Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part I: Effect of carbon nanotubes on stabilization

Addition of carbon nanotubes (CNTs) in polyacrylonitrile (PAN) fibers significantly improves the mechanical properties of the resulting carbon fibers. This study focuses on the effect of different types of CNTs on chemical, mechanical and structural changes during the stabilization of gel-spun CNT/PAN composite fibers. Among the different types of CNTs, it was observed that CNTs containing more walls had lower reinforcement efficiency than CNTs containing fewer walls. Similarly CNTs containing fewer walls exhibited higher orientation of the ladder polymer and greater effect on the formation of β-amino nitrile in the stabilized fibers. Wide angle X-ray diffraction, infrared spectroscopy, and scanning electron microscopy were used to determine the optimum stabilization time. Additionally, it was found that the higher tension applied during stabilization improved the properties of the stabilized fibers, and the addition of CNTs increased the maximum tension that the fiber can bear.     

Investigation of the ultradrawing properties of gel spun fibers of ultra‐high molecular weight polyethylene/carbon nanotube blends

The carbon nanotubes (CNTs) contents, ultrahigh‐molecular‐weight polyethylene (UHMWPE) concentrations and temperatures of UHMWPE, and CNTs added gel solutions exhibited significant influence on their rheological and spinning properties and the drawability of the corresponding UHMWPE/CNTs as‐prepared fibers. Tremendously high shear viscosities (ηs) of UHMWPE gel solutions were found as the temperatures reached 140°C, at which their ηs values approached the maximum. After adding CNTs, the ηs values of UHMWPE/CNTs gel solutions increase significantly and reach a maximum value as the CNTs contents increase up to a specific value. At each spinning temperature, the achievable draw ratios obtained for UHMWPE as‐prepared fibers prepared near the optimum concentration are significantly higher than those of UHMWPE as‐prepared fibers prepared at other concentrations. After addition of CNTs, the achievable draw ratios of UHMWPE/CNTs as‐prepared fibers prepared near the optimum concentration improve consistently and reach a maximum value as their CNTs contents increase up to an optimum value. To understand these interesting drawing properties of the UHMWPE and UHMWPE/CNTs as‐prepared fibers, the birefringence, thermal, morphological, and tensile properties of the as‐prepared and drawn fibers were investigated. Possible mechanisms accounting for these interesting properties are proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A comparison of reinforcement efficiency of various types of carbon nanotubes in polyacrylonitrile fiber

Polyacrylonitrile (PAN)/carbon nanotubes (CNTs) composite fibers were spun from solutions in dimethyl acetamide (DMAc), using single wall (SWNTs), double wall (DWNTs), multi wall (MWNTs) carbon nanotubes, and vapor grown carbon nanofibers (VGCNFs). In each case, CNT content was 5 wt% with respect to the polymer. Structure, morphology, and properties of the composite fibers have been characterized using X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, tensile tests, dynamic mechanical tests, as well as thermal shrinkage. While all nanotubes contributed to property improvements, maximum increase in modulus (75%) and reduction in thermal shrinkage (up to 50%) was observed in the SWNT containing composites, and the maximum improvement in tensile strength (70%), strain to failure (110%), and work of rupture (230%) was observed in the MWNTs containing composites. PAN orientation is higher in the composite fiber (orientation factor up to 0.62) than in the control PAN fiber (orientation factor 0.52), and the PAN crystallite size in the composite fiber is up to 35% larger than in the control PAN (3.7 nm), while the overall PAN crystallinity diminished slightly. Nanotube orientation in the composite fibers is significantly higher (0.98 for SWNTs, 0.88 for DWNTs, and 0.91 for MWNTs and VGCNFs) than the PAN orientation (0.52-0.62). Improvement in low strain properties (modulus and shrinkage) was attributed to PAN interaction with the nanotube, while the improvement in high strain properties (tensile strength, elongation to break, and work of rupture) at least in part is attributed to the nanotube length. Property improvements have been analyzed in terms of nanotube surface area and orientation.     

Multiwalled carbon nanotube/polyacrylonitrile composite fibers prepared by in situ polymerization

Multi‐walled carbon nanotubes (CNTs) were mixed with polyacrylonitrile (PAN) by in situ polymerization or by mechanically mixing. The mixtures were then wet‐spun into fibers, respectively. The effects of mixing method on the interfacial bonding between the components in the fibers and the properties of the fiber were investigated by Raman spectroscopy, TEM, SEM, and tensile strength testing. By in situ polymerization mixing, a thin layer of PAN molecules is observed to cover the surface of the CNT, which increases the diameter of CNT evidently. Results of Raman spectroscopy indicate that the layer of PAN molecules are strongly attached onto the surface of CNT through grafting polymerization, leading to strong chemical bonding between CNTs and PAN matrix in the obtained fibers. In contrast, no obvious chemical interactions are observed between them in the fibers prepared by mechanically mixing. In both cases, the CNTs have significantly strengthened the PAN fibers. However, the fibers prepared from in situ polymerization mixing are much stronger because of the interfacial bonding effect between the PAN molecules and CNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enhanced compatibilization and orientation of polyvinyl alcohol/gelatin composite fibers using carbon nanotubes

