Surface modification of polyacrylonitrile-based carbon fiber and its interaction with imide

In this work, sized polyacrylonitrile (PAN)-based carbon fibers were chemically modified with nitric acid and maleic anhydride (MA) in order to improve the interaction between carbon fiber surface and polyimide matrix. Bismaleimide (BMI) was selected as a model compound of polyimide to react with modified carbon fiber. The surface characteristic changing after modification and surface reaction was investigated by element analysis (EA), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and surface enhanced Raman scattering (SERS). The results indicated that the modification of carbon fiber surface with MA might follow the Diels Alder reaction mechanism. In the surface reaction between modified fibers and BMI, among the various surface functional groups, the hydroxyl group provided from phenolic hydroxyl group and bridged structure on carbon fiber may be the most effective group reacted with imide structure. The results may shed some light on the design of the appropriate surface structure, which could react with polyimide, and the manufacture of the carbon fiber-reinforced polyimide matrix composites.     

快速生长超长定向碳纳米管阵列的制备及机理

 采用一种无模板的化学气相沉积法裂解金属有机物,以二茂铁为催化剂,二甲苯为碳源,利用单温炉加热装置在100 min内成功制备了2.7 mm超长定向碳纳米管阵列,生长速率高达27 μm·min^-1。运用扫描电子显微镜、透射电子显微镜、拉曼光谱对定向碳纳米管阵列进行形貌观察和表征,结果表明:制得的碳纳米管阵列具有优越的定向性和管结构,并且石墨化程度高。给出了快速生长超长定向碳纳米管阵列的优化制备条件,结合表征结果讨论了碳纳米管阵列的生长机制,认为超长碳纳米管阵列采用的是一种催化剂固定不动的开口生长方式,碳源和催化剂的连续供应保证了超长碳纳米管阵列的快速生长。     

快速生长超长定向碳纳米管阵列的制备及机理

采用一种无模板的化学气相沉积法裂解金属有机物,以二茂铁为催化剂,二甲苯为碳源,利用单温炉加热装置在100 min内成功制备了2.7 mm超长定向碳纳米管阵列,生长速率高达27 μm·min-1。运用扫描电子显微镜、透射电子显微镜、拉曼光谱对定向碳纳米管阵列进行形貌观察和表征,结果表明:制得的碳纳米管阵列具有优越的定向性和管结构,并且石墨化程度高。给出了快速生长超长定向碳纳米管阵列的优化制备条件,结合表征结果讨论了碳纳米管阵列的生长机制,认为超长碳纳米管阵列采用的是一种催化剂固定不动的开口生长方式,碳源和催化剂的连续供应保证了超长碳纳米管阵列的快速生长。     

Enhanced interfacial strength of carbon nanotube/copper nanocomposites via Ni-coating: Molecular-dynamics insights

The molecular bridging between carbon nanotube (CNT) within the meta matrix is hopeful for enhancing nanocomposite's mechanical performance. One of the main problems for nanocomposites is the inadequate bonding between nonstructural reinforcement and meta matrix. Ni-coating on CNT is an effective method to overcome the drawback of the inadequate strength, but the enhancing mechanism has not well interpreted yet. In this paper, the enhancing mechanism will be interpreted from the molecular-dynamics insights. The pullout process of CNT and Ni-coated CNT against copper matrix is investigated. The effects of geometric parameters, including CNT length and diameter, are taken into considerations and discussed. Results show that the interfacial strength is significantly improved after the Ni-coated CNT, which shows a good agreement with the experimental results available in the open literature. Besides, the sliding mechanism of Ni-coated CNTs against copper matrix is much more like a kind of friction sliding and directly related to the embedded zone. However, the pullout force of the CNT without Ni-coating is nearly proportional to its diameter, but independent of embedded length.     

Growth of aligned carbon nanotube arrays on metallic substrate and its application to supercapacitors

Aligned carbon nanotube arrays (ACNTAs) with lengths up to 150 μm were fabricated on metallic alloy (Inconel 600) substrates by pyrolysis of iron (II) phthalocyanine (FePc) in the presence of ethylene (C₂H₄). The as-grown ACNTAs, formed by aligned multi-walled carbon nanotubes with high purity, were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and Raman spectroscopy techniques. The ACNTAs were used directly as electrode materials in supercapacitors with (Et)₄NBF₄ + propylene carbonate (PC) as electrolyte, and their electrochemical properties were investigated. A rectangular-shaped cyclic voltammetry (CV) curve was observed even at a sweep rate of 1000 mV s⁻¹. The specific capacitance measured at 1000 mV s⁻¹ was about 57 % (47 F g⁻¹) of that obtained at 1 mV s⁻¹ (83 F g⁻¹), and an equivalent series resistance (ESR) of 0.55 Ω was measured for the ACNTA and activated carbon pair electrodes embedded in a coin cell. The results indicated that the ACNTAs could be a promising candidate as electrode materials in supercapacitors.     

