Moreover, a small amount of MWNTs‐PCL (0.5%) improved the thermal stability of PLA matrix, while excess MWNTs‐PCL (3.0%) induced the decrease of the thermal stability of PLA resin due to the agglomeration of MWNTs‐PCL. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effective reinforcement of carbon nanotubes in polypropylene matrices

This study describes an attempt to mechanically reinforce polypropylene (PP) using multi‐wall carbon nanotubes (MWNTs) through a melt compounding process followed by hot‐pressing and solid state drawing. The effect of a high density polyethylene (HDPE) coating on MWNTs and melt flow index (MFI) of PP on the dispersion of MWNTs and composite properties are studied by means of mechanical tests, transmission electron microscopy (TEM), scanning electron microscope (SEM), differential scanning calorimetry (DSC), and wide angle x‐ray diffraction (WAXD). Highly orientated composite tapes are prepared to fully utilize the properties of MWNTs in uniaxial direction. Highly aligned MWNTs are shown by SEM, while highly oriented polymer chains are characterized by WAXD. Composite theory is used to analysis the results and indicate that effective reinforcement of PP by MWNTs is highest at relatively low filler content and draw ratios. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multiwalled carbon nanotube polymer composites: Synthesis and characterization of thin films

The aim of this article was to elucidate the basic relationships between processing conditions and the mechanical and electrical properties of multiwalled carbon nanotube reinforced polymer composites. In conventional chopped fiber reinforced polymer composites, uniform distributions of fibers throughout the matrix are critical to producing materials with superior physical properties. Previous methods have dispersed carbon nanotubes by aggressive chemical modification of the nanotubes or by the use of a surfactant prior to dispersion. 1 , 2 Here, ultrasonic energy was used to uniformly disperse multiwalled nanotubes (MWNTs) in solutions and to incorporate them into composites without chemical pretreatment. Polystyrene (PS) solutions containing MWNTs were cast and spun to yield thin film MWNT composites. The rheology of PS/MWNT suspensions was modeled using the Carreau equation. MWNTs were found to align at the shear rates generated by the spin casting process. The tensile modulus and strain to failure of samples compared well to classical micromechanical models, increasing with MWNT loading. The composite films showed lower strains at the yield stress than neat PS films. The presence of MWNTs at 2.5 vol % fraction approximately doubles the tensile modulus, and transforms the film from insulating to conductive (surface resistivity, ρ, approaching 10³ Ω/□). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2660–2669, 2002     

Polyethylene composite fibers. I. Composite fibers of high‐density polyethylene

Polymer matrix composites are generally studied in the form of bulk solids, and very few works have examined composite fibers. The research described here extended such bulk studies to fibers. The question is whether or not what has been reported for bulk polymers will be the same in fibers. In this article are reported studies of high‐density polyethylene (HDPE), whereas those of linear low‐density polyethylene are reported in part II of this article series. Two types of filler were used, that is, organically modified montmorillonite (OMMT), in which the nanosized filler particles had a high aspect ratio, and microsized calcium carbonate (CaCO₃), with an aspect ratio nearer to unity. Composite fibers of both as‐spun and highly drawn forms were prepared, and their structures, morphology, and mechanical properties were studied. It was found that the microsized particles gave HDPE composite fibers with mechanical properties that were the same as those of the neat polymer. In the case of clay composite fibers, the clay interfered with the yield process, and the usual yield point could not be observed. The particle shape did not affect the mechanical properties. The fibers showed different deformation morphologies at low draw ratios. The CaCO₃ composite fibers showed cavities, which were indicative of low interaction between the polymer and the filler. The OMMT composite fibers showed platelets aligned along the fibers and good polymer–filler interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mass production of carbon nanotube‐reinforced polyacrylonitrile fine composite fibers

A facile and large‐scale production method of polyacrylonitrile (PAN) fibers and carboxyl functionalized carbon nanotube reinforced PAN composite fibers was demonstrated by the use of Forcespinning® technology. The developed polymeric fibers and carbon nanotube‐reinforced composite fibers were subsequently carbonized to obtain carbon fiber systems. Analysis of the fiber diameter, homogeneity, alignment of carbon nanotube and bead formation was conducted with scanning electron microscopy. Thermogravimetric analysis, electrical, and mechanical characterization were also conducted. Raman and FTIR analyses of the developed fiber systems indicate interactions between carbon nanotubes and the carbonized PAN fibers through π–π stacking. The carbonized carbon nanotube‐reinforced PAN composite fibers possess promising applications in energy storage applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40302.     

多壁碳纳米管/炭黑/顺丁橡胶导电复合材料的研究

采用机械共混法制备多壁碳纳米管(MWNTs)/炭黑/顺丁橡胶(BR)复合材料,研究其导电性和物理性能。结果表明,与炭黑相比,MWNTs能够更好地改善BR的电性能;当炭黑用量为40份时,加入1份MWNTs可使复合材料的体积电阻率从1.2×1010Ω.cm降至7.0×105Ω.cm;当MWNTs/炭黑用量比为5/40时,MWNTs和炭黑在BR中的协同补强作用较明显,复合材料的邵尔A型硬度、拉伸强度、拉断伸长率和撕裂强度均显著提高。