Polyvinyl alcohol (PVA)/gelatin composite fibers containing carbon nanotubes (CNTs) had been prepared by wet‐spinning method. A remarkable increase of tensile strength of the PVA/gelatin fibers was achieved by adding small amount of CNT. The mechanism of reinforcement has been studied using a combination of differential scanning calorimetry (DSC), 2D wide‐angle X‐ray diffraction (2D‐WAXD) and scanning electron microscopy (SEM). SEM showed a decreased gelatin domain size by adding CNTs, suggesting a possible compatibilization effect between PVA and gelatin. On the other hand, an increased crystallinity and degree of orientation of PVA/gelatin fibers has been observed by adding CNTs. Thus, the increased compatibilization, crystallinity and degree of orientation in PVA/gelatin/CNTs composite fibers should be the reasons for the observed increase of mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

Correlation between inhomogeneity in polyacrylonitrile spinning dopes and carbon fiber tensile strength

The nano‐scale and micro‐scale inhomogeneity of polyacrylonitrile (PAN) spinning dopes obtained from dynamic light scattering (DLS) experiment is correlated with the tensile strength of the resulting carbon fiber. The nanoscale inhomogeneity was estimated by calculating the diffusion coefficients from the slow relaxation mode of polymer solutions in DLS. The nanoscale inhomogeneity in the spinning dopes was found to be in the range of 1–45 nm. We also demonstrate mean of the count rate (MCR) obtained from DLS of PAN solution as a tool to detect the microscale inhomogeneity in the spinning dope for the first time. The MCR of spinning dopes varied from ~10.0 to 77.5 kcps (kilo‐counts per second). The tensile strength of carbon fibers from the precursor fiber spun from the spinning dopes in this study varied from 3 to 5.2 GPa. Correlation studies show that the microscale inhomogeneity in the spinning dope was a major contributor to the decrease in the tensile strength of carbon fibers in the range of 3–4.5 GPa. Contaminants causing microscale inhomogeneity in PAN powder were removed by using micelles, reverse micelles and frothing. The surfactant treated PAN polymer was characterized using a fourier transform infrared spectroscope, differential scanning calorimeter, and thermal gravimetic analyzer to demonstrate complete removal of surfactants. POLYM. ENG. SCI., 59:478–482, 2019. © 2018 Society of Plastics Engineers     

Investigations of the preparation technology for polyglycolic acid fiber with perfect mechanical performance

Polyglycolic acid (PGA) fibers were prepared by melt‐spinning process in this report. The effects of spinning parameters, such as windup rates and drawn ratio, on the mechanical properties of the fibers were discussed by analyzing the internal stress of as‐spun fibers, axial sound velocity, fiber tenacity, etc. The results showed that windup rate had a slight effect on the macromolecular orientation degree of the as‐spun fibers, which was quite unusual for melt spinning, whereas, the subsequent drawing process effectively increased the macromolecular orientation degree of the PGA fibers and consequently increased the tensile strength of the fibers. Low internal stress of as‐spun fibers obtained at lower windup rate led to higher drawing ratio, and the drawn fibers possessed relatively excellent mechanical properties. As a contrast, higher windup rate resulted in the strong internal stress of the as‐spun fibers, which had a negative influence on the drawing process, and so the tensile strength of the drawn fibers was relatively poor. Therefore, PGA fiber with perfect mechanical performance could be prepared at the technical parameters of lower windup rate and higher drawing multiples as well as slow drawing rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Force field in coagulation bath at low temperature induced microfibril evolution within PAN nascent fiber and precursor fiber

The coagulation process was vital for the microfibril evolution and mechanical properties of polyacrylonitrile (PAN) fibers. The PAN nascent fibers and precursor fibers were prepared by controlling drawing ratio of coagulation bath at low temperature during the dry-jet wet spinning process. The microfibril morphological changes induced by force fields in coagulation bath were investigated by scanning electron microscopy and high-resolution transmission electron microscopy. During the coagulation process, the spinning solution evolved into an interconnected network composed of random microfibrils and tie joints as a building block of the network. At low drawing ratio, the random interconnected network existed in nascent fibers. Increasing drawing ratio, the fiber filaments underwent shrinkage and the network was transformed into the transverse lamellae. Furthermore, the lamellar thickness also decreased. After the treatment of post-spinning, similar transverse lamellae were formed in all of precursor fibers, and random microfibrillar network was stretched and oriented to develop into the aligned microfibrils in precursor fibers. The transverse fold-chain crystal layers were densely stacked in the microfibrils. Increasing drawing ratio, the lamellae and microfibrils in precursor fibers were packed more densely and orderly. Consequently, the order and homogeneity of microfibrils in nascent fibers and precursor fibers were improved by increasing drawing ratio, which were benefit to increase fiber tensile strength and modulus.     

