Interfacial load transfer in carbon nanotube/ceramic microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance the composite delamination resistance, and possibly improve its toughness and any matrix-dominated elastic property as well. In the present work aligned CNTs were grown upon ceramic fibers (silica and alumina) by chemical vapor deposition (CVD) at temperatures of 650 °C and 750 °C. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on pristine as well as on CNT-grown fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Significant increases (up to 50%) are observed in the fiber tensile strength and in the interfacial adhesion (which was sometimes doubled) with all fiber types upon which CNTs are CVD-grown at 750 °C. We discuss the likely sources of these improvements as well as their implications.     

Effect of γ-ray irradiation grafting on the carbon fibers and interfacial adhesion of epoxy composites

A special technique using γ-ray irradiation-induced graft-polymerization was applied to carbon fibers. Epoxy resin and chloroepoxy propane reacted with carbon fibers by a co-irradiation grafting method and acrylic acid was graft-polymerized onto the fiber surface via a pre-irradiation grafting method. The roughness, amount of containing-oxygen functional groups and surface energy were all found to increase significantly after irradiation grafting. Gamma-ray irradiation grafting improved marginally the tensile strength of carbon fibers, which was evaluated by statistical analysis using the Weibull distribution. The interlaminar shear strength of treated carbon fiber/epoxy was enhanced by at least 17.5%, compared with that of untreated carbon fiber/epoxy. The mechanisms of irradiation grafting are proposed by radical reactions. The γ-ray co-irradiation grafting and pre-irradiation grafting are both an effective method for modifying the physicochemical properties of carbon fibers and improving the interfacial adhesion of composites.     

Effect of ZnO nanowire morphology on the interfacial strength of nanowire coated carbon fibers

The ability to tailor interfacial shear strength for a particular fiber and resin system is critical to the development of composite materials that perform optimally in specific applications. One approach to tailor the interface is to introduce a secondary phase between the fiber and matrix, which can act to functionally grade the material properties and enhance load transfer across the interface. This approach has been applied in the past using nanowires, nanotubes, and whiskers and was demonstrated to significantly enhance interface performance. Unfortunately, these processes lack control over the interphase morphology to allow design of the interface for optimal properties. Recently, ZnO nanowires grown on the surface of carbon fibers have demonstrated more than a 110% increase in interfacial strength [1]. Unlike other treatments, this interfacial reinforcement allows precise morphology control. Here, we develop the parameters for the growth of nanowires with varying lengths and diameters and study the influence of the nanowire’s morphology on the interfacial shear strength. ZnO nanowire arrays are grown on carbon fibers, with nanowire diameters ranging from 50 to 200 nm and lengths up to 4 μm. The interfacial shear strength with varying nanowire dimensions is shown to increase by up to 228%, ranging from 45.72 to 154.64 MPa. Unlike existing whiskerization approaches, it is shown that the tensile strength of the ZnO nanowire coated fibers remains constant throughout all growth procedures. The development of an interphase offering control over the interface strength and toughness will provide a means to produce multifunctional composites with optimized performance for multiple applications.     

Interfacial properties and impact toughness of methylphenylsilicone resin composites by chemically grafting POSS and tetraethylenepentamine onto carbon fibers

Octaglycidyl polyhedral oligomeric silsesquioxane (gly-POSS) was successfully grafted on carbon fibers (CFs) surface to enhance interfacial properties and impact toughness of CFs reinforced methylphenylsilicone resin (MPSR) composites. After gly-POSS modification, POSS grafted CF (CF-POSS) with many epoxy functional groups was modified with tetraethylenepentamine (TEPA) to further enhance the interfacial strength. Atomic force microscopy (AFM) images showed that POSS and TEPA were grafted onto CFs surface uniformly and the surface roughness enhanced obviously. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the chemical bonding nature between CFs and POSS, as well as between POSS and TEPA. POSS and TEPA modification could increase the fiber polarity, wettability and surface energy significantly. The interlaminar shear strength (ILSS) and impact toughness of composites showed a dramatic improvement, especially for grafting with POSS and further with TEPA (CF-POSS-TEPA). Additionally, the reinforcing and toughening mechanisms were also analyzed. Meanwhile, single fiber tensile strength (TS) had no decrease after modification.     

