Microstructure and properties of polyacrylonitrile based carbon fibers

The microstructure of polyacrylonitrile (PAN)-based carbon fibers with different mechanical properties was investigated. It was found that the tensile strength of the PAN-based carbon fibers generally decrease with the increase in the modulus. The properties of PAN-based carbon fiber are mainly controlled by the microstructure and microvoids. The increase in size and orientation of graphite crystallites follows the decrease in interlayer space of graphite sheets, which accompanies the increase in modulus and decrease in tensile strength of the carbon fibers. Simultaneously, the increase in the modulus of the carbon fibers accompanies the merging of the elliptical microvoids along the fiber axis and the turbostratic graphite in the carbon fibers transforms into 3D ordered graphite lamellar structure. This work provides useful information on tailoring the mechanical properties of carbon fibers by adjusting the microstructure.     

Mechanical properties of polyimide/multi-walled carbon nanotube composite fibers

A series of polyimide (PI)/multi-walled carbon nanotube (MWCNT) composite fibers were prepared by copolymerizing a mixture of monomers and carboxylic-functionalized MWCNTs, followed by dry-jet wet spinning, thermal imidization, and hot-drawing process. The content of the carboxylic groups of MWCNTs significantly increased when treated with mixed acid, whereas their length decreased with treatment time. Both the carboxylic content and length of MWCNTs influenced the mechanical properties of the composite fibers. Fiber added with 0.1 wt% MWCNTs treated for 4 h exhibited the best mechanical properties, i.e., 1.4 GPa tensile strength and 14.30% elongation at break, which were 51% and 32% higher than those of pure PI fibers, respectively. These results indicated that a suitable MWCNT content strengthened and toughened the resultant PI composite fibers, simultaneously. Moreover, raising draw ratio resulted in the increase of tensile strength and tensile modulus of the composite fibers.     

Annealing induced variation of crystalline structure and mechanical properties of syndiotactic polypropylene fibers

<正>Syndiotactic polypropylene(sPP) as-spun fiber(sPP1) and drawn fiber(sPP2) were prepared by melt-spinning and melt-spinning/hot-drawing,respectively.The structure transition of the two fibers induced by annealing at different temperatures and the corresponding mechanical properties were subsequently investigated by the combination of Fourier transform infrared spectroscopy(FTIR),wide-angle X-ray diffraction(WAXD) and tensile testing.The results indicate that the chain conformation and crystal forms of the two sPP fibers are not obviously changed at low annealing temperature (40℃).With increasing the annealing temperature,the trans-planar conformation and mesophase in sPP1 and sPP2 fibers can be completely transformed to helical conformation and crystal form I under tension.Upon removing the tension,a small amount of mesophase and trans-planar conformation will be regained.The mechanical properties of the annealed fibers are manifestly dependent on their initial structure and the annealing temperature.     

Effects of ultra-high temperature treatment on the microstructure of carbon fibers

The microcrystalline structure and microvoid structure in carbon fibers during graphitization process(2300-2700 °C) were characterized employing laser micro-Raman scattering(Raman), X-ray diffraction(XRD), small angle X-ray scattering(SAXS), and high-resolution transmission electron microscopy(HR-TEM). The crystalline sizes(L_a, L_c) increased and interlayer spacing(d_(002)) decreased with increasing heat treatment temperature(HTT). The microvoids in the fibers grew up and contacted to the neighbors with the development of microcrystalline. In addition, the preferred orientation of graphite crystallite along fiber axis decreased and microvoids increased. The results are crucial for analyzing the evolution of microstructure of carbon fibers in the process of heat treatment and important for the preparation of high strength and high modulus carbon fibers.     

The effect of surface modification with nitric acid on the mechanical and tribological properties of carbon fiber‐reinforced thermoplastic polyimide composite

Polyacrylamideacrylate (PAN)‐based carbon fibers were submitted to nitric acid oxidation treatments to improve the interfacial adhesion of the carbon fiber (CF)‐reinforced polyimide (CF/PI) composite. The carbon fiber surfaces were characterized by X‐ray photoelectron spectroscopy (XPS). Nitric acid oxidation not only affects the oxygen concentration but also produces an appreciable change in the nature of the chemical functions, namely the conversion of hydroxy‐type oxygen into carboxyl functions. Nitric acid oxidation treatment modifies the element constituting the fiber, the nitrogen concentration being about 1.2 times higher at the fiber external surface compared to the untreated one. The mechanical and tribological properties of the polymide (PI) composites reinforced by the carbon fibers treated with nitric acid oxidation were investigated. Results showed that the tensile strength of the CF/PI composites improved remarkably due to nitric acid treatment along with enhancement in friction and wear performance. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure and properties of polyimide fibers containing benzimidazole and Amide Units

