高性能聚丙烯腈碳纤维中纳米级微孔分析表征研究

高性能碳纤维由于其优异的性能,在各行各业中具有广泛应用。为深入研究碳纤维内结构与其性能之间的相关性,本文应用小角X射线散射研究了一系列典型的聚丙烯腈碳纤维样品,分析了样品内微孔的尺寸及取向,讨论了强度和模量与微孔的相关性,研究结果表明:高性能碳纤维的力学强度和模量与碳纤维内微孔缺陷的长度和长径比有关,控制碳纤维内微孔缺陷的长度有望实现高强碳纤维的制备,控制牵伸倍率从而控制碳纤维内微孔的长径比有望实现高模碳纤维的制备。     

溶胶-凝胶法在聚酰亚胺衬底上制备c轴取向ZnO薄膜

通过溶胶-凝胶工艺, 采用两步加热法在聚酰亚胺表面制备了具有c轴取向的ZnO薄膜. 通过差式扫描量热-热重分析(DSC-TGA)得出最佳的前热处理温度和后热处理温度分别为300和390 ℃. 通过X射线衍射(XRD)和扫描电子显微镜(SEM)对薄膜的晶体取向和表面形貌进行了分析, 描述了ZnO薄膜在聚酰亚胺上的生长过程. 拉伸实验结果表明, ZnO薄膜与聚酰亚胺衬底有较强的附着力.     

溶胶-凝胶和浸渍-水热制备方法对TiO_2/AC光催化剂结构和性能的影响

分别采用溶胶-凝胶法和浸渍-水热法制得负载于活性炭(AC)的TiO2催化剂,并用扫描电镜(SEM)、X射线衍射(XRD)、拉曼光谱和氮气吸附等方法对催化剂进行了表征.结果表明:溶胶-凝胶法制得的TiO2以不规则碎片形式涂附在载体表面,而浸渍-水热法制得的球形TiO2颗粒呈柱形生长均匀覆盖在载体表面;不同温度处理的浸渍-水热法制得的TiO2/AC光催化剂的中孔和微孔比表面积均大于溶胶-凝胶法制得的样品,负载的TiO2粒径则小于溶胶-凝胶法制得的样品.对甲基橙(MO)溶液的光催化降解测试结果表明,600℃煅烧为两种方法的最佳热处理温度,浸渍-水热法制得的催化剂光催化效果明显强于溶胶-凝胶法的.     

静电纺丝法制备交联多孔纳米碳纤维膜及其电化学电容性能

以聚丙烯腈(PAN)和三聚氰胺为原料,通过静电纺丝法制备了三聚氰胺改性聚丙烯腈纳米纤维前驱体,经预氧化、碳化后得到交联的多孔纳米碳纤维.采用红外光谱(FTIR)仪、热重分析(TGA)仪、扫描电子显微镜(SEM)、X射线衍射(XRD)仪、拉曼光谱仪和比表面积分析仪等对前驱体及纤维进行了表征.结果表明,经过三聚氰胺改性的聚丙烯腈纳米纤维前驱体在碳化后有效地交联,形成含有微孔、介孔和大孔多级的合理孔道结构,氮掺杂量高达14.3%,纤维直径大幅缩减,平均直径仅约89 nm.电化学测试结果表明,交联多孔纳米碳纤维电极在0.05 A·g^-1电流密度下未经活化时的质量比电容值高达194 F·g^-1(0.05 A·g^-1),在2 A·g^-1的电流密度下经过1000次循环充放电后的比电容仍然保持99.2%,表现出优异的电化学特性.     

碳纤维基PtPb阳极催化剂的制备及其电催化性能

以静电纺丝技术与烧结工艺相结合的方式制备了碳纤维基PtPb纳米催化剂,并采用X射线衍射(XRD)、红外光谱(FT-IR)、扫描电镜(SEM)等分析测试手段对其进行了表征。结果表明,在预氧化温度为300℃、碳化温度为800℃的条件下,所制备的PtPb阳极纳米催化剂结晶程度好、比表面积大,粒径约为3.05 nm,催化活性颗粒均匀分散在多孔碳纤维骨架上。采用循环伏安法(CV)及交流阻抗(EIS)评价了该催化剂对乙醇氧化反应的电催化性能。结果表明,最大峰电流密度达到125 mA/cm2,电荷转移电阻相较于700℃下降了近60%。     

