Processing and properties of polysulfone hollow fibre membranes for gas separation filled with sub‐micron carbon fibres

Polysulfone hollow fibre membranes, of the type produced previously with enhanced gas separation properties, were filled with vapour grown carbon fibres (VGCF) of sub‐micron diameter. The effect of filler content on mechanical and gas permeation characteristics was studied. Hollow fibre membranes filled with up to 2.8 vol. % of VGCF were produced using forced convection dry jet/wet spinning. Fibre stiffness increased with increasing VGCF filler content. The fibres with the highest concentration of filler were about 30% more stiff than unfilled membranes. The addition of VGCF lead to a rise in permeability and some decrease in selectivity.     

气相生长碳纤维的表面改性及表征

用浓硝酸(65%~68%)对气相生长碳纤维(VGCF)进行了不同时间的表面化学改性。X射线衍射(XRD)分析表明：改性使得VGCF的石墨晶型结构改变，其改变的程度随改性时间的延长而加深；BET比表面积(S_BET)测试表明：改性后的VGCF的S_BET有一定的变化，经120 min长时间的改性处理后，S_BET明显降低；傅立叶变换红外光谱(FTIR)测定得出：改性后VGCF表面上生长了不同类型的含氧基团，其总含量随改性时间的增大而增加；程序升温还原(TPR)得出：改性后VGCF表面上生成有2类以上的热稳定性不同的含氧基团，计算求得含氧基团的氧总含量为2 mmol·g^-1以上；NH₃吸附微量量热测定得出：表面酸性基团的强度和含量随改性时间增加而增大；透射电子显微镜(TEM)结果表明：改性没有明显破坏VGCF的外观结构；吸油值(AOV)实验给出：改性后VGCF的AOV显著降低而亲水性增强；双液法接触角测试给出：改性后VGCF的表面能(SE)明显增大；偶联剂与VGCF作用的FTIR研究表明：改性后VGCF表面含氧基团和偶联剂发生反应，增强了偶联剂在VGCF表面上的结合强度。     

Analytical investigation of plasma-treated carbon fibres

As-grown and heat-treated vapour grown carbon fibres (VGCF) in the as-prepared state, washed in HCl/H(2)O, and treated in O(2) plasma for different periods have been investigated by means of XPS and scanning electron microscopy (SEM). The surface energy of the carbon fibres before and after plasma treatment was determined from the wetting contact angle. Washing introduced hydroxyl, carbonyl and carboxyl groups onto the fibre surfaces and oxygen plasma treatment increases the total atomic concentration of oxygen up to 17%. This is in good agreement with the value of the polar component of the surface energy. Plasma treatment also enhanced the fibre surface porosity (by etching).     

加工工艺对气相生长碳纤维填充聚苯乙烯复合体系导电逾渗与动态流变特性的影响

研究了加工工艺对气相生长碳纤维(VGCF)填充聚苯乙烯(PS)复合体系导电逾渗与动态流变特性的影响.结果表明,低转速、短时间混合有利于VGCF形成较为完善的逾渗网络结构,其复合体系逾渗阈值低、导电性能好.使用作者提出的两相模型描述VGCF/PS复合体系的流变特性,发现低转速、短时间(30 r/min、5 min)混合条...     

表面改性对VGCF分散性质的影响

针对气相生长碳纤维极易团聚及与树脂基体界面结合能力较差的难题,采用双氧水-浓硝酸二步法对VGCF进行表面改性处理。利用X射线衍射仪、热重分析仪、傅立叶红外光谱仪、紫外可见分光光度计等测试分析了改性前后VGCF的表面结构和在溶剂中的分散性,并以形状记忆聚氨酯为基体,采用溶液混合法制备了气相生长碳纤维/形状记忆聚氨酯的复合材料,测试了复合材料的力学性能。经过改性后,VGCF的石墨晶型结构几乎没有改变,VGCF表面的含氧官能团浓度得到较大提高,且其在有机溶剂中的分散性及分散稳定性也得到很大提高;在气相生长碳纤维/形状记忆聚氨酯的复合材料截面中,扫描电镜观察表明表面改性使得VGCF在基体中的分散性及与基体的界面结合能力都得到一定程度的提高;经二步法改性处理后的气相生长碳纤维比未处理气相生长碳纤维对复合材料的力学性能的增强效果更为明显。     