Co‐polyimide (co‐PI) fibers with outstanding mechanical properties were fabricated via thermal imidization of polyamic acids, derived from a new design of combining the amide and benzimidazole diamine monomers, 4‐amino‐N‐(4‐aminophenyl)benzamide (DABA) and 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (BIA), with 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA). The crystalline structure and micromorphology of the prepared co‐PI fibers were investigated by synchrotron wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS). The two‐dimensional WAXD spectra imply that the co‐PI fibers possess a structure between smectic‐like and three‐dimensionally ordered crystalline phase, and all the obtained fibers are highly oriented along the fiber axis. SAXS patterns exhibit a pair of meridional scattering streaks for the homo‐PI (BPDA/BIA) fiber, suggesting the presence of periodic lamellar structure. The incorporation of DABA into the polymer chains destroyed the lamellar structure but led to smaller size of microvoids upon increasing DABA moiety, based on SAXS analysis. The co‐PI fibers, with the molar ratio of BIA/DABA being 7/3, exhibited the optimum tensile strength and modulus of 1.96 and 108.3 GPa, respectively, attributed to the well‐defined ordered and dense structure. The chemical structure and molecular packing significantly affected the thermal stability of fibers, resulting in the different glass transition temperatures (T_g) from 350 to 380 °C. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 183–191     

Preparation of High-performance Polyimide Fibers with Wholly Rigid Structures Containing Benzobisoxazole Moieties

In this work, a fully rigid coplanar symmetric heterocyclic unit was introduced into the rigid polyimide macromolecular backbone structure to prepare high-performance polyimide fibers. The novel co-polyimide(co-PI) fibers based on 3,3',4,4'-biphenyltetracarboxylic anhydride(BPDA), p-phenylenediamine(PDA) and 2,6-(4,4'-diaminodiphenyl) benzo[1,2-d:5,4-d'] bisoxazole(PBOA) were fabricated via a twostep wet-spinning method. The effects of benzobisoxazole moiety on spinnability, aggregation structure, and mechanical properties of fibers were systematically discussed. The detailed structural analysis revealed that the well-defined aggregation structures of co-PI fibers were obtained from initial amorphous structure when post hot-drawing temperature was higher than 460 ℃ under proper drawing ratio, and the incorporation PBOA into BPDA-PDA structures produced more compact structural co-PI fiber than homo BPDA-PDA fiber. The BPDA-PDA/PBOA co-PI fibers exhibited optimum tensile strength and modulus of 2.65 and 103 GPa, which increased by 182% and 84% compared to the homo BPDA-PDA fiber, respectively.     

BPDA/PPD/OTOL聚酰亚胺纤维的力学性能、形貌和结构

在3,3’,4,4’-联苯四酸二酐(BPDA)和对苯二胺(PPD)体系中引入3,3’-二甲基联苯胺(OTOL),显著改善了纤维的力学性能。当n(PPD)∶n(OTOL)=70∶30时,纤维的拉伸强度可达到改性前的2倍,其拉伸强度和拉伸模量分别为1.50和80 GPa。SEM照片显示了纤维的断面为圆形且没有孔穴,也没有明显的"皮芯"结构和原纤结构。WAXD和SAXS分析表明,纤维的轴向堆积和分子链取向在热牵伸过程中得到改善。     

Properties,Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers

The mechanical properties of fibers were notably improved by incorporating 2,2′-bis(trifluoromethyl)- benzidine(TFMB) into 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA) and p-phenylenediamine(PPD) backbone. The best strength and modulus of BPDA/PPD/TFMB polyimide(PI) fiber(diamine molar ratio of PPD/TFMB= 90/10) were 1.60 and 90 GPa, respectively, which was over two times that of BPDA/PPD PI fiber. SEM image showed that the cross-section of fibers at each stage was round and voids free. Besides, the “skin-core” and microfibrillar structure were not observed. The thermal properties of PI fibers were also investigated. The results showed that the fibers owned excellent thermal stability, moreover, the structural homogeneity of fibers were significantly improved by heat-drawn stage. The T_g values were found to be around 300℃ by dynamic mechanical analysis(DMA). Wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS) experiments indicated that the order degree of longitudinal and lateral stacks, the molecular orientation and the structural homogeneity of fibers were improved in the preparation process of fibers.     

