Plasma functionalization of nanotubes and carbon fibres for application in composites

During his PhD studies, Zhiqiang published 5 journal paper and 7 conference paper and also participated in the development of the first Plasma Research Laboratory at Institute of Frontier Materials.

Coating and functionalization of carbon fibres using a three-step plasma treatment

A three-step plasma treatment—activation, functionalization and polymerization—has been used to deposit a thin plasma polymer with amine groups on carbon fibres (CFs). This plasma polymer has strong adhesion to the CF surface and the amine groups enable strong bonding to a matrix. The CFs were first treated by Ar plasma to activate and clean the surface, followed by O2 plasma to incorporate oxygen-containing functional groups, and finally a heptylamine thin film was deposited using combined continuous wave and pulsed plasma polymerization. Strong adhesion between the plasma polymer and the CF was observed. The fibre strength was not affected by the treatment.

Enhancing the carbon yield of cellulose based carbon fibres with ionic liquid impregnates

Here we show that ionic liquids (ILs), protic or aprotic in nature containing a phosphate anion, can be used as effective impregnating compounds resulting in a 50% improvement of the carbon yield of cellulose based carbon fibres and a 70 °C reduction in the onset of the depolymerization temperature. Using 13C NMR and FTIR spectra, we characterize the carbonized fibres with and without IL impregnates. The oxidative step in the formation of carbon fibres from cellulose precursors is very important in determining the final material properties, as such we examine this stage and show that the IL reduces the onset of the cellulose depolymerization temperature while improving the oxidative stability. This study highlights the ability of ILs to act as novel impregnates which can successfully reduce the formation of tar and volatile substances during carbonization of cellulose based carbon fibres resulting in an improved carbon yield and significant cost savings due to reduced maintenance and wear of equipment. This journal is

Effect of surface functionality of PAN-based carbon fibres on the mechanical performance of carbon/epoxy composites

The performance of composite laminates depends on the adhesion between the fibre reinforcement and matrix, with the surface properties of the fibres playing a key role in determining the level of adhesion achieved. For this reason it is important to develop an in-depth understanding of the surface functionalities on the reinforcement fibres. In this work, multi-scale surface analysis of carbon fibre during the three stages of manufacture; carbonisation, electrolytic oxidation, and epoxy sizing was carried out. The surface topography was examined using scanning electron microscopy (SEM), which revealed longitudinal ridges and striations along the fibre-axis for all fibre types. A small difference in surface roughness was observed by scanning probe microscopy (SPM), while the coefficient of friction measured by an automated single fibre tester showed 51% and 98% increase for the oxidised and sized fibres, respectively. The fibres were found to exhibit heterogeneity in surface energy as evidenced from SPM force measurements. The unsized fibres were much more energetically heterogeneous than the sized fibre. A good correlation was found between fibre properties (both physical and chemical) and interlaminar shear strength (ILSS) of composites made from all three fibre types. © 2014 Elsevier Ltd.

Rapid surface functionalization of carbon fibres using microwave irradiation in an ionic liquid

The modification of carbon fibre surfaces has been achieved using a novel combination of low power microwave irradiation (20 W) in both an ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and an organic solvent (1,2-dichlorobenzene). The use of the ionic liquid was superior to the organic solvent in this application, resulting in a higher density of surface grafted material. As a consequence, carbon fibres treated in the ionic liquid displayed improved interfacial adhesion in the composite material (+28% relative to untreated fibres) compared to those treated in organic solvent (+18%). The methodology presented herein can be easily scaled up to industrially relevant quantities and represent a drastic reduction in both reaction time (30 min from 24 h) and energy consumption, compared to previously reported procedures. This work opens the door to potential energy and time saving strategies which can be applied to carbon fibre manufacture for high performance carbon fibre reinforced composites.

Hierarchical composites from carbon fibres electrosprayed with carbon nanotubes

 This research developed a novel method for coating carbon nanotubes onto carbon fibre surfaces. It provided valuable guidance for producing various CNT morphologies on fibre surfaces. More importantly, the produced hybrid structures improved interfacial bonding in composites significantly, and this research will explore more potential applications of new generation composites.

Glass/carbon fibre hybrid composite laminates for structural applications in automotive vehicles

Light-weight structure is one of the keys to improve the fuel efficiency and reduce the environmental buden of transport vehicles (automotive and rail). While fibreglass composites have been increasingly used to replace steel in automotive industry, the adoption rate for carbon fibre composites which are much lighter, stronger and stiffere than glass fibre composites, remains low. The main reason is the high cost of carbon fibres. To further reduce vehicle weight without excessive cost increase, one technique is to incorporate carbon fibre reinforcement into glass fibre composites and innovative design by selectively reinforcing along the main load path. Glass/carbon woven fabrics with epoxy resin matrix were utilised for preparing hybrid composite laminates. The in-plane mechanical properties such as tensile and three-point-bending flexural properties were investigated for laminates with different carbon fibre volume and lay-up scheme. It is shown that hybrid composite laminates with 50% carbon fibre reinforcement provide the best flexural properties when the carbon layers are at the exterior, while the alternating carbon/glass lay-up provides the highest compressive strength.