气相生长碳纤维/形状记忆聚氨酯复合薄膜的力学及形状记忆性能研究

采用溶液混合法制备了不同含量的气相生长碳纤维(VGCF)增强形状记忆聚氨酯(SMPU)的复合材料薄膜,测试分析了纯SMPU及VGCF/SMPU复合材料薄膜的力学性能及形状记忆性能.结果表明,制得的复合材料薄膜在VGCF含量达到9 wt%时,VGCF在SMPU基体中仍具有较好的分散性;SMPU与VGCF复合后,得到的复合材料薄膜的拉伸强度和刚度有较大程度的提高,含量达到9 wt%时复合材料薄膜的拉伸强度比纯SMPU提高66%,弹性模量提高300%,储能模量也有较大程度提高;SMPU与VGCF复合后,形状记忆性能有一定的下降,但经过适当预处理后,其形状记忆性能可以基本接近纯SMPU.     

气相生长碳纤维填充聚苯乙烯的熔体动态流变行为

采用修正的两相模型讨论加工条件对不同体积分数(ψ=0～0.05)气相纳米碳纤维(VGCF)填充聚苯乙烯(PS)熔体(200℃)频率(ω)依赖性动态流变的影响.与弱剪切条件(190℃;30 r/min-5 min)下所制备的材料相比,VGCF在强剪切条件(190℃;120 r/min-10 min)下所制备材料中分散均匀,“粒子相”应变放大因子A,(ψ)较低,而松弛指数n较高.将应变(γ)依赖性G″(ω,ψ)应变放大因子A,(ψ,γ)与“粒子相”特征模量G″fψ(,γc),G″f(ψ,γc)引入两相模型,讨论加工条件对γ依赖性非线性流变行为的影响.研究结果表明,两相模型可定量讨论填充熔体动态流变行为.加工条件影响VGCF在基体中的分散性,但不影响“粒子相”弹性贡献R′f(ψ)与n的关系、G′f(ψ,γc)与非线性应变幂律指数x的关系以及G″f(ψ,γc)与非线性应变幂律指数y的关系,说明“粒子相”对填充熔体黏弹性的贡献与其弛豫特性及结构稳定性密切相关.     

Fabrication and characterization of poly(butylene succinate)‐grafted carbon fiber/poly(L‐lactide) nanocomposites

A new poly(butylene succinate) (PBS)‐grafted vapor grown carbon fiber (VGCF)/poly(L ‐lactide) (PLLA) nanocomposites were successfully prepared by an in situ condensation reaction between PBS (M_w = 6,000) and surface oxidized VGCF, followed by direct melt mixing technique, and their mechanical and thermal properties were evaluated. Fourier transform infrared spectroscopy and scanning electron microscopy studies indicate a chemical interaction between the PBS and the surface of VGCF. It was found that the maximum tensile strength and modulus of PBS‐grafted VGCF/PLLA nanocomposites were 135 MPa (27% increase relative to neat PLLA) and 4,400 MPa (29% increase relative to neat PLLA), respectively. The results indicate that significant improvement in the mechanical properties can be accomplished by optimizing the surface modification conditions for VGCF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4433–4441, 2008     

Thermal conductivity of exfoliated graphite nanocomposites

Since the late 1990’s, research has been reported where intercalated, expanded, and/or exfoliated graphite nanoflakes could also be used as reinforcements in polymer systems. The key point to utilizing graphite as a platelet nanoreinforcement is in the ability to exfoliate graphite using Graphite Intercalated Compounds (GICs). Natural graphite is still abundant and its cost is quite low compared to the other nano–size carbon materials, the cost of producing graphite nanoplatelets is expected to be ~$5/lb. This is significantly less expensive than single wall nanotubes (SWNT) (>$45000/lb) or vapor grown carbon fiber (VGCF) ($40–50/lb), yet the mechanical, electrical, and thermal properties of crystalline graphite flakes are comparable to those of SWNT and VGCF. The use of exfoliated graphite flakes (xGnP) opens up many new applications where electromagnetic shielding, high thermal conductivity, gas barrier resistance or low flammability are required. A special thermal treatment was developed to exfoliate graphite flakes for the production of nylon and high density polypropylene nanocomposites. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the degree of exfoliation of the graphite platelets and the morphology of the nanocomposites. The thermal conductivity of these composites was investigated by three different methods, namely, by DSC, modified hot wire, and halogen flash lamp methods. The addition of small amounts of exfoliated graphite flakes showed a marked improvement in thermal and electrical conductivity of the composites.     