常温合成硫掺杂微孔碳及其二氧化碳的吸附性能

常温下以间苯三酚和3-甲醛苯并噻吩作为原料,一步法合成了含硫酚醛树脂。在氩气保护下碳化,成功制备出了硫掺杂多孔碳(S-PC)。并利用扫描电镜(SEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)和氮气吸附-脱附仪对材料进行了形貌、结构和性能的表征。实验结果表明,所得样品具有较高比表面积和大量的微孔,经过调控,可以使制备的硫掺杂多孔碳的BET比表面积达到997 m2·g~(-1),并使其微孔孔体积达到0.44 cm3·g~(-1)。得益于较高的比表面积以及其富含微孔的特性,当材料应用于二氧化碳吸附时,具有较高的CO2吸附量,在273和298 K时分别高达5.13,3.22 mmol·g~(-1),并具有良好的选择性。     

热处理对[NiFe/Cu/Co/Cu]_n多层纳米线磁性能的影响

采用双槽控电位法在阳极氧化铝(AAO)模板中制备了有序均一的[NiFe/Cu/Co/Cu]n多层纳米线阵列,并在不同温度下进行了热处理.利用X射线衍射(XRD)对热处理前后多层线的晶体结构进行了测试.考察了不同退火温度对多层线矫顽力、剩磁比、巨磁电阻(GMR)效应、磁灵敏度的影响.随热处理温度升高,多层纳米线中磁性微晶晶型取向越来越明显,晶体结构更均匀;多层纳米线的矫顽力和剩磁比先增大后减小.300°C下多层纳米线矫顽力达到最大值,GMR最大值可达59%,对应的磁电阻灵敏度(SV)为0.233%Oe-1.     

纤维催化剂的孔结构特征Ⅱ．碳纤维载体的孔结构研究

测量了不同氧化深度的三类碳纤维(丙烯腈长丝、丙烯腈碳毡和粘胶碳毡)的低温氮吸附等温线。Pickett修正三参数BET方程能很好地关联这些等温线,三类碳纤维具有不同的n值。应用V—n作图法获得了它们的主要孔结构参数,利用Mp—Wp和D-R—Wp的组合方法获得了它们的孔分布数据。结果指出,总表面积、总孔体积、微孔表面积和微孔体积的大小与碳化温度和碳化原料有关,并且随氧化深度而增加;但非微孔表面积基本保持恒定,约为4—12m~2/g。微孔分布的最可几孔半径随氧化深度增加而减小,各类样品的非微孔分布几乎落在同一条孔分布曲线上。     

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.     

熔融拉伸法制备聚丙烯微孔膜成孔机理的原位小角X射线散射研究

采用熔融拉伸法制备聚丙烯微孔膜,在避免冷拉会自然回缩和热处理后样品需降温检测等因素对冷拉伸样品影响的情况下,在线研究了冷拉、热定型、热拉过程中样品结构变化.原位小角X射线散射检测与扫描电子显微镜、示差扫描量热仪结合深入研究了不同的冷拉拉伸比对微孔膜片晶和孔洞结构的影响.结果表明不同的冷拉伸比其成孔机理不同,冷拉15%,仅拉伸方向长周期发生微弱的变化,其成孔机理是冷拉产生缺陷,热拉成孔;冷拉30%拉伸主要是将薄弱片晶拉伸转变为不稳定的架桥,热定型阶段部分架桥断裂,竖直方向上产生明显的Streak信号;冷拉40%拉伸方向信号显示实际片晶长周期的增长率小于宏观应变,部分骨架片晶在冷拉阶段已被拉伸破坏成孔.随着冷拉拉伸比增大架桥长度变短,孔径减小,30%是制备微孔膜较合适的冷拉拉伸比.     

金(I)配合物催化乙烯加氢的反应机理

采用密度泛函理论B3LYP方法, 对两类金(I)配合物AuX (X=F, Cl, Br, I)和AuPR₃⁺(R=F, Cl, Br, I, H, Me,Ph)催化C₂H₄加氢反应的机理进行了理论研究. 计算显示Au(I)配合物对C₂H₄氢化具有较好的催化效果, 其作用下的加氢反应存在“活化H―H键后再与C₂H₄反应”和“活化C＝C键后再与H₂反应”两种途径, 前者的活化能较后者低90-120 kJ·mol^-1, 因而具有明显的能量优势. 研究表明AuPR₃⁺ 的催化能力明显强于AuX. 此外, X/PR3基团供、吸电子能力的变化对配合物的催化能力也具有较为显著的影响. 电子结构分析显示Au(I)配合物在C₂H₄ 加氢反应中不仅能够削弱H―H、C＝C 键的强度, 还使H₂ σ_H―H^*、C₂H₄ π_C＝C^* 轨道能级下降, 从而缩小了π_C＝C-σ_H―H^*或σ_H―H-π_C＝C^*轨道间的能级差, 促进了C₂H₄-H₂反应中的电子离域, 从而降低禁阻反应发生的难度.σ_H―H^*、π_C＝C^*轨道能级改变量与加氢反应活化能E_a的降低值之间存在较好的一致性关系, 因此使上述轨道能级下降幅度越大的Au(I)配合物可以获得较好的催化效果.     

