Improving preferred orientation and mechanical properties of PAN-based carbon fibers by pretreating precursor fibers in nitrogen

Polyacrylonitrile fibers were heat-treated and stretched appropriately in nitrogen to make the nitrile groups cyclized partially and enhance the molecular orientation. A further reaction in air made the pretreated fibers fully stabilized, showing a higher preferred orientation than those of conventionally stabilized fibers. The resultant carbon fibers had a higher density, smaller interlayer spacing, lower porosity and better preferred orientation, which gave rise to considerable increases in tensile strength and Young’s modulus.     

Thermal properties of carbon fibers at very high temperature

Thermal properties such as specific heat C_p, thermal diffusivity a, and thermal conductivity λ of carbon fibers are important parameters in the behaviour of the carbon/carbon composites. In this study, the specific heat and the thermal diffusivity are measured at very high temperatures (up to 2500 K). The experimental thermal conductivity estimated by the indirect relation λ = aρC_p is presented as a function of the temperature. Validations are carried out on isotropic metallic (tungsten) and ceramic (Al₂O₃) fibers. Measurements were obtained on three carbon fibers (rayon-based, PAN-based and pitch-based). Thermal conductivity results allow us to classify fibers from the most insulated to most conductive. The main result is that insulated carbon fibers have an increasing thermal conductivity when the temperature and the heat treatment temperature rise. Relationships between thermal conductivity and the structural properties (L_c and d₀₀₂) of such carbon fibers are studied. We also describe the influence of heat treatment on the thermal conductivity of carbon fibers.     

PAN原丝成形工艺与碳纤维晶体结构和性能的关联性研究

采用广角X射线衍射方法对不同成形工艺的PAN原丝与碳纤维晶体结构和性能的关联性进行了实验和分析。研究表明:PAN原丝的晶体结构与凝固浴成形和纺丝牵伸工艺有直接关联性,由干喷湿纺成形和高倍纺丝牵伸制备的原丝具有晶粒尺寸较大、晶面间距较小和结晶度较高的特点。干喷湿纺成形工艺制备的原丝在碳化过程中石墨晶体的生长速率大于湿法纺丝,且原丝的PAN准晶体结构对碳纤维乱层石墨晶体结构具有遗传型。干喷湿纺成形和高倍数纺丝牵伸更容易获得兼具较高拉伸强度和较高拉伸模量的碳纤维。     

PAN基碳纤维预氧丝的取向结构及力学性能表征

利用傅立叶变换红外光谱仪对不同预氧化程度的聚丙烯腈(PAN)基碳纤维预氧丝进行偏振光谱分析,以反应程度参数(EOR)衡量试样的预氧化反应程度,用红外二向色性比来表征试样的取向程度,并对其力学性能进行了表征。结果表明:PAN纤维在预氧化过程中其化学组成和微观结构都发生了很大变化,纤维的取向程度随EOR的增大而减小,而力学性能也随之下降。     

Pitch-based ribbon-shaped carbon-fiber-reinforced one-dimensional carbon/carbon composites with ultrahigh thermal conductivity

Ribbon-shaped carbon fibers have been prepared from mesophase pitch by melt-spinning, oxidative stabilization and further heat treatment. The internal graphitic layers of ribbon-shaped carbon fibers graphitized at 2800 °C show a highly preferred orientation along the longitudinal direction. Parallel stretched and unidirectional arranged ribbon-shaped carbon fibers treated at about 450 °C were sprayed with a mesophase pitch powder grout, and then hot-pressed at 500 °C and subsequently carbonized and graphitized at various temperatures to produce one-dimensional carbon/carbon (C/C) composite blocks. The shape and microstructural orientation of ribbon fibers have been maintained in the process of hot-pressing and subsequent heat treatments and the main planes of the ribbon fibers are orderly accumulated along the hot-pressing direction. Microstructural analyses indicate that the C/C composite blocks have a typical structural anisotropy derived from the unidirectional arrangement of the highly oriented wide ribbon-shaped fibers in the composite block. The thermal conductivities of the C/C composites along the longitudinal direction of ribbon fibers increase with heat-treatment temperatures. The longitudinal thermal conductivity and thermal diffusivity at room temperature of the C/C composite blocks graphitized at 3100 °C are 896 W/m K and 642 mm²/s, respectively.     