Fabrication and characterization of recyclable carbon nanotube/polyvinyl butyral composite fiber

A surface-draw method to fabricate recyclable carbon nanotube/polyvinyl butyral (CNT/PVB) composite fibers is reported. This method is effective for both single-walled carbon nanotube (SWCNT) and multi-walled carbon nanotube. The CNT mass content of CNT/PVB composite fibers can vary from 0 to 80 wt.%, which is higher than most CNT/polymer composites reported to date. The diameter of the composite fibers can be controlled in the range of 10-100 μm, with essentially unlimited draw length. The composite fibers with 7.4 wt.% SWCNTs showed optimal tensile properties. Compared with pure PVB fibers, the tensile strength, failure strain, and elastic modulus of the composite fiber have improved about 127%, 27%, and 73%, respectively. In addition, SWCNT/PVB composites with 66.7 wt.% SWCNTs have the highest conductivity of 42.9 S m⁻¹. More importantly, the major benefit is the “greenness” of the method, which involves environment friendly ethanol-water solvent with no functionalization of the nanotube required, and only simple apparatus are needed. The CNT/PVB composite fibers obtained can be dissolved in ethanol solution and reformed with the surface draw method without any additional treatment; and the material properties after recycle is comparable to those fabricated in the first round.     

Enhanced mechanical properties of multiscale carbon fiber/epoxy composites by fiber surface treatment with graphene oxide/polyhedral oligomeric silsesquioxane

Graphene oxide (GO) and polyhedral oligomeric silsesquioxane (POSS) grafted carbon fiber (CF) was demonstrated to reinforce the mechanical properties of fiber composites. Such a fiber composite was prepared by grafting POSS onto the CF surface using GO as the linkage. The presence of GO linkage and POSS could significantly enhance both the area and wettability of fiber surface, leading to an increase in the interfacial strength between fibers and resin. Compared with the desized CF composites, the grafted CF composites fabricated by compression molding method exhibited 53.05% enhancement in the interlaminar shear strength. The changed surface morphology, surface composition and surface energy were supposed to be related with the interfacial performance of unidirectional composites, as revealed by scanning electron microscopy, atomic force microscope, dynamic contact angle test and X-ray photoelectron microscopy charaterizations.     

Hierarchical composites of carbon nanotubes on carbon fiber: Influence of growth condition on fiber tensile properties

Growing carbon nanotubes (CNT) on the surface of high performance carbon fibers (CF) provides a means to tailor the thermal, electrical and mechanical properties of the fiber–resin interface of a composite. However, many CNT growth processes require pretreatment of the fiber, deposition of an intermediate layer, or harsh growth conditions which can degrade tensile properties and limit the conduction between the fiber and the nanotubes. In this study, high density multi-wall carbon nanotubes were grown directly on two different polyacrylonitrile (PAN)-based carbon fibers (T650 and IM-7) using thermal Chemical Vapor Deposition (CVD). The influence of CVD growth conditions on the single-fiber tensile properties and CNT morphology was investigated. The mechanical properties of the resultant hybrid fibers were shown to depend on the carbon fiber used, the presence of a sizing (coating), the CNT growth temperature, growth time, and atmospheric conditions within the CVD chamber. The CNT density and alignment morphology was varied with growth temperature and precursor flow rate. Overall, it was concluded that a hybrid fiber with a well-adhered array of dense MWCNTs could be grown on the unsized T650 fiber with no significant degradation in tensile properties.     