The effect of electrophoretic deposition p-aminobenzenesulfonamide grafted CNT on mechanical properties of carbon fiber filled polyamide 6 composite

The surface treatment of carbon fiber is carried out by electrophoretic deposition of p-aminobenzenesulfonamide grafted carbon nanotube (CNT), and it is used as a reinforcement of polyamide 6. The monofilament tensile test and XPS were used to study the effect of p-aminobenzenesulfonamide concentration on the tensile strength and surface functional groups of carbon fiber monofilaments. The results show that the higher the p-aminobenzenesulfonamide concentration, the greater the decrease in the mechanical properties of carbon fibers, and the greater the content of oxygen-containing functional groups on the surface. It is preferred that carbon fiber and thermoplastic polyamide 6 with higher retention rate of monofilament tensile strength and rich oxygen-containing functional group content are made into composite materials, and the interlaminar shear strength (ILSS) is evaluated.     

The direct architecture of carbon fiber‐carbon nanofiber hierarchical reinforcements for superior interfacial properties of CF/epoxy composites

A simple and efficient chemical method was developed to graft directly carbon nanofibers (CNFs) onto carbon fiber (CF) surface to construct a CF‐CNF hierarchical reinforcing structure. The grafted CF reinforcements via covalent ester linkage at low temperature without any usage of dendrimer or catalyst was investigated by FTIR, X‐ray photoelectron spectroscopy, Raman, scanning electron microscopy, atomic force microscopy, dynamic contact angle analysis, and single fiber tensile testing. The results indicated that the CNFs with high density could effectively increase the polarity, wettability, and roughness of the CF surface. Simultaneous enhancements of the interfacial shear strength, flexural strength, and dynamic mechanical properties as well as the tensile strength of CFs were achieved, for an increase of 75.8%, 21.9%, 21.7%, and 0.5%, respectively. We believe the facile and effective method may provide a novel and promising interface design strategy for next‐generation advanced composite structures.     

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.     

The investigation of the friction and wear properties of surface‐treated carbon fiber/SiO2 reinforced PMMA composites

The mechanical properties of SiO₂ filler particles on carbon fibers have been under discussion for several decades; the diverse models, and the properties of the components relevant to retention, are critically reviewed in the first part of this study. In addition, to gain an insight into some possible combined effect of the carbon fiber/poly(methyl methacrylate) (CF/PMMA), interfacial adhesion strength and the tensile properties and dielectric strength of the hybrid composites were studied. Simple modified rules of mixtures are used to estimate the fiber efficiency factors for the strength and modulus of the hybrid composites. Except, with the increasing fraction of CFs in PMMA, the weld line area's elongation percent is decreased. Whereas for case of SiO₂, the 10 wt% is the threshold for micro injection molded weld line tensile strength and dielectric strength turning from decrease trend to increase. Same as CF, elongation of micro weld line samples is in general lower than neat PMMA as well, due to the addition of SiO₂ particles.     

Study on structure and performance of surface‐metallized carbon fibers reinforced rigid polyurethane composites

The simultaneous promotion in mechanical and electrical properties of rigid polyurethane (RPU) is an important task for expanding potential application. In this work, carbon fibers (CFs) reinforced RPU composites were prepared with the goal of improving mechanical and electrical properties. Metallized CFs meet our performance requirements and can be easily achieved via electrodeposition. However, the weak bonding strength in fiber‐metal‐RPU interface restricts their application. Inspired by the reducibility and wonderful adhesion of dopamine (DA), we proposed a new and efficient electrochemical method to fabricate metallized CFs, where DA polymerization was simultaneously integrated coupled with the reduction of metal ions (Ni²⁺). The characterization results helped us to gain insight about the reaction mechanism, which was never reported as far as we know. Compared with pure RPU, the tensile, interlaminar shear and impact strength of polydopamine (PDA)‐nickel (Ni) modified CFs/RPU composites were improved by 11.2%, 21.0%, and 78.0%, respectively, which attributed to the strong interfacial adhesion, including mechanical interlocking and chemical crosslinking between treated CFs and RPU. In addition, the PDA‐Ni surface treatment method also affected the dispersion of short CFs in the RPU, which increased the possibility of conductor contact and reduced insulator between fibers networks, resulting in higher electrical conductivity.     