The effect of degree of polymerization on the structure and properties of polyvinyl alcohol fibers with high strength and high modulus

Polyvinyl alcohol (PVA) fibers were prepared using PVA with different degree of polymerization (DP) under the same wet spinning process. The effect of the DP of PVA on the structures and properties of PVA and PVA fibers were studied by using nuclear magnetic resonance hydrogen spectroscopy (¹H-NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimeter (DSC), thermo gravimetric analysis (TGA), and environmental scanning electron microscope (ESEM). The results showed that DP had little effect on the crystallinity and tacticity of PVA, but had a positive effect on melting temperature, and initial decomposition temperature of PVAs. The hot drawing ratio determined by the spinning process where the PVA fibers could be continuously collected without breaking. The drawing ratio was decreased with an increase of DP, resulting in an increase of the final fiber diameter. The PVA fibers with medium DP and medium size demonstrated high strength and high modulus, but relatively low breaking elongation. It suggested that high DP of PVA was not a guarantee of high strength and high modulus PVA fibers, but rather a primary structure factor. The fiber performance was determined by a comprehensive effect combining a variety of factors including polymer properties and spinning conditions. It provided a guideline for PVA fiber manufacture that the PVAs with different DP require different spinning processes to obtain optimal fiber performance.     

不同线密度粘胶原丝及其碳纤维的结构性能对比

用Weibull分析处理 10mm长的 4种不同线密度粘胶原丝和相应碳纤维的单丝断裂强度 ,得到原丝线密度、强度分布和碳纤维强度的对应关系。采用透射电镜 (TEM )和小角X散射 (SAXS)分析粗旦原丝 ,发现孔洞较多 ,并存在大于 70nm的大孔洞。截面和表面照片也揭示出细旦原丝截面相对规整 ,表面较光滑 ,粗旦原丝则反之。结果表明 ,原丝线密度小 ,截面形状圆整 ,缺陷少 ,所制得的碳纤维强度高。     

The mesophase and high modulus carbon fibers from pitch

The evolution of the basic carbonization studies which led to the development of carbon fibers from mesophase pitch is described. The structure and properties of these fibers and comparisons with carbon fibers from other precursors are also discussed. Several basic areas related to fibers, the mesophase, and the mechanism of carbonization require further investigation.     

高性能碳纤维表面特性及其对浸润性能的影响

以4种不同型号的高性能碳纤维T700、UTS50、T800和IM7为研究对象,采用扫描电子显微镜和原子力显微镜对碳纤维直径、表面形貌和粗糙度进行表征,通过表面/界面张力仪对纤维表面能和树脂体系的表面张力进行分析,利用旋转流变仪对树脂体系的粘度进行测试。最后对碳纤维与不同温度和不同丙酮质量分数的618环氧树脂浸润性能进行测试,以分析纤维表面性能、温度和溶剂质量分数对碳纤维浸润性能的影响。结果表明,升高温度或提高溶剂质量分数有利于降低树脂体系的表面张力和粘度,从而有效改善碳纤维的浸润性能。纤维直径、表面粗糙度和表面能对碳纤维的浸润性能均有一定影响,其中纤维直径是影响浸润速率的主导因素,表面能和表面粗糙度对浸润质量的影响更加显著。     