Long-term moisture effects on the interfacial shear strength between surface treated carbon fiber and epoxy matrix

In recent years, carbon fiber reinforced polymer (CFRP) composites have found increasing applications in marine and offshore area, where the CFRP components are subjected to a persistent attack of moisture. The performance degradation of composites under those critical service conditions becomes a key issue. In this work, silane coating and multiwalled carbon nanotubes were applied on carbon fibers to enhance the fiber/matrix interfacial bonding strength. The long-term effects of moisture on the interfacial shear strength (IFSS) of the composites in underwater environments, such as de-ionized water and simulated seawater, have been studied using single fiber microbond method. The silane coating and carbon nanotube-modified silane coating are found to contribute 14.5% and 26.3% increase in IFSS of the CFRP in dry air, and well maintain this improvement during a 120-day immersion test in de-ionized water and simulated seawater.     

Effect of a multiscale reinforcement by carbon fiber surface treatment with graphene oxide/carbon nanotubes on the mechanical properties of reinforced carbon/carbon composites

An effective carbon fiber/graphene oxide/carbon nanotubes (CF-GO-CNTs) multiscale reinforcement was prepared by co-grafting carbon nanotubes (CNTs) and graphene oxide (GO) onto the carbon fiber surface. The effects of surface modification on the properties of carbon fiber (CF) and the resulting composites was investigated systematically. The GO and CNTs were chemically grafted on the carbon fiber surface as a uniform coating, which could significantly increase the polar functional groups and surface energy of carbon fiber. In addition, the GO and CNTs co-grafted on the carbon fiber surface could improve interlaminar shear strength of the resulting composites by 48.12% and the interfacial shear strength of the resulting composites by 83.39%. The presence of GO and CNTs could significantly enhance both the area and wettability of fiber surface, leading to great increase in the mechanical properties of GO/CNTs/carbon fiber reinforced composites.     

Influence of functionalized carbon nanofibers on the single carbon fiber–epoxy matrix interface

Amine-functionalized carbon nanofibers (A-CNFs) were deposited on the surface of individual sized carbon fibers using electrophoretic deposition (EPD), and the average interfacial shear strength (IFSS) was determined using the single fiber fragmentation test in conjunction with Weibull analysis. The IFSS decreased by 25% for fibers acting as the negative electrode in water without CNFs, and the impact of agglomerates on IFSS estimation is discussed. Further, a 187% IFSS increase was achieved for fibers undergoing a two-stage A-CNF EPD approach.     

Interfacial shear strength of a glass fiber/epoxy bonding in composites modified with carbon nanotubes

In recent years, carbon nanotubes (CNTs) grown on fibers have attracted a lot of interest as an additional reinforcing component in conventional fiber-reinforced composites to improve the properties of the fiber/matrix interface. Due to harsh growth conditions, the CNT-grafted fibers often exhibit degraded tensile properties. In the current study we explore an alternative approach to deliver CNTs to the fiber surface by dispersing CNTs in the fiber sizing formulation. This route takes advantage of the developed techniques for CNT dispersion in resins and introduces no damage to the fibers. We focus on unidirectional glass fiber/epoxy macro-composites where CNTs are introduced in three ways: (1) in the fiber sizing, (2) in the matrix and (3) in the fiber sizing and matrix simultaneously. Interfacial shear strength (IFSS) is investigated using single-fiber push-out microindentation. The results of the test reveal an increase of IFSS in all three cases. The maximum gain (over 90%) is achieved in the composite where CNTs are introduced solely in the fiber sizing.     

A numerical study on carbon nanotube pullout to understand its bridging effect in carbon nanotube reinforced composites

Carbon nanotube (CNT) reinforced polymeric composites provide a promising future in structural engineering. To understand the bridging effect of CNT in the events of the fracture of CNT reinforced composites, the finite element method was applied to simulate a single CNT pullout from a polymeric matrix using cohesive zone modelling. The numerical results indicate that the debonding force during the CNT pullout increases almost linearly with the interfacial crack initiation shear stress. Specific pullout energy increases with the CNT embedded length, while it is independent of the CNT radius. In addition, a saturated debonding force exists corresponding to a critical CNT embedded length. A parametric study shows that a higher saturated debonding force can be achieved if the CNT has a larger radius or if the CNT/matrix has a stronger interfacial bonding. The critical CNT embedded length decreases with the increase of the interfacial crack initiation shear stress.     