超高相对分子质量PET纤维的拉伸和热处理工艺

研究了超高相对分子质量ＰＥＴ纤维后拉伸和热处理工艺。结果表明,提高拉伸倍数和一定条件下的热处理可明显提高纤维的强度和模量,聚合体相对分子质量和纺丝浓度及拉伸温度对纤维的可拉伸性有重要影响。乙二醇作为一种热处理介质,可提高纤维强度和模量。增加热处理张力,可以明显地提高纤维的强度。     

Polyacrylonitrile solution homogeneity study by dynamic shear rheology and the effect on the carbon fiber tensile strength

Poly(acrylonitrile‐co‐methacrylic acid) (PAN‐co‐MAA)/N,N‐dimethylformamide (DMF) solutions were prepared and dynamic shear rheology of these solutions were investigated. With increasing stirring time up to 72 h at 70°C, the polymer solution became less elastic (more liquid‐like) with a ～60% reduction in the zero‐shear viscosity. Relaxation spectra of the PAN‐co‐MAA/DMF solutions yield a decrease in relaxation time (disentanglement time, τ_d), corresponding to an about 8% decrease in viscosity average molecular weight. The log‐log plot of G′ (storage modulus) versus G″ (loss modulus) exhibited an increase in slope as a function of stirring time, suggesting that the molecular level solution homogeneity increased. In order to study the effect of solution homogeneity on the resulting carbon fiber tensile strength, multiple PAN‐co‐MAA/DMF solutions were prepared, and the precursor fibers were processed using gel‐spinning, followed by continuous stabilization and carbonization. The rheological properties of each solution were also measured and correlated with the tensile strength values of the carbon fibers. It was observed that with increasing the slope of the G′ versus G″ log‐log plot from 1.471 to 1.552, and reducing interfilament fiber friction during precursor fiber drawing through the addition of a fiber washing step prior to fiber drawing, the carbon fiber strength was improved (from 3.7 to 5.8 GPa). This suggests that along with precursor fiber manufacturing and carbonization, the solution homogeneity is also very important to obtain high strength carbon fiber. POLYM. ENG. SCI., 56:361–370, 2016. © 2016 Society of Plastics Engineers     

Polylactide. II. Discontinuous dry spinning–hot drawing preparation of fibers

The mechanical properties and morphology of poly(L-lactide) fibers, prepared by the dry spinning–hot drawing process using different nonsolvent/chloroform spinning solutions, were studied in relation to fiber in vitro degradability. Acetone, methanol, ethanol, and cyclohexane were used as nonsolvents in the spinning mixture with as-polymerized PLLA, i.e., PLLA containing 10% of residual L-lactide. The tensile strength, structure, and degradability of obtained fibers were mainly governed by the nonsolvent volatility. Generally, the higher the volatility, the higher the strength, and the faster the degradation. The acetone/chloroform spinning system produced fiber with an increased degradation rate in comparison to the pure chloroform spinning system. © 1994 John Wiley & Sons, Inc.     

PAN接枝CNTs的制备及其复合溶液的流变行为

采用浓硝酸、氯化亚砜、三乙烯四胺先后对碳纳米管(CNTs)进行氧化、酰氯化和胺化,通过原位聚合将聚丙烯腈(PAN)接枝到CNTs端头或表面制得改性CNTs;研究了含改性CNTs的PAN复合溶液的流变行为。结果表明:PAN接枝到CNTs上并形成网络结构,被接枝的聚合物的质量分数约59%,接枝率约为144%。通过原位聚合,改性CNTs可均匀分散到PAN/二甲基亚砜溶液中,复合溶液体系存在网络结构,流变行为稳定,具备可纺性。     

High strength micron size carbon fibers from polyacrylonitrile–carbon nanotube precursors

An improved, high strength, carbon fiber derived from islands-in-a-sea bi-component gel spun polyacrylonitrile (PAN)–carbon nanotube (CNT) precursor fibers containing 1 wt% mixture of single, double, and few walled CNTs was developed. Microscale experiments with properly designed MEMS tools provided the mechanical properties of individual, 1-μm diameter carbon filaments, which were isolated from bundles of 407 fibers. The statistics of the mechanical strength were described well by the cumulative Weibull probability density function that resulted in characteristic strength of 6.2 GPa and a Weibull modulus of 4.5, while the highest tensile strength and Young’s modulus values were 7.3 GPa and 318 GPa, respectively. At the lower end of the spectrum, the strength values correlated well with predictions based on an effective flaw size obtained from fracture cross-sections. On the other hand, the failure cross-sections of the high strength carbon fibers contained a large number of long and oriented CNTs but no discernible flaws. The high interfacial strength between the CNTs and the surrounding carbon resulted in fracture and telescopic pull-out of the CNTs, which was corroborated by individual CNT pull-out experiments with MEMS tools inside an SEM, and in situ fiber failure observations of telescopic pull-out of CNTs inside a TEM.     

