WAXD/SAXS study and 2D fitting (SAXS) of the microstructural evolution of PAN-based carbon fibers during the pre-oxidation and carbonization process北大核心CSCD

Microstructutal evolution in polyacrylonitrile (PAN) fibers at different temperatures during pre-oxidation and carbonization under stretching was studied by. synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). Microvoids were characterized by the classical SAXS method, and were compared with simulation results obtained by fitting 2D SAXS patterns to a model based on a dilute system of cylindrical microvoids randomly distributed and preferentially orientated along the fiber axis and having a log-normal size distribution. The WAXD results showed that the crystal size, d-spacing and preferred orientation decreased during pre-oxidation, and increased during carbonization. A diffraction peak for PAN fibers at 2 theta = 13. 6 degrees disappeared during the final stage of pre-oxidation, meanwhile a new peak at 2 theta = 23.6 degrees appeared, whose intensity increased during carbonization, indicating the formation of the graphite structure. The average length of the microvoids increased, and new microvoids were formed, which became oriented along the fiber axis as the fiber manufacturing process proceeded. The length of microvoids from simulation results is consistent with that from the classical method, indicating that the model is valid to describe the microvoid structure of fibers.     

颗粒分散技术在真空液相浸渗制备Cf/Al复合材料中的应用

采用真空反压液相浸渗工艺,以碳纤维增强铝为研究对象,探讨了M40J纤维增强AlMg10复合材料制备工艺中,SiC及淀粉分散颗粒对复合材料微观组织及性能的影响。结果表明,碳化硅可以减少铝液在束内的浸渗阻力,并使纤维分布均匀,从而提高复合材料构件的成型性和力学性能。经过5%SiC+3%淀粉溶液的分散后,复合材料的体积分数由72%降低到51%,而复合材料的拉伸强度提高了131MPa,达到498MPa。     

Formation of composites comprised of calcium deficient HAp and cross-linked gelatin

Cross-linked gelatin/calcium deficient hydroxyapatite (CDHAp) composites were prepared at or near physiologic temperature. alpha-tricalcium phosphate (alpha-TCP) or a mixture of tetracalcium phosphate and dicalcium phosphate were used as CDHAp precursors. Glutaraldehyde was used to cross-link the gelatin fibers. CDHAp formation reached completion in the presence of cross-linked gelatin fibers. Effects of cross-linking concentrations, proportions of gelatin fiber, molecular weight of gelatin and the temperature of the hydration reaction on the formation of CDHAp were studied. Cross-linked gelatin acts as a nucleating agent for CDHAp formation. The pH variations during CDHAp formation are lower at the onset of the reactions in the presence of cross-linked gelatin fibers. Although cross-linked gelatin fibers enhance CDHAp formation their composites have low mechanical strengths. Swelling of gelatin appears to be a major factor that limits the strengths of the CDHAp/cross-linked gelatin composites.     

Phosphate salts facilitate the electrospinning of hyaluronic acid fiber mats

Electrospinning is a cost effective and facile method to manufacture fiber mats appropriate for biomedical applications. Due to its high molecular weight and charged backbone, hyaluronic acid (HA) fiber mats with consistent fiber morphology have been difficult to electrospin from neutral pH solutions. Here, we present that the electrospinning of HA fibers in aqueous dimethylformamide solutions is facilitated by the addition of three phosphate salts. The salts—glycerol phosphate (GP), sodium phosphate (SP), and tripolyphosphate (TPP)—facilitated electrospinning of the solutions as characterized by conductivity measurements and fiber morphology. From tensile experiments, HA mats electrospun with SP demonstrated improved Young’s modulus (12 MPa) over HA mats spun with either GP or TPP (5 and 3 MPa, respectively). This work demonstrates that a new neutral solvent system can be employed to spin HA fibers, which offers the potential for using the fibers for biomedical applications, such as a bone biomimetic.     