The effect of surface modification with carbon nanotubes upon the tensile strength and Weibull modulus of carbon fibers

Carbon fibers are widely used as reinforcements in composite materials because of their high specific strength and modulus. Today, a number of ultrahigh strength polyacrylonitrile (PAN)-based (more than 6?GPa), and ultrahigh modulus pitch-based (more than 900?GPa) carbon fibers have been commercially available. In contrast, carbon nanotube (CNT) with the extremely high tensile strength have attracted attention as reinforcements. An interesting technique to modify the carbon fiber is CNT grafting on the carbon fiber surface. CNT-grafted carbon fibers offer the opportunity to add the potential benefits of nanoscale reinforcement to well-established fibrous composites to create micro-nano multiscale hybrid composites. In the present study, the tensile properties of CNT grown on T1000GB PAN- and K13D pitch-based carbon fibers have been investigated. Single filament tensile test at gauge lengths of 1, 5, and 25?mm were conducted. The effect of gauge length on tensile strength and Weibull modulus of CNT-grafted PAN- and pitch-based carbon fibers were evaluated. It was found that grafting of CNT improves the tensile strength and Weibull modulus of PAN- and pitch-based carbon fibers with longer gauge length (≥5?mm). The results also clearly show that for CNT-grafted and as-received PAN- and pitch-based carbon fibers, there is a linear relation between the Weibull modulus and the average tensile strength on log–log scale.     

Mechanical properties of injection-molded carbon fiber/polypropylene composites hybridized with nanofillers

Short-carbon-fiber/polypropylene composites (CF/PP composites) have high processability and recyclability but low strength. To improve the strength, various nanofillers were hybridized to form fiber-reinforced composites. Adding nanofillers improves not only the strength but also the elastic modulus, with the exception of clay nanofillers. To understand the strengthening mechanism resulting from the addition of nanofillers, the residual fiber length and interfacial shear strength were measured. For CF/PP composites, the addition of alumina, silica, and CNT improves the interfacial shear strength, and thereby, the mechanical properties. On the basis of this result, proper choice of nanofiller type and content for improving the mechanical properties of PP/CF composites is discussed.     

Mixed resin and carbon fibres surface treatment for preparation of carbon fibres composites with good interfacial bonding strength

The objective of this work is to improve the interlaminar shear strength of composites by mixing epoxy resin and modifying carbon fibres. The effect of mixed resin matrix’s structure on carbon fibres composites was studied. Anodic oxidation treatment was used to modify the surface of carbon fibres. The tensile strength of multifilament and interlaminar shear strength of composites were investigated respectively. The morphologies of untreated and treated carbon fibres were characterized by scanning electron microscope and X-ray photoelectron spectroscopy. Surface analysis indicates that the amount of carbon fibres chemisorbed oxygen-containing groups, active carbon atom, the surface roughness, and wetting ability increases after treatment. The tensile strength of carbon fibres decreased little after treatment by anodic oxidation. The results show that the treated carbon fibres composites could possess excellent interfacial properties with mixed resins, and interlaminar shear strength of the composites is up to 85.41 MPa. The mechanism of mixed resins and treated carbon fibres to improve the interfacial property of composites is obtained.     

Modelling of the carbon nanotube bridging effect on the toughening of polymers and experimental verification

The effect of aligned and randomly oriented carbon nanotube (CNT), with respect to the crack growth plane, on the fracture toughness of polymers is modelled in this paper using the Elastic Plastic Fracture Mechanics. According to a critical length, two dominant toughening mechanisms for CNT-modified polymers are presented, i.e. CNT pull-out and CNT rupture. The model is then used to identify the effect of CNTs geometrical and mechanical properties on the enhancement of fracture toughness in CNT-modified polymers. The key CNT properties are the CNT radius, average length, ultimate strength, elongation before failure, interfacial shear strength between CNTs and the polymer and nanotube volume fraction. Finally, experimental results are compared with the model predictions. The correlation shows that processing of long, aligned CNTs remains the main barrier in achieving major fracture toughness enhancement.     