Optical properties and orientation of thermally treated acrylic fibers

Acrylic fibers containing methyl acrylate copolymer have been thermally treated in the temperature range 473°–573°K in an inert, oxygen-free environment. The optical properties and an x-ray diffraction orientation parameter have been studied in these fibers, with special attention to correlation with the essential chemical reactions and to the behavior of polymer chain orientation. Densification of the fibers, illustrated by specific gravity and refractive index changes during the thermal treatment, is interpreted as a more efficient packing of the polymer chains in addition to the development of more highly refractive and dense chemical species. An extrapolated value of refractive index of 1.70 for 100% nitrile polymerization supports the presence of naphthyridine structures. Birefringence changes from ?0.003 to +0.27 imply a high degree of retention of the preferred orientation of polymer chains, despite the severe change in the chemical identity of the chains. The contrary behavior of the orientation parameter from the 100 arc of the x-ray diffraction of polyacrylonitrile as the thermal treatment proceeds indicates that the residual polyacrylonitrile sequences have reduced orientation.     

PAN基碳纤维连续石墨化过程中的取向性

利用XRD研究了PAN基碳纤维在连续高温石墨化和热牵伸石墨化过程中纤维内石墨微晶沿纤维轴择优取向性的变化。结果表明：碳纤维中石墨微晶的择优取向性随石墨化温度的提高和热牵伸的增大而增加。两种工艺中纤维的拉伸模量均随微晶取向性的增加而增大,但在获得相同的模量下其取向参数却不同;碳纤维的拉伸模量不仅仅取决于石墨微晶的择优取向,而且与晶体的大小有关。另外,经过3000℃的高温处理后,纤维的择优取向参数Z仅为14.71°,说明纤维中乱层石墨的层面仍没有高度取向。     

High strength and high modulus carbon fibers

Carbon fibers have been processed from gel spun polyacrylonitrile copolymer on a continuous carbonization line at Georgia Tech (GT) with a tensile strength in the range of 5.5–5.8 GPa, and tensile modulus in the range of 354–375 GPa. This combination of strength and modulus is the highest for any continuous fiber reported to date, and the gel spinning route provides a pathway for further improvements in strength and modulus for mass production of carbon fibers. At short gauge length, fiber tensile strength was as high as 12.1 GPa, which is the highest value ever reported for a PAN based carbon fiber. Structure analysis shows random flaws of about 2 nm size, which results in limiting tensile strength of higher than 20 GPa. Inter-planar turbostratic graphite shear modulus in high strength carbon fibers is 30 GPa, while in graphite the corresponding value is only 4 GPa.     

Evolution of structure and properties of PAN precursors during their conversion to carbon fibers

The formation and evolution of structure, and the changes of properties during the preoxidation, precarbonization, and carbonization of different PAN precursors were studied by the combination of DSC, FT-IR, SEM and some traditional measurements, such as density and mechanical properties of various fibers. The exothermic regime of polyacrylonitrile-based precursors made of acrylonitrile/itaconic acid (AN/IA) copolymers or acrylonitrile/acrylamide (AN/AM) copolymers is much broader and the cyclization reaction starts at lower temperature, compared to that of PAN homopolymer precursors, but AM appears to be more effective in separating the exothermic reactions corresponding to preoxidation stages in DSC curves as compared to IA. If AN/IA (97.5/2.5 w/w) precursors and AN/AM (97.5/2.5 w/w) precursors are designated as P1 and P2, respectively, the AM-containing commercial precursors (P3) are thermally more stable than the P2 ones, and the density of P3 is higher than that of P1 or P2. This may result from the difference of aggregation morphology among the original precursors, since it is dense for P3 precursors, whereas P2 and P1 precursors have some voids. The tensile strength of resultant carbon fibers from P3 precursors was better than that of carbon fibers from P2 or P1 after identical conditions of preoxidation are employed.     

Dynamic mechanical properties of carbon fibers

We have determined the dynamic mechanical properties in a low frequency range (0.01–10 Hz) of carbon and graphite fibers at different temperatures and evaluated the influence of fiber stretching. The results, showing frequency and extension dependent losses and changes in Young's moduli, indicate the presence of relatively large, independently mobile fiber constituents, which appear to correspond to the slowly undulating ribbons recognized earlier as the basic carbon fiber components.