Structural and surface features of multiwall carbon nanotube

We present the direct evidence of defective and disorder places on the surface of multiwall carbon nanotube (MWCNT), visualizing the presence of amorphous carbon at those sites. These defective surfaces being higher in energy are the key features of functionalization with different materials. The interaction of the π orbital electrons of different carbon atoms of adjacent layers is more at the bent portion, than that of regular portion of the CNT. Hence the tubular structure of the bent portion of nanotubes is spaced more than that of regular portion of the nanotubes, minimizing the stress.     

Ultrasonic treatment of aramid fiber surface and its effect on the interface of aramid/epoxy composites

Aramid fiber/epoxy composites have been treated by ultrasound during the winding process to enhance the adhesion. According to the ultrasonic treatment interlaminar shear strength (ILSS) of composites has been greatly improved. Dynamic wetting method, XPS and AFM are used to examine the microscopic properties of resultant composites. The enhanced ILSS is attributed to the ultrasonic cavitation, which improves the wetting between aramid fibers and resins.     

Structural and morphological dependence of carbon nanotube arrays on catalyst aggregation

Catalyst aggregation affects the growth of carbon nanotube (CNT) arrays in terms of tubular structures, waviness, entanglement, lengths, and growth density etc., which are important issues for application developments. We present a systematic correlation between the aggregation of catalyst on the SiO₂/Si substrate and the structure and morphology of CNT arrays. The thickness of the catalyst film has a direct effect on the areal density of the catalytic particles and then the alignment of the CNT array. Introducing alumina as buffer layer and annealing the catalyst film at low pressure are two effective approaches to downsize the catalyst particles and then the diameter, wall number of the CNTs. Both the size and areal density of the catalyst also change with the CNT growth in accordance with Ostwald ripening process, with the bottom of the CNT array varying from well-aligned to disordered and adhesion between catalyst particles and the substrate getting enhanced. Strategies including tuning the thickness of the catalyst film, changing buffer layer, controlling on the growth time and the system pressure were used to regulate the aggregation of the catalyst. CNT arrays from disordered to well-aligned, from multi-walled to few-walled and further to single-walled were reproducibly synthesized by chemical vapor deposition of acetylene.     

Bound states of solitons in a fiber laser mode locked with carbon nanotube saturable absorber

We report on the experimental observation of bound states of solitons in an erbium-doped fiber laser passively mode-locked by the carbon nanotube saturable absorber. Bound states of solitons with various pulse separations are obtained. While the tightly bound solitons always exhibit the same set of fixed discrete pulse separations with π or π/2 phase difference, the feature becomes less obvious for the loosely bound solitons. The result that various states of the bound solitons were obtained in the same fiber laser makes a systematic experimental study on them and a comparison of their properties possible. Our results once again show that the bound soliton emission is an intrinsic feature of the mode-locked soliton fiber lasers.     

A refined method for estimating fiber and interfacial shear strength by using a single-fiber composite

In estimating interfacial shear strength from the fragmentation process of fibers in single-fiber composites, a problem arises as to the value of the fiber strength if the fiber strengths distribute widely and strongly depend on the fiber length. To overcome this problem, a refined analysis method for simultaneously estimating the fiber and the interfacial shear strength from the fragmentation process has been shown. Agreements between the values estimated with the proposed method and the results of the single-fiber tensile and the direct shear tests have been obtained. It has been shown that the estimation of the interfacial shear strength using the proposed method is insensitive to the matrix properties if the interfacial shear strength is unaltered by the matrix properties, and that the variations of the distribution parameters of the fiber strength is significantly smaller for the proposed method as compared with the single-fiber tensile tests. The results obtained by applying the proposed method to various carbon fibers have been shown.     