Basic analytical investigation of plasma-chemically modified carbon fibers

The background of the present investigation is to enhance the overall adherence of vapor grown carbon fibers (VGCF) to the surrounding polymer matrix in different applications by forming polar groups at their surfaces and by modifying the surface morphology. This has been done by plasma treatments using a low-pressure plasma with different gases, flow rates, pressures and powers. Two different types of carbon fibers were investigated: carbon microfibers and carbon nanofibers. The characterization of fiber surfaces was achieved by photoelectron spectroscopy (XPS), contact angle measurements and titration. These investigations were accompanied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The oxygen plasma treatment of the fibers changes the surfaces by forming a layer with a thickness of the order of one nanometer mainly consisting of functional groups like hydroxyl, carbonyl and carboxyl. After functionalization of the complete surface, a further plasma treatment does not enhance the superficial oxygen content but changes slightly the portions of the functional groups. A comparison of the methods applied provides a largely consistent image of the effect of plasma treatment.     

A novel enzymatic bioelectrode system combining a redox hydrogel with a carbon NanoWeb

A novel bioelectrode system has been prepared in which an enzyme and a conducting polymer hydrogel are combined in a nanostructured scaffold. The latter consists of fibres of carbon NanoWeb, grown by chemical vapour deposition onto reticulated vitreous carbon (RVC). The catalytic currents produced by this new bioelectrode system are significantly larger than those obtained using conventional electrodes.     

In vivo monitoring of the gastrooesophageal system using optical fibre sensors

In the present paper optical fibre sensors for the detection of foregut diseases are described, in particular, sensors for the detection of bile, carbon dioxide and pH. Bile-containing refluxes are measured by means of a sensor which uses bilirubin as natural marker. The sensor, which is already present on the market, has been clinically validated by various hospitals. The clinically relevant parameter is the exposure time of the stomach/oesophagus mucosa to the bile. When measured in the oesophagus, it has been shown to be closely correlated with the onset of Barrett's oesophagus or general oesophagitis. Recently, optical fibres have been proposed for the continuous monitoring of carbon dioxide in the stomach: an important parameter in critically ill patients. A clinically validated prototype has shown its superiority in comparison with the traditional method, that is based on gastric tonometry. For the sake of completeness, also gastric pH sensors are considered, although at the moment their development is stationary at the laboratory stage.     

Phase stability of nanocarbon in one dimension: nanotubes versus diamond nanowires

Since their discovery in 1990, the study of sp2 bonded carbon nanotubes has grown into a field of research in it's own right; however the development of the sp3 analog, diamond nanowires, has been slow. A number of theoretical models have been proposed to compare the relative stability of diamond and graphite at the nanoscale; and more recently, to compare nanodiamonds and fullerenes. Presented here is a study of the phase stability of nanocarbon in one-dimension. The structural energies of carbon nanotubes and diamond nanowires have been calculated using density functional theory within the generalized gradient approximation, and used to determine the atomic heat of formation as a function of size.     

Polycarbonate Crystallization by Vapor‐Grown Carbon Fiber with and without Magnetic Field

Polycarbonate (PC)/vapor‐grown carbon fiber (VGCF™) composite was prepared through melt compounding. It was unexpectedly found from differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) that the crystallization of PC was substantially accelerated in the presence of the ordered graphite surface of VGCF™. To make an aligned structure of PC crystallization together with the orientation of VGCF™, a magnetic field of 2.4 T was applied to the composite under several temperature profiles. The WAXD pattern revealed that not only dispersed VGCF™ but also matrix PC crystallization was magnetically aligned through the optimization of processes. The evidence for PC crystallization by VGCF™ with and without magnetic force is described.

Optical micrograph (a) and WAXD pattern (b) of PC/VGCF™ (95:5 wt. ratio) composite which was treated under a magnetic field (vertical direction) of 2.4 T under an optimized heating profile.     