聚丙烯腈基碳纤维中微孔洞的一维多取向小角X射线散射研究

应用一维多取向小角X射线散射(SAXS)方法研究了聚丙烯腈(PAN)基碳纤维中微孔洞的形态.结果表明,这些微孔洞沿纤维轴方向呈针状,并与纤维轴呈Φ=14°角的取向排列;微孔洞投影在碳纤维横截面上的平均半径R=1.14nm,投影在碳纤维轴向上的平均长度L=17.97nm.建立的一维多取向SAXS方法可以得到若干二维SAXS方法才能得到的微孔洞形态及分布信息等参数(如Φ和L),且在各种纤维的微孔洞或微纤维的表征方面具有一定的普适性.     

高密度聚乙烯/全同立构聚丙烯共混物超拉伸纤维的热行为与力学行为

用热拉法制备了高密度聚乙烯(HDPE)/全同立构聚丙烯(iPP)共混物超拉伸纤维,研究了拉伸比对其热行为及力学行为的影响,随拉伸比增加,纤维中HDPE与iPP的结晶度增大,熔融温度升高、熔程变宽;纤维中HDPE与iPP的结晶度低于其纯组分,熔融湿度与熔程基本不受组分比的影响,随拉伸比增加,纤维的模量增高,以HDPE为主的纤维的拉伸强度增大,以iPP为主的纤维拉伸强度增至一定值后,不再随拉伸比增加而增大,并有下降趋势。     

热亚胺化过程中气氛和拉力对BPDA-PDA聚酰亚胺纤维结构与性能的影响

研究了3,3',4,4'-联苯四酸二酐-对苯二胺(BPDA-PDA)型聚酰胺酸(PAA)纤维热亚胺化过程中气氛和拉力对聚酰亚胺(PI)纤维结构和性能的影响. 热处理过程中, 恒温处理5 min时, 虽然不同气氛下纤维的表面形貌并无明显差异, 但N₂气下所得纤维的力学性能明显优于空气下的样品, N₂气保护作用下, 最高断裂强度和初始模量分别达到1.25和65.0 GPa. 恒温处理40 min时, N₂气对纤维表面形貌有明显的保护作用. 但对于力学性能, 气氛的影响仅在450 ℃时表现得非常明显. 低于450 ℃时, 长时间的热处理成为影响纤维力学性能的主要因素, 气氛的影响变得不明显. 高于450 ℃时, 在N₂气和空气中的纤维皆发生明显的降解, 从而严重影响其力学性能. 热亚胺化过程中施加的拉力会促进纤维热酰亚胺化过程中的膨胀. 随着拉力的增加PI纤维长度增加, 同时直径减小. PI纤维轴上(004)晶面的间距、 晶粒尺寸、 线性热膨胀系数(为负值)的绝对值及玻璃化转变温度都随热处理时拉力的增加而增大. 纤维的断裂强度随拉力的变化基本保持在0.90 GPa左右, 断裂伸长率随着拉力增加稍有下降, 纤维的初始模量随拉力的增大而增加.     

DSC experiments on gel-spun polyethylene fibers

The tensile strength of gel-spun polyethylene fibers obtained after hot-drawing depends on spinning conditions such as spinning speed, spinning temperature, spinline stretching, polymer concentration, and molecular weight/molecular weight distribution. High deformation rates in the spinline result in shish-kebab structures which after hot-drawing lead to fibers with poor properties. This is in contrast to hot-drawn fibers obtained from gel-spun fibers with a lamellar structure. Lamellar or shish-kebab structures in the gel-spun fibers can be distinguished by means of DSC experiments on strained fibers. On the basis of these experiments a qualitative prediction of the final tensile properties can be made. DSC experiments on (un)strained hot-drawn fibers show that in the case of shish-kebab structures an incomplete transformation into a fibrillar structure takes place which partly explains the low tensile strength. Chain slippage which becomes possible after the orthorhombic-hexagonal phase transition is involved in the fracture mechanism. The shift of the orthorhombic-hexagonal phase transition to higher temperatures with increasing tensile strength indicates that the increase in strength corresponds to an increase in length of the crystal blocks. Consequently, creep failure also occurs at higher stresses. The melting behavior of cold-drawn and hot-drawn fibers is qualitatively similar, but the transformation into a fibrillar structure is more complete in the latter case.     