Improvement of surface wettability and interfacial adhesion of poly-(p-phenylene terephthalamide) by incorporation of the polyamide benzimidazole segment

In order to investigate the effect of the polyamide benzimidazole group on the surface wettability and interfacial adhesion of fiber/matrix composites, surface features of two kinds of aramid fibers, poly (p-phenylene terephthalamide) fiber (Kevlar-49) and poly-(polyamide benzimidazole-co-p-phenylene terephthalamide) (DAFIII), have been analyzed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and contact angle analysis (CAA) system, respectively.The results show that with the incorporation of the polyamide benzimidazole segment, more polar functional groups exist on DAFIII surface. The contact angles of water and diiodomethane on DAFIII surface get smaller. The surface free energy of DAFIII increases to 36.5 mJ/m², which is 2.3% higher than that of Kevlar-49. In addition, DAFIII has a larger rough surface compared with that of Kevlar-49 due to different spinning processes. The interfacial shear strength (IFSS) of DAFIII/matrix composite is 25.7% higher than that of Kevlar-49/matrix composite, in agreement with the observed results from surface feature tests. SEM micrographs of failed micro-droplet specimens reveal a strong correlation between the fracture features and the observed test data.     

Preparation of large-area double-walled carbon nanotube films and application as film heater

Large-area (larger than 30×30 cm²) double-walled carbon nanotube (DWCNT) films are prepared and application as a heating element for film heaters is demonstrated. A high heating efficiency is observed. Measurements indicate that the use of the DWCNT film heater would save energy consumption up to 20–30% when compared with a commercial film-like metal-based heater. Morphological analysis reveals that the special surface structure, appropriate electric and high thermal conductivities of the film formed by the network of entangled nanotube bundles may lead to the high heating performance. Considering large-area, shape flexibility, negligible weight and easy manipulation, the film exhibits promising potential applications as a film heater for thermal control in aircrafts, medical equipment, home appliances and other industrial fields at low temperature (below 400 °C).     

Effects of plasma surface modification on the mechanical properties of carbon fiber and carbon fiber/epoxy composite

_The effect of surface treatment on mechanical properties of carbon fibers has been investigated by application of plasma polymerization of selected monomers in the vapor phase. The role of the fiber-matrix interface on carbon fiber-reinforced epoxy resin composites has also been studied. Composites have been prepared separately by the use of plasma-modified and unmodified carbon fibers in the epoxy resin matrix. The mechanical properties of carbon fibers (Hercules and Grafil) as well as of fiber/epoxy composites were examined by using single filament and three-point bending tests, respectively. It was observed that plasma polymerization treatment at selected plasma conditions led to significant improvement of interlaminar shear and flexural strength values of composites.     

Effect of the surface roughness on interfacial properties of carbon fibers reinforced epoxy resin composites

The effect of the surface roughness on interfacial properties of carbon fibers (CFs) reinforced epoxy (EP) resin composite is studied. Aqueous ammonia was applied to modify the surfaces of CFs. The morphologies and chemical compositions of original CFs and treated CFs (a-CFs) were characterized by Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS). Compared with the smooth surface of original CF, the surface of a-CF has bigger roughness; moreover, the roughness increases with the increase of the treating time. On the other hand, no obvious change in chemical composition takes place, indicating that the treating mechanism of CFs by aqueous ammonia is to physically change the morphologies rather than chemical compositions. In order to investigate the effect of surface roughness on the interfacial properties of CF/EP composites, the wettability and Interfacial Shear Strength (IFSS) were measured. Results show that with the increase of the roughness, the wettabilities of CFs against both water and ethylene glycol improves; in addition, the IFSS value of composites also increases. These attractive phenomena prove that the surface roughness of CFs can effectively overcome the poor interfacial adhesions between CFs and organic matrix, and thus make it possible to fabricate advanced composites based on CFs.     

Relation between interfacial shear strength and compressive strength of carbon fiber/epoxy resin composite strands

The mechanism with which the fiber-matrix interfacial strength exerts its influence on the compressive strength of fiber reinforced composites has been studied by measuring the axial compressive strength of carbon fiber/epoxy resin unidirectional composite strands having different levels of interfacial shear strength. The composite strands are used for experiments in order to investigate the compressive strength which is not affected by the delamination taking place at a weak interlayer of the laminated composites. The interfacial strength is varied by applying various degrees of liquid-phase surface treatment to the fibers. The efficiency of the compressive strength of the fibers utilized in the strength of the composite strands is estimated by measuring the compressive strength of the single carbon filaments with a micro-compression test. The compressive strength of the composite strands does not increase monotonically with increasing interfacial shear strength but showes lower values at higher interfacial shear strengths. With increasing interfacial shear strength, the suppression of the interfacial failure in the misaligned fiber region increases the compressive strength, while at higher interfacial shear strengths, the enhancement of the crack sensitivity decreases the compressive strength.     