羰基化合物在Si(100)表面[2+2]环加成和α-H裂解反应的选择性

最近研究表明: 丙酮能与半导体Si(100)表面发生[2+2]环加成和α-H 裂解反应形成相应的Si―C键或Si―O键, 在半导体材料的合成方面具有重要意义. 为进一步弄清不同羰基化合物在Si(100)表面的反应机理,本文应用密度泛函理论方法在B3LYP/6-311++G(d,p)//6-31G(d)水平上较为系统地研究了一系列羰基化合物CH₃COR (R=CH₃, H, C₂H₅, C₆H₅)与Si(100)表面的反应. 研究结果表明: 不论是[2+2]环加成反应还是α-H 裂解反应都对应较低的反应势垒(小于25 kJ·mol^-1); 环加成反应的势垒比α-H 裂解反应的势垒略高; 羰基上的取代基对反应势垒的影响较少; α-H裂解反应产物为动力学和热力学控制产物; 对丁酮来说, 1-位和3-位H原子的裂解反应都比较容易, 势垒相差很小. 这些结果表明羰基化合物与Si(100)表面的反应将得到多种产物.     

Strength and toughness of carbon fibers reinforced rigid polyurethane composites by adsorbing tannic acid and refining Ni grains on carbon fibers surface

In this article, short carbon fibers (CFs) reinforced rigid polyurethane (RPU) composites were prepared with the aim of improving both strength and toughness. A tannic acid (TA)‐nickel (Ni) composite coating was spontaneously co‐deposited onto CFs surface by a one‐step electrodeposition method to strengthen the interface bonding of the composites. The satisfactory mechanical properties of the composites were mainly attributed to the superior interfacial adhesion. On the one hand, TA could play a role in refining Ni grain during electrodeposition. On the other hand, the hydroxyl groups attached to composite coating, which were introduced by TA, could react with the RPU matrix to form chemical bonds. When the composites were under stress, the chemical bonds could effectively transfer the stress from matrix to the interface, while the refined Ni crystals could greatly increase the stress transfer path, and thus improve the strength and toughness of the material. Compared with pure RPU, the tensile strength, bending strength,interlaminar shear strength, and impact strength of TA‐Ni‐coated CFs/RPU composites were improved by 14.8%, 83.1%, 28.7%, and 121.4%, respectively.     

Pretreatment of Cylindrical Coconut Activated Carbon and Performance as Catalyst Support

Cylindrical coconut activated carbon(CCAC) support was graphitized at a high temperature(1900 ℃) in argon, then oxidized with an O₂-N₂-H₂O mixture, and treated with nitric acid. Pretreatment of carbon support on its mechanical strength, physical structure, chemical composition and surface properties of cylindrical CCAC support was investigated by X-ray diffraction(XRD), surface area analysis, scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), thermogravimetric-differential thermogravimetric(TG-DTG) analysis and temperature programmed desorption-mass spectrometry(TPD-MS), and the effect of CCAC support on the catalytic activities was also studied. The results show that the degree of graphitization, the purity(phosphorus, sulphur), pore structure(micropore, mesopore) and oxygen-containing functional groups(―COOH, ―OH, ―COOR) of carbon supports are obviously different, which have a great influence on the performance of Ru-based catalysts. After a series of pretreatments, the surface physical and chemical properties of the commercial CCAC are modified and improved, and the activity of as-prepared Ru/AC catalyst is increased significantly.     

The tensile properties of HNO3‐treated carbon fiber reinforced ABS/PA6 composites

In this study, acrylonitrile‐butadiene‐styrene (ABS) terpolymer was reinforced with HNO₃‐treated short carbon fibers (SCFs) [(hollow carbon fibers (HCFs)]. The effects of HCF concentration on the tensile properties of the composites were examined. Increasing the HCF concentration in the ABS matrix from 10 to 30 wt% resulted in improved tensile strength and tensile modulus. To obtain a strong interaction at the interface, polyamide 6 (PA6) at varying concentrations was introduced into the ABS/10 wt% SCF composite. The incorporation and increasing amount of PA6 in the composites increased tensile properties of the ABS/PA6/HCF systems due to the improved adhesion at the interface, which was confirmed by the ratio of tensile strength as an adhesion parameter. These results were also supported by scanning electron micrographs of the ABS/PA6/HCF composites, which exhibited an improved adhesion between the SCFs and the ABS/PA6 matrix. Copyright © 2009 John Wiley & Sons, Ltd.