Morphology and tensile property relations of high-strength/high-modulus polyethylene fiber

High-strength/high-modulus polyethylene (PE) fibers have been obtained from linear polymers by melt-spinning the polyethylene followed by hot-drawing the spun filaments. Fibers with different tensile properties were made by changing the extrusion, solidification, and drawing conditions and by use of different types of polyethylene. Potential correlations of fiber strength with morphological parameters such as crystallite dimensions, and crystalline and amorphous orientation were examined. The integrated meridional small-angle x-ray scattering intensity is the only morphological parameter which was found to correlate well with the strength of fibers prepared under different conditions and from different polymer types. Implications with respect to the molecular mechanism of PE fiber drawing are also discussed.     

2D SAXS/WAXD analysis of pan carbon fiber microstructure in organic/inorganic transformation

Structure of PAN fibers during pre-oxidation and carbonization was studied using two dimensional small angle X-ray scattering/wide angle X-ray diffraction(2D SAXS/WAXD).The SAXS results show that during pre-oxidation between 180 ℃ and 275 ℃,the volume content of microvoids increases with the temperature increasing,which may be one of reasons for the decrease of tensile strength of pre-oxidized fibers.253 ℃ was the critical transition temperature,the length,diameter,aspect ratio and orientation distribution of microvoids increased with temperature before this temperature and decreased after this temperature.After the high temperature carbonization,lots of spindly microvoids formed.WAXD patterns demonstrate that the crystallite size of PAN fibers first increased before 230 ℃ and then decreased with the increase of temperature during the pre-oxidation.The diffraction peak of PAN fibers at 2θ≈ 17° almost disappeared at the end of preoxidation while the diffraction peak of aromatic structure at 2θ≈ 25° appeared at 253 ℃.During carbonization,the peak intensity at 2θ≈ 25° increased apparently due to the formation of graphite structure.The results obtained give a deep understanding of the microstructure development in the PAN fibers during pre-oxidation and carbonization,which is important for the preparation of high performance carbon fibers.     

Mechanically-induced dimensional extensibility of fibers towards tough fiber networks

The beneficial effect of materials with high aspect ratio as composite reinforcement has prompted continuous interest towards cellulosic fibers. Besides providing stiffness, fibers can potentially contribute to composite extensibility. While mechanical treatments are typically used to adjust the physical and surface properties of fibers, less is known about ensuing effects on their extensibility and that of associated networks. Fiber network dimensional extensibility of 16% was achieved by processing the precursor aqueous fiber dispersions following a simple mechanical treatment with a judicious combination of low (PFI refining) and high concentrations and temperatures (Wing defibrator). Consequently, deformation of fibers and increased inter-fiber bonding resulted in a three-fold increase in strength to rupture of the fiber network leading to the structures with unprecedented toughness.     

表面复合纳米SiO_2和碳纳米管玻璃纤维增强尼龙6的结构与性能

利用静电相互作用在玻璃纤维(GF)表面分别复合纳米二氧化硅(SiO2)和多壁碳纳米管(MWNTs),制备了GF-SiO2、GF-MWNTs复合增强体,并通过转矩流变仪制备了尼龙6(PA6)/GF-SiO2和尼龙6(PA6)/GF-MWNTs复合材料.利用扫描电子显微镜(SEM),示差扫描量热仪(DSC),热机械分析仪(DMA)等手段研究了复合材料的微观结构、热学及力学性能.结果表明,静电复合的方法可以使纳米二氧化硅(nano-SiO2)、多壁碳纳米管(MWNTs)在GF表面达到均匀吸附,复合增强体能加快尼龙6的结晶速度,并使材料的玻璃化温度、动态模量、拉伸强度、结晶温度等明显提高,其中GF-MWNTs对复合材料性能的提高最明显,拉伸强度提升了21%,模量提高了28%.     