Hygrothermal effects on painted carbon fibre composite surfaces

In this article, the effect of hygrothermal aging on the painted surface finish of unidirectional and fabric carbon fibre composite laminates, with and without surfacing film was investigated. The results highlighted the importance of ensuring that the composite surface directly beneath the paint layer is made from a uniform material with a consistent thickness in order to minimise surface defects from occurring during aging. The surfacing film was found to minimise the print through development on the painted unidirectional and twill composite surfaces. However, the surfacing film layer was found to intermingle with the carbon fibre plies during cure, which resulted in an uneven film thickness that caused increased levels of orange peel. The twill laminate painted surface produced high levels of print through and surface waviness that was caused by the large resin rich regions located within the tow intersections at the surface which enlarged due to thermal expansion and swelling of the matrix with hygrothermal aging. It was also noted that the small resin rich regions between the individual carbon fibres on the unidirectional composite surface were sufficiently large to print through the painted surface.

Energy absorption behaviour of rapidly manufactured carbon/epoxy and glass/polypropylene structures

In this thesis the crashworthiness of composite tubular structures was investigated along with the property structure relationships of a glass/polypropylene material. The energy absorption capacity of tubular structures in a number of different testing configurations was made. Two materials; carbon/epoxy pre-preg and a glass/polypropylene dry pre-preg were investigated.

A novel approach to the functionalisation of pristine carbon fibre using azomethine 1,3-dipolar cycloaddition

We demonstrate the utilisation of an azomethine 1,3-dipolar cycloaddition reaction with carbon fibre to graft complex molecules onto the fibre surface. In an effort to enhance the interfacial interaction of the fibre to the matrix, the functionalised fibres possessed a pendant amine that is able to interact with epoxy resins. Functionalisation was supported by X-ray photoelectron spectroscopy and the grafting process had no detrimental effects on tensile strength compared with the control (untreated) fibres. Also, microscopic roughness (as determined by atomic force microscopy) and fibre topography were unchanged after the described treatment process. This methodology complements existing methodology aimed at enhancing the surface of carbon fibres for advanced material applications while not compromising the desirable strength profile. Single-fibre fragmentation tests show a statistically significant decrease in fragment length compared with the control fibres in addition to transverse cracking within the curing resin, both of which indicate an enhanced interaction between fibre and resin.

Facile fabrication of superhydrophobic conductive graphite nanoplatelet/vapor-grown carbon fiber/polypropylene composite coatings

The fabrication of superhydrophobic surfaces with mechanical durability is challenging because the surface microstructure is easily damaged. Herein, we report superhydrophobic conductive graphite nanoplatelet (GNP)/vapor-grown carbon fiber (VGCF)/polypropylene (PP) composite coatings with mechanical durability by a hot-pressing method. The as-prepared GNP/VGCF/PP composite coatings showed water contact angle (WCA) above 150° and sliding angle (SA) less than 5°. The superhydrophobicity was improved with the increase of VGCF content in the hybrid GNP and VGCF fillers. The more VGCFs added in the GNP/VGCF/PP composite coating, the higher porosity on the surface was formed. Compared to the GNP/PP and VGCF/PP composite coatings, the GNP and VGCF hybrid fillers exhibited more remarkable synergistic effect on the electrical conductivity of the GNP/VGCF/PP composite coatings. The GNP/VGCF/PP composite coating with GNP:VGCF = 2:1 possessed a sheet resistance of 1 Ω/sq. After abrasion test, the rough microstructure of the GNP/VGCF/PP (2:1) composite coating was mostly restored and the composite coating retained superhydrophobicity, but not for the VGCF/PP composite coating. When the superhydrophobic surface is mechanically damaged with a loss of superhydrophobicity, it can be easily repaired by a simple way with adhesive tapes. Moreover, the oil-fouled composite surface can regenerate superhydrophobicity by wetting the surface with alcohol and subsequently burning off alcohol.

A systematic study of carbon fibre surface grafting via in situ diazonium generation for improved interfacial shear strength in epoxy matrix composites

A recently established means of surface functionalization of unsized carbon fibres for enhanced compatibility with epoxy resins was optimised and evaluated using interfacial shear stress measurements. Interfacial adhesion has a strong influence on the bulk mechanical properties of composite materials. In this work we report on the optimisation of our aryl diazo-grafting methodology via a series of reagent concentration studies. The fibres functionalised at each concentration are characterised physically (tensile strength, modulus, coefficient of friction, and via AFM), and chemically (XPS). The interfacial shear strength (IFSS) of all treated fibres was determined via the single fibre fragmentation test, using the Kelly-Tyson model. Large increases in IFSS for all concentrations (28-47%) relative to control fibres were observed. We show that halving the reagent concentration increased the coefficient of friction of the fibre and the interfacial shear strength of the composite while resulting in no loss of the key performance characteristics in the treated fibre.