高透明羧甲基纤维素/纤维素纤维复合薄膜的制备及其力学性能

针对传统电子器件衬底柔韧性差、不可生物降解的问题,研究了以羧甲基纤维素（CMC）和纤维素纤维为原料,结合抄纸和浸渍工艺,制备在柔性电子器件领域具有潜在应用的高透明CMC/纤维素纤维复合薄膜衬底。分别探究了CMC与北木纤维的配比和CMC分子量对薄膜透明度和力学性能的影响。研究了纤维素纤维的种类（北木、桉木、马尼拉麻和蔗渣纤维）对高透明CMC/纤维素纤维复合薄膜力学性能的影响。结果表明：CMC与北木纤维质量比为7∶3、CMC分子量为700 000时,所制备CMC/北木纤维复合薄膜的透明度为90%,拉伸强度约为111 MPa,耐折度达到2 526次。这种可生物降解、高柔韧性、高强度和高透明的CMC/纤维素纤维复合薄膜有望作为衬底用于构建下一代绿色、柔性电子器件,促进人类社会的可持续发展。     

Mechanical properties of acrylate-grafted henequen cellulose fibers and their application in composites

The properties of cellulose fiber and PMMA- or PBA-grafted cellulose fibers are investigated as a function of the initiator (ceric-ammonium nitrate) concentration and the amount of grafted polymer onto cellulose fiber. The molecular weight of cellulose decreases while the crystallinity increases with an increment of initiator concentration because of the partial degradation of the amorphous zone of the fibers exposed to the oxidation by the initiator. This results in a reduction of the elastic modulus and tensile strength at high initiator concentrations. Degradation of cellulose is partially inhibited during the grafting process and, therefore, the effect of initiator on the mechanical properties is less notorious in the grafted cellulose fiber. The grafting of PMMA or PBA on the fiber results in lower mechanical properties than those of the ungrafted cellulose fiber. The reduction of the elastic modulus is independent of the amount of grafted PMMA or PBA, but the tensile strength decreases with the PBA content on the PBA-grafted fiber. Either the grafted or the ungrafted cellulose fibers improve the mechanical properties of plasticized PVC composites, and the best results are obtained for PMMA-grafted cellulose fibers because of the better fiber–matrix adhesion. The Halpin–Tsai equation seems to better agree with the experimental data when there is a good fiber–matrix adhesion. In contrast, for poor fiber–matrix adhesion the experimental data has a better agreement with the parallel arrangement equation.     

Multi-length scale computational derivation of Kevlar<Superscript>®</Superscript> yarn-level material model

The results of an extensive set of molecular-level computational analyses regarding the role of various microstructural/morphological defects on the Kevlar^® fiber mechanical properties are used to upgrade the associated yarn-level model of the same material. While carrying out this analysis, the hierarchical multi-scale (atoms/ions—molecular chains—fibrils—fibers—yarn) of the problem was taken into account. To construct various defects, the appropriate open-literature experimental and computational results were used while the concentration of defects was set to the values comparable with their counterparts observed under “prototypical” polymers synthesis and fiber fabrication conditions. Due to the stochastic nature of the defect distributions, their effect on the yarn-level strength and ductility are included in the form of the corresponding two-level Weibull distribution. As far as the material stiffness is concerned, it was assumed that the first-order effect of the defects is to change the mean value of the stiffness parameters and that this effect is of a deterministic character. While upgrading the yarn-level material model for Kevlar^® it was recognized that a yarn is an assembly of nearly parallel fibers (often lightly twisted, or tied with wrap-around filaments) with relatively weak lateral coupling.     

醋酸羟丙基甲基纤维素琥珀酸酯溶液的高压静电场纺丝

研究了醋酸羟丙基甲基纤维素琥珀酸酯(HPMCAS)溶液高压静电场纺丝过程中高聚物分子量、溶液浓度、静电场强度对成纤性和纤维直径的影响,制备出直径范围为0.43μm～1.0μm的纤维。当溶剂、溶液浓度及静电场强度一定时,重均分子量-Mw分别为2.6万、4.8万和7.2万,HPMCAS溶液中只有7.2万者能纺丝得到光滑纤维。在静电场强度、溶剂组成一定条件下,HPMCAS可纺丝浓度范围为8%～15%(质量分数,下同),且随着纺丝溶液浓度的增大,所得纤维的平均直径逐渐增大。当其它条件保持一定时,随着纺丝电压的增大,所得纤维的平均直径呈下降的趋势,所得纤维结晶度略微增大。     