Synthesis and properties of novel polyimide fibers containing phosphorus groups in the side chain (DATPPO)

A series of polyamic acid copolymers(co-PAAs) containing phosphorous groups in the side chains were synthesized from [2,5-bis(4-aminophenoxy) phenyl] diphenylphosphine oxide(DATPPO) and 4,4′-oxydianiline(ODA) with 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA) through the polycondensation in N,N′-dimethyacetamide(DMAc). The co-PAA solutions were spun into fibers by a dry-jet wet spinning process followed by thermal imidization to obtain co-polyimide(co-PI) fibers. FTIR spectra and elemental analysis confirmed the chemical structure of PI fibers. SEM results indicated that the resulting PI fibers had a smooth and dense surface, a uniform and circle-shape diameter. The thermogravimetric measurements showed that with the increase of DATPPO content, the resulting PI fibers possessed high decomposition temperature and residual char yield, indicating that the PI fibers had good thermal stability. The corresponding limiting oxygen index(LOI) values from the experiment results showed that the co-PI fibers possessed good flame-retardant property. Furthermore, the mechanical properties of the co-PI fibers were investigated systematically. When the DATPPO content increased, the tensile strength and initial modulus of the co-PI fibers decreased. However, the mechanical properties were improved by increasing the draw ratio of the fibers. When the draw ratio was up to 2.5, the tensile strength and initial modulus of the co-PI fibers reached up to 0.64 and 10.02 GPa, respectively. The WAXD results showed that the order degree of amorphous matter increased with increased stretching. In addition, the SAXS results displayed that valuably drawing the fibers could eliminate the voids inside and lead to better mechanical property. WAXD revealed that the orientation of the amorphous polymer influenced the mechanical properties of the fibers.     

石墨烯诱导水凝胶成核的高强韧人造蛛丝

天然蜘蛛丝是由β-sheet交联的蛛丝蛋白溶剂流入S-型导管后经牵引拉伸形成,它显示了高强度与高韧性的完美结合。其优异的力学性质主要源于它的多级结构：交联、线性排列的纳米组装体以及核壳结构。受此启发,我们合成了一种交联的水凝胶,通过牵引拉丝的方法,制备了交联的、含有取向排列的纳米组装体结构以及核壳结构的凝胶纤维,并通过少量引入二维纳米材料—氧化石墨烯(0.01%),进一步调控纳米组装体的取向和尺寸,实现了蜘蛛丝般优异的力学性能(断裂强度560 MPa,断裂韧性200 MJ·m^–3,缓冲能94%)。这种纤维可以用于高速下落物体的能量耗散和降低冲击力。     

Structure and properties of regenerated cellulose fibers from aqueous NaOH/thiourea/urea solution

Regenerated cellulose fibers were successfully prepared through dissolving cotton linters in NaOH/thiourea/urea aqueous solution at ?2 °C by a twin-screw extruder and wet-spinning process at varying precipitation and drawing conditions. The dissolution process of an optimized 7 wt% cellulose was controlled by polarizing microscopy and resulted in a transparent and stable cellulose spinning dope. Rheological investigations showed a classical shear thinning behavior of the cellulose/NaOH/thiourea/urea solution and a good stability towards gelation. Moreover, the mechanical properties, microstructures and morphology of the regenerated cellulose fibers were studied extensively by single fiber tensile testing, X-ray diffraction, synchrotron X-ray investigations, birefringence measurements and field-emission scanning electron microscopy. Resulting fibers demonstrated a smooth surface and circular cross-section with homogeneous morphological structure as compared with commercial viscose rayon. At optimized jet stretch ratio, acidic coagulation composition and temperature, the structural features and tensile properties depend first of all on the drawing ratio. In particular the crystallinity and orientation of the novel fibers rise with increasing draw ratio up to a maximum followed by a reduction due to over-drawing and oriented crystallites disruption. The microvoids in the fiber as analysed with SAXS were smaller and more elongated with increasing drawing ratio. Moreover, a higher tensile strength (2.22 cN/dtex) was obtained in the regenerated fiber than that of the viscose rayon (2.13 cN/dtex), indicating higher crystallinity and orientation, as well as more elongated and orientated microvoid in the regenerated fiber. All in all, the novel extruder-based method is beneficial with regard to the dissolution temperature and a simplified production process. Taking into account the reasonable fiber properties from the lab-trials, the suggested dissolution and spinning route may offer some prospects as an alternative cellulose processing route.