High-pressure phase equilibria of some carbon dioxide–organic–water systems

Homogeneous catalysts offer better activity and selectivity than heterogeneous catalysts, but their use is limited by the need to separate them from product and reuse them. Preferential dissolution of gaseous carbon dioxide has been shown to alter phase boundaries and facilitate recovery of such homogenous catalysts. The addition of a polar organic co-solvent to a water/organic biphasic system, coupled with subsequent phase splitting induced by the dissolution of gaseous carbon dioxide creates the opportunity to run homogeneous reactions in an organic/aqueous mixture with a water-soluble catalyst. In homogeneous catalyzed reactions, the catalyst can be tuned to be soluble or insoluble with carbon dioxide present, thus allowing for high catalyst recovery.High-pressure phase equilibria for the systems containing carbon dioxide, an organic (tetrahydrofuran, acetonitrile, or 1,4-dioxane), and water were measured using a variable-volume view cell, by a method capable of rapid and facile measurement of compositions and density in both phases with no sampling or calibration. These systems are well predicted with the Peng–Robinson Equation of State with Huron–Vidal type mixing rules from correlations of the binary systems, with the modified Huron–Vidal 1 (MHV1) and Huron–Vidal–Orbey–Sandler (HVOS) model with UNIQUAC excess energy model performing the best. Applications of the phase behavior on reaction conditions and separations are addressed.     

Improvement of electrochemical properties of PTMA cathode by using carbon blacks with high specific surface area

A PTMA (poly(4-methacryloyloxy-2,2,6,6-tetramethyl-piperidine-N-oxyl)) electrode with high energy density is prepared with Black Pearl 2000 (BP-2000). For comparisons, vapor grown carbon fiber (VGCF) and acetylene black (AB) are also employed to fabricate the PTMA-electrodes. The electrochemical properties of the electrode are improved obviously by employing BP-2000. The specific capacity of the PTMA-BP electrode based on the mass of PTMA is 26.7% larger than that of the PTMA-VGCF and PTMA-AB electrodes at a 1 C rate. At higher discharge rates, the polarization degree of the Li/PTMA-BP cell is the minimum one. At a discharge rate of 50 C, the specific capacity of the PTMA-BP electrode is 104.9 mA h g^?1, and is 27.6 and 16.7% larger than that of the PTMA-VGCF and PTMA-AB electrodes, respectively. Besides, the discharge plateau of the Li/PTMA-BP cell is 3.35 V, and is 0.03 and 0.13 V higher than that of the Li/PTMA-AB and Li/PTMA-VGCF cells, respectively. The larger specific capacity of BP-2000 and the improved electrochemical kinetics of PTMA at the surface of BP carbon, resulted from the larger surface area of BP-2000, are the main factors for improving the capacity and rate capability of the PTMA-electrode. The high specific surface area of BP-2000 is also beneficial to the thorough contact of PTMA with BP carbon, resulting in the improved conductivity of the PTMA-BP composites. The cycling performance of the PTMA-BP electrode is also satisfied.     

Signature of nanodiamond in Raman spectra: a density functional theoretical study

Nanocrystalline diamond (NCD) has attracted great attention both experimentally and theoretically in the past few years. The identification of the presence and the amount of NCD in amorphous carbon film has been a challenging issue. Although Raman spectroscopy has become a standard tool for the characterization of various carbon phases, a simple criterion for identifying NCD has not yet been well-established. In the present work, a theoretical study of the Raman spectra of the model compounds of NCD is presented on the basis of the density functional calculations. The reliability of the computational approach has been tested by comparing the predicated Raman spectra of several reference molecules to those obtained experimentally. To show the unique Raman spectrum of a NCD phase, a series of the model compounds of various carbon materials including tetrahedral and hexagonal clusters, and trans-polyacetylene fragments, were considered, and subsequently their Raman spectra below 2000 cm(-1) were calculated and compared with each other. The calculated results indicate that the relatively stronger broad peak at about 480 cm(-1) could be used as the signature of a NCD phase in the sample.     

Onset of Chiral Adenine Surface Growth

The structure and stability of adenine crystals and thin layers has been studied by using scanning tunneling microscopy, X‐ray diffraction, and density functional theory calculations. We have found that adenine crystals can be grown in two phases that are energetically quasi‐degenerate, the structure of which can be described as a pile‐up of 2D adenine planes. In each plane, the structure can be described as an aggregation of adenine dimers. Under certain conditions, kinetic effects can favor the growth of the less stable phase. These results have been used to understand the growth of adenine thin films on gold under ultra‐high vacuum conditions. We have found that the grown phase corresponds to the α‐phase, which is composed of stacked prochiral planes. In this way, the adenine nanocrystals exhibit a surface that is enantiopure. These results could open new insight into the applications of adenine in biological, medical, and enantioselective or pharmaceutical fields.