混杂短纤维增强尼龙1010的热水老化

本文研究了经80℃热水老化2600小时的短碳纤维和玻璃纤维混杂增强尼龙1010复合材料的性能与结构变化,并对复合材料中的纤维长度分布进行了统计.研究表明,纤维长度减小主要发生在挤出造粒阶段.碳纤维与玻璃纤维的长度分布差异不大.混杂增强的尼龙1010复合材料在许多力学性能和摩擦磨损行为上表现出正的“混杂效应”.热水老化后仍然存在这种情况.热水老化使尼龙1010的分子量降解,降解率随玻璃纤维含量增加而增大.老化使尼龙1010晶粒增大,但并无形成球晶.热水老化后复合材料的力学性能保留率随玻璃纤维含量增加而下降.热水老化使玻璃纤维与尼龙1010之间的界面粘结受到严重破坏,界面剪切强度严重下降.碳纤维与尼龙的界面粘结所受的破坏轻一些.     

A promising approach for modeling biological fibers

The final-to-initial stiffness ratio is very large (>100) for many biological fibers, and as such, these materials have been modeled as being strain limiting. We propose an unconventional structure for a stored energy function that leads to a constitutive relation capable of describing this observed strain-limiting behavior. The model can attain infinite stress at a finite strain while storing a finite amount of internal energy. Many biological fibers have a mechanical response that starts out as being compliant and nonlinear, and transitions into one that is stiff and linear. We present a biological fiber model comprised of a strain-limiting fiber (strain being attributed to molecular reconfiguration) loaded in conjunction with a Hookean fiber (strain being attributed to molecular stretch). The model’s parameters are physical, intuitive and readily extracted from a stress/strain curve. Chordæ tendineæ data are used to demonstrate the efficacy of the model.     

Investigation of structure,mechanical and tribological properties of short carbon fiber reinforced UHMWPE-matrix composites

Structural, mechanical and tribological properties of composite materials based on ultra-high molecular weight polyethylene reinforced with carbon fibers were investigated. The effect of surface modification of carbon fibers on the interaction at the fiber–matrix interface in UHMWPE based composites was studied. It was found that the thermal oxidation of carbon fibers by air oxygen at 500 °C can significantly enhance the interfacial interaction between the polymer matrix and carbon fibers. This allowed us to form composite materials with improved mechanical and tribological properties.     

Full vectorial modal analysis of specialty fibers and their Bragg grating characterization

Optical fibers and specialty waveguides are the bases of the majority of today's telecommunication, biomedical, sensing, and light-delivery applications. Modal analysis plays an important role in optimizing the optical performance of these fibers when they are integrated with optical systems. We present a full vectorial modal theoretical analysis of specialty cylindrical symmetric fibers with arbitrary index profiles, using a staircase approximation and scattering matrix approach with no constraints on the refractive index profile. We demonstrate the generality of this method by investigating the modal characteristics of two specialty fibers: graded-index fiber and concentric-shell multicore fiber. The calculated modal effective indices for the graded-index fiber are compared with those calculated by the WKB method, stressing the main differences between the scalar and vectorial approaches. Using the same approach, we calculate the Bragg grating response of a holographic grating written in the guiding regions of a concentric-shell fiber and compared them with experimental measurements.     