Optimum dispersion conditions and interfacial modification of carbon fiber and CNT–phenolic composites by atmospheric pressure plasma treatment

Electric resistance measurements were used to determine the optimal dispersion conditions for carbon nanotubes (CNTs) in phenolic resins. Plasma treatment is frequently used to modify carbon fiber surfaces to improve adhesion of the fibers to matrices. Such treatment might also influence carbon fiber tensile strength. In order to determine the effect of atmospheric pressure plasma treatment on carbon fiber tensile strength and interfacial bonding strength, change in tensile strength of the fiber was studied at different gage lengths before and after the plasma treatment. The wettability of carbon fibers was improved significantly after only 10 s of plasma treatment. Such plasma treatment resulted in a decrease in the advancing contact angle from 65° to 28°. Surface energies of carbon fiber and CNT–phenolic composites were measured using the Wilhelmy plate technique, indicating that the work of adhesion between plasma treated carbon fibers and CNT–phenolic composites was higher than it before plasma modification. The interfacial shear strength (IFSS) and apparent modulus were also increased by plasma treatment of the carbon fibers.     

A chemical method to graft carbon nanotubes onto a carbon fiber

A simple method is developed for grafting carbon nanotubes (CNTs) onto a carbon fiber surface. CNT and carbon fiber undergo an oxidation treatment. Oxidation generates oxygen, like carboxyl, carbonyl or hydroxyl groups, or amine groups on nanotubes and carbon fiber surface. Functionalized CNTs are dispersed in a solvent and deposited on carbon fibers. The bonds between CNT and carbon fiber are operated by esterification, anhydridation or amidization of the chemical surface groups. The resulting materials are characterized by scanning electron microscopy (SEM). CNTs form a 3D network around the carbon fibers. Likewise, CNT bonding between two fibers is observed.     

A facile method for preparing CNT-grafted carbon fibers and improved tensile strength of their composites

Carbon nanotube (CNT)-grafted carbon fibers (CFs) have emerged as new reinforcements for improving the mechanical properties of CF-reinforced composites but such enhancement in macroscale composites has not been realized. This paper reports a facile method for preparing CNT-grafted CFs and improving the tensile strength of their composites. A CNT/polyacrylonitrile solution was sprayed onto the surface of the CF woven fabrics, and the CNTs were grafted by a thermal treatment at 300 °C. CNT-grafted CF composites were fabricated using the CNT-grafted CF woven fabrics using a vacuum-assisted resin transfer molding process with epoxy resin. The CNT-grafted CF composite exhibited 22% enhancement in the tensile strength compared to that of the pristine CF composite. Fracture surfaces of the CNT-grafted CF composites showed that the grafted CNTs obstructed the propagation of micro-cracks and micro-delamination around the CFs and also yarn boundaries, resulting in improved tensile strength of CNT-grafted CF composites.     

Carbon nanotube grafted silica fibres: Characterising the interface at the single fibre level

Model polymer composites containing carbon nanotube (CNT) grafted fibres provide a means to investigate the influence of nanostructures on interfacial properties. Well-aligned nanotubes, with controllable length, were grown on silica fibres by using the injection chemical vapour deposition method, leading to a significant increase of the fibre surface area. In single fibre tensile tests, this CNT growth reaction reduced the fibre strength, apparently due to catalyst etching; however, the fibre modulus increased significantly. Contact angle measurements, using the drop-on-fibre method, indicated an excellent wettability of the CNT-grafted fibres by poly(methyl methacrylate) (PMMA). PMMA model composites were fabricated and studied using the single fibre fragmentation tests. A dramatic improvement (up to 150%) of the apparent interfacial shear strength (IFSS) was obtained for the composites containing CNT-grafted fibres. The improvement of IFSS was also influenced by the length and morphology of the grafted CNTs.