Preparation and characterization of aligned carbon nanotubes/polylactic acid composite fibers

Aligned functionalized multiwalled carbon nanotubes/polylactic acid (MWNTs-PCL/PLA) composite fibers were successfully prepared by electrospinning processing. The MWNTs bonded with the polycaprolactone chains exhibited excellent uniform dispersion in PLA solution by comparing with the acid-functionalized MWNTs and amino-functionalized MWNTs. Optical microscopy was used to study the aligned degree of the fibers and to investigate the influences of the electrodes distance on the alignment and structure of the fibers, and results showed that the best quality of aligned fibers with dense structure and high aligned degree were obtained at an electrodes distance of 3 cm. Moreover, the MWNTs embedded inside the MWNTs-PCL/PLA fibers displayed well orientation along the axes of the fibers, which was demonstrated by field emission scanning electron microscopy, transmission electron microscopy and Raman spectroscopy.     

The effects of carbon nanotube addition and oxyfluorination on the glucose-sensing capabilities of glucose oxidase-coated carbon fiber electrodes

Glucose-sensing electrodes were constructed from carbon fibers by electrospinning and heat treatment. By controlling the pore size, the specific surface area and pore volume of the electrospun carbon fibers were increased for efficient immobilization of the glucose oxidase. Carbon nanotubes were embedded as an electrically conductive additive to improve the electrical property of the porous carbon fibers. In addition, the surface of the porous carbon fibers was modified with hydrophilic functional groups by direct oxyfluorination to increase the affinity between the hydrophobic carbon surface and the hydrophilic glucose oxidase molecules. The porosity of the carbon fibers was improved significantly with approximately 28- and 35-fold increases in the specific surface area and pore volume, respectively. The number of chemical bonds between carbon and oxygen were increased with higher oxygen content during oxyfluorination based on the X-ray photoelectron spectroscopy results. Glucose sensing was carried out by current voltagram and amperometric methods. A high-performance glucose sensor was obtained with high sensitivity and rapid response time as a result of carbon nanotube addition, physical activation and surface modification. The mechanism of the highly sensitive prepared glucose sensor was modeled by an enzyme kinetics study using the Michaelis-Menten equation.     

Investigating the effect of different asphaltene structures on surface topography and wettability alteration

This paper aims at investigation of the effect of asphaltene structure on wettability and topography alteration of a glass surface as a result of asphaltene precipitation. In order to provide a better insight into the topography alteration, a bi-fractal approach was employed. Such an approach is capable of discriminating topography alteration in two different surface types, namely, macro-asperities and micro-asperities. The observed variation of the fractal dimension in the two surface types could be considered as the consequence of different asphaltene sources. Therefore, the structure of different asphaltene sources was carefully examined. The effect of asphaltene structure is more pronounced for asphaltene precipitation at higher pressure. It was revealed that asphaltene particles of high complexity and with larger poly-aromatic rings tend to be detached easier at higher pressure than those with smaller poly-aromatic rings. Another evidence to emphasize the significance of asphaltene structure was given through wettability alteration. It was found that asphaltene particles with larger poly-aromatic rings turn the surface less oil wet at higher pressure. It seems that the difference in wetting condition and surface topography alteration of different asphaltene sources roots in their different structures.     

Improvement and mechanism of interfacial adhesion in PBO fiber/bismaleimide composite by oxygen plasma treatment

The improved interfacial adhesion of PBO fiber-reinforced bismaleimide composite by oxygen plasma processing was investigated in this paper. After treatment, the maximum value of interlaminar shear strength was 57.5 MPa, with an increase of 28.9%. The oxygen concentration of the fiber surface increased, as did the surface roughness, resulting in improvement of the surface wettability. The cleavage and rearrangement of surface bonds created new functional groups OCO, NCO and NO, thereby activating the fiber surface. And long-time treatment increased the reaction degree of surface groups while destroyed the newly-created physical structures. The enhancement of adhesion relied primarily on the strengthening of chemical bonding and mechanical interlocking between the fiber and the matrix. The composite rupture planes indicated that the fracture failure shifted from the interface to the matrix or the fiber.