干-喷湿纺聚丙烯腈纤维拉伸工艺研究

研究了干 -喷湿纺聚丙烯腈 (PAN)初生纤维的喷丝头拉伸比和三级拉伸 (空气拉伸、DMF浴拉伸、热水和沸水拉伸、干热拉伸 )工艺中各拉伸比对纤维性能的影响。结果表明 :提高喷丝头拉伸比可明显地降低初生纤维的线密度 ,提高强度 ;三级拉伸工艺中各拉伸比的提高均有利于PAN纤维线密度的减小及其强度、声速取向度和抗张模量的提高 ;合理调配三级拉伸中各拉伸比可制得强度超过 7.0cN/dtex的PAN纤维     

碳纳米管/聚丙烯腈导电纤维的结构与性能

使用浓硫酸和浓硝酸的混合溶液将多壁碳纳米管进行功能化处理后与聚丙烯腈(PAN)进行共混,采用湿法成形技术制备出了多壁碳纳米管/PAN导电纤维。采用扫描电镜、动态力学分析等手段对纤维的结构进行了分析,对纤维的物理机械性能及导电性能进行了测试。结果表明:添加碳纳米管5%时PAN纤维的强度、储存模量及玻璃化转变温度提高,断裂伸长率下降;添加经过功能化处理的碳纳米管可以有效地提高纤维的导电性能,当含量为5%时,电导率可达10-3S/cm。     

Influence of spinning/hot drawing conditions on the tensile strength of porous high molecular weight polyethylene

Summary Hot drawing in a temperature gradient has been applied to porous high molecular weight polyethylene fibers. The porous fibers were produced by spinning a 5% solution in paraffin oil and subsequently extracting the paraffin oil in n-hexane. Spinning/drawing under appropriate conditions resulted in a fiber with a tensile strength at break of 4.1 GPa. The porosity and tensile strength of a fiber were measured as a function of draw ratio. The influence of spinning/drawing conditions is discussed in relation to fiber texture and entanglement topology.     

The influence of pyrolysis on physical properties and microstructure of modified PAN fibers during carbonization

Modification of polyacrylonitrile (PAN) fibers with potassium permanganate has reduced the time required for stabilization and also improved the mechanical properties of the resulting carbon fibers. In this study, the effect of modification on the physical properties, microstructure, and elemental composition of fibers during the carbonization process was examined for the first time. The resulting carbon fibers developed from modified PAN fibers had a higher density, a greater stacking size (Lc), and a higher preferred orientation than those developed from unmodified PAN fibers. The carbon fibers developed from the modified PAN fibers also showed an improvement in tensile strength from 20 to 40%. These fibers showed a radial structure in the fracture surface and were somewhat different structurally in the cross section than were the carbon fibers developed from the original PAN fibers. A model for the structure of both carbon fibers is presented. The relationship between the formation of closed pores from open pores and the variety of cumulative pore area during the heat-treatment stage is also discussed.     

聚丙烯腈/多壁碳纳米管共混纤维的研制

碳纳米管经表面改性后与聚丙烯腈溶液共混制备了纺丝浆液,采用湿法纺丝技术制备了聚丙烯腈/多壁碳纳米管(PAN/MWNT)共混纤维。研究了碳纳米管对共混溶液动态流变性能的影响,探讨了共混纤维的物理机械性能和结晶特性。结果表明:MWNTs的加入降低了纺丝原液的黏度,明显提高了共混纤维的力学性能,降低了延伸率,并对纤维的结晶度有一定的影响。     

Fiber preparation and mechanical properties of recycled polypropylene for reinforcing concrete

Polypropylene (PP) fibers have been widely used to reinforce concrete footpaths as an alternative to steel mesh. The reinforcing effect of the PP fiber is directly proportional to its tensile strength and Young modulus. This research explored the feasibility of using an improved melt spinning and hot drawing process to produce virgin and recycled PP fibers of high mechanical properties in an industrial scale. Commercial grade granules of virgin PP, recycled PP and HPDE were mixed in different proportions in preparing five different types of fibers. All the fibers obtained high tensile strength and Young modulus. A relationship between the structural parameters and mechanical properties was then established. It was observed that the melt spinning and hot drawing process formed both α‐form and β‐form crystals in the PP fibers, and significantly improved crystallinity from about 50% to 80%. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41866.