Modeling and numerical simulation of the mechanical behavior of woven SiC/SiC regarding a three-dimensional unit cell

The mechanical behavior of a two-dimensional woven SiC/SiC ceramic matrix composite (CMC) under tensile loading is modeled by regarding a three-dimensional unit cell of the composite which takes the waveness of the fiber yarns in two directions into account. The numerical evaluation of the model is accomplished by means of the finite element method (FEM). Because of the small diameter (15 μm) of the fibers in the bundles, these fibers are not considered as single entities in the finite element mesh. Instead the mesh is constructed on the yarn scale considering the fiber bundles as homogeneous with ‘fiber bundle' properties. The brittle cracking of interyarn matrix as well as transverse cracking of the fiber bundles are considered by defining a fracture criterion for these components. The increasing degradation of the fiber bundles in fiber direction during progressive loading is described by three damage variables. Damage and cracks are modeled by reducing the elastic coefficients of the finite elements. The scattering of the strength values of the single components is regarded by using Weibull distribution. Before mechanical loading, the structure is subjected to thermal loading to consider the residual thermal stresses in the structure resulting from the cooling down process after fabrication of the composite. The effect of the scattering of the strength values on the behavior of the unit cell will be examined.     

Determination of mechanical strength properties of hemp fibers using near-infrared fourier transform Raman microspectroscopy

Fourier transform near-infrared (FT-NIR) Raman microspectroscopy was adopted for analyzing the micro mechanical tensile deformation behavior of cellulosic plant fibers. Mechanical strength parameters such as tensile strength, failure strain, and Young's modulus of diversified hemp fibers were determined within the range of single fiber cells and fiber filaments. The analysis of fiber deformation at the molecular level was followed by the response of a characteristic Raman signal of fiber cellulose that is sensitive to the tensile load applied. The frequency shift of the Raman signal at 1095 cm(-1) to lower wavenumbers was observed when the fibers were subjected to tensile strain. Microstructural investigations using electron microscopy under environmental conditions supported the discussion of mechanical properties of hemp fibers in relation to several fiber variabilities. Generally, mechanical strength properties of diversified hemp fibers were discussed at the molecular, microstructural, and macroscale level. It was observed that mechanical strength properties of the fibers can be controlled in a broad range by appropriate mercerization parameters such as alkali concentration, fiber shrinkage, and tensile stress applied to the fibers during the alkaline treatments.     

CF/Epoxy复合材料的界面自组装

提出了一种新的炭纤维表面改性方法——分子自组装, 即在表面金属化的炭纤维上进行有机分子的自组装。表面增强拉曼散射光谱 (SERS)分析证实了含氮或含硫的芳杂环化合物化学吸附在银的表面, 并形成了平躺取向的自组装膜结构。X射线光电子能谱 (XPS)测试进一步证实了自组装膜通过S或N原子和Ag形成配位共价键吸附在炭纤维表面。表面经组装改性后的炭纤维和环氧复合后界面粘结强度得到了不同程度的提高, 揭示了界面区域微观结构与性能的关系。      

Research on the interaction of three contact fibers in the fiber suspensions

Based on the slender-body theory, the governing equations for the mechanical interaction of one settling fiber with two fixed fibers in fiber suspensions were derived and solved numerically. In order to validate the model and method used in the paper, the interactions of two contact fibers were simulated and the results are in good accordance with the experiments. The results of three interacting fibers show that the initial contact point and the initial orientation angle of settling fiber have a significant effect, however, the angle between two fixed fibers has an insignificant effect, and the initial angular velocity of settling fiber has no effect on the interaction process of fibers. The settling fiber aspect ratio is not an independent parameter involving in the interaction between the fibers. The interaction duration increases as the fiber aspect ratio increases, however, the effect caused by reducing the diameter is more significant than that caused by increasing the length. The interaction duration is directly proportional to the solvent viscosity and verse directly to the fiber specific weight remarkably. Finally, a synthetic parameter A which contains the quantities affecting the interaction duration is derived to uniquely describe the total duration of interaction of the fibers.     

碱处理对干法纺二步法甲纶聚酰亚胺纤维微观形貌及结构性能的影响

研究了NaOH处理对聚酰亚胺纤维细度、力学性能、热失重性能、化学结构、表面微观形貌及微观聚集态结构的影响。结果表明,纤维经碱处理后细度和力学性能下降,且随着碱浓度和温度提高、处理时间延长,纤维细度和力学性能下降趋势加快;纤维的酰亚胺环在OH~-作用下,开环水解为聚酰胺酸或其盐,使得部分聚合物分子链发生断裂,导致纤维热失重性能、化学结构及微观聚集态结构发生改变,纤维表面凹凸不平,粗糙度增加,局部发生刻蚀。因此,采用适当的NaOH处理工艺,有助于聚酰亚胺纤维表面进行功能化改性。     

Characterization of interfacial and mechanical properties of “green” composites with soy protein isolate and ramie fiber

Environment-friendly fiber-reinforced composites were fabricated using ramie fibers and soy protein isolate (SPI) and were characterized for their interfacial and mechanical properties. Ramie fibers were characterized for their tensile properties and the parameters for the Weibull distribution were estimated. Effect of glycerol content on the tensile properties of SPI was studied. Interfacial shear strength (IFSS) was determined using the microbond technique. Based on the IFSS results and fiber strength distribution, three different fiber lengths and fiber weight contents (FWC) were chosen to fabricate short fiber-reinforced composites. The results indicate that the fracture stress increases with increase in fiber length and fiber weight content. Glycerol was found to increase the fracture strain and reduce the resin fracture stress and modulus as a result of plasticization. For 10% (w/w) of 5 mm long fibers, no significant reinforcement effect was observed. In fact the short fibers acted as flaws and led to reduction in the tensile properties. On further increasing the fiber length and FWC, a significant increase in the Young's modulus and fracture stress and decrease in fracture strain was observed as the fibers started to control the tensile properties of the composites. The experimental data were compared to the theoretical predictions made using Zweben's model. The experimental results are lower than the predicted values for a variety of reasons. However, the two values get closer with increasing fiber length and FWC.     

Effects of three parameters on the diameter of electrospun poly(ethylene oxide) nanofibers

The combined use of two techniques namely electrospray and spinning is made use in a highly versatile technique called electrospinning, which produces the diameter of polymer fibers range from nanometer to sub-micron. In this work, we have studied effects of adding LiCl on the morphology and diameter of electrospun poly(ethylene oxide), and we have also evaluated systematically the effect of three important solution parameters on the morphology of electrospun poly(ethylene oxide): molecular weight, solution viscosity and electrical conductivity. We find that molecular weight is strongly correlated with the formation of bead defects in the fibers, the smaller molecular weight, the more beads defect density. As a result, the fibers have beads-in-string structures. Electrical conductivity increases, then decreases as molecular weight increases. Solution viscosity has been found to most strongly affect fiber size, with fibers diameter increasing with increasing solution viscosity according to a power law relationship. In addition, we find evidence that solution viscosity and electrical conductivity affect the interesting morphology of the electrospun nanofibers, and result in doubling and forming membrances phenomena.     

低温炭化温度梯度对聚丙烯腈预氧纤维结构演变及碳纤维性能的影响

聚丙烯腈(PAN)预氧纤维在低温炭化阶段经热裂解重组而转化为具有乱层石墨结构雏形的低温炭化纤维,此阶段的温度调控对最终碳纤维的结构与性能有着重要影响。采用¹³C固体核磁共振谱图(¹³C-NMR)、拉曼光谱(Raman)、X射线衍射(XRD)和力学性能分析等手段,研究预氧纤维在低温炭化阶段的反应进程、温度梯度调控对预氧纤维的结构演变和碳纤维结构及性能的影响。结果表明:PAN预氧纤维在低温炭化过程中,经450℃热处理后碳结构的支链化程度达到最大值0.99,当处理温度达到550℃后,以芳环链段的重组交联为主要反应。低温炭化温度梯度影响预氧纤维的结构演变进程,当采用350—450—650℃的梯度升温模式时,先经450℃处理的低碳纤维中—C—C基团的¹³C-NMR位移最大,表明纤维内的支化交联反应最多,再经650℃处理的纤维d₀₀₂以及相应高碳纤维的I_A/I_G达到最大,说明其无定形碳相对含量最多,因而最终碳纤维的力学性能最差;当采用350—550—650℃的梯度升温模式时,纤维内裂解与重组交联反应有序开展,低碳和高碳纤维的碳结构更优,最终碳纤维的致密性及力学性能得到提升。