Liquid crystal polymer-carbon fiber composites. Molecular orientation

The objective of this work has been to study composite systems in which carbon fibers are dispersed in a liquid crystal polymer matrix. The fundamental point of interest here has been the interfacial response that fiber surfaces can potentially induce in self-ordering polymers. The matrix material used was a thermotropic liquid crystal polyester synthesized in our laboratory from the monomers p-acetoxybenzoic acid, diacetoxyhydroquinone, and pimelic acid. The aromatic-aliphatic polymer was characterized by NMR as a chemically disordered polymer of the three structural units which exhibits a nematic phase at temperatures above 150°C. Breadline proton NMR above the solid to liquid crystal transition was used to measure the rate of magnetic alignment of molecules in the matrix and polarized optical microscopy was used to analyze interfacial zones in composite samples. Fiber surfaces were found to influence the orientation and orientational dynamics of a liquid crystal polymer matrix. This was revealed by enhanced rates of magnetic orientation in the polymer melt when carbon fibers are dispersed in the medium. Fiber surfaces were also found to stabilize nematic ordering of the polymer as the melt was heated towards complete isotropization. The phenomena discovered here may originate in the development of zones around fibers with a common molecular orientation anchored by the carbon surface.     

In situ melt grafting in carbon black/polyolefin composites and its influence on conductive performance

To improve the conductive properties of carbon‐black‐filled low‐density polyethylene, in situ grafting of certain monomers was applied during the melt compounding process. The experimental data obtained demonstrated that chemical bonding could thus be established between the fillers and the matrix polymer. The degree of enhancement of the filler/matrix interfacial interactions in the composites prepared in this way depends on the species of the grafting monomers being employed. When compared with the untreated carbon black composites, the composites manufactured through in situ melt grafting exhibited reduced room temperature resistivities and greatly increased positive temperature coefficient intensities, as well as favorable performance reproducibility. This proposed technical route has several advantages, including simplicity, low cost and easy control. Copyright © 2004 Society of Chemical Industry     

Multiwalled carbon nanotube/polyacrylonitrile composite fibers prepared by in situ polymerization

Multi‐walled carbon nanotubes (CNTs) were mixed with polyacrylonitrile (PAN) by in situ polymerization or by mechanically mixing. The mixtures were then wet‐spun into fibers, respectively. The effects of mixing method on the interfacial bonding between the components in the fibers and the properties of the fiber were investigated by Raman spectroscopy, TEM, SEM, and tensile strength testing. By in situ polymerization mixing, a thin layer of PAN molecules is observed to cover the surface of the CNT, which increases the diameter of CNT evidently. Results of Raman spectroscopy indicate that the layer of PAN molecules are strongly attached onto the surface of CNT through grafting polymerization, leading to strong chemical bonding between CNTs and PAN matrix in the obtained fibers. In contrast, no obvious chemical interactions are observed between them in the fibers prepared by mechanically mixing. In both cases, the CNTs have significantly strengthened the PAN fibers. However, the fibers prepared from in situ polymerization mixing are much stronger because of the interfacial bonding effect between the PAN molecules and CNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on long fiber–reinforced thermoplastic composites prepared by in situ solid‐state polycondensation

Long glass fiber–reinforced thermoplastic composites were prepared by a new process, in situ solid‐state polycondensation (INSITU SSP). In this process reinforcing continuous fibers were impregnated by the oligomer of PET melt, and then the impregnated continuous fibers were cut to a desired length (designated prepreg); finally, the prepreg was in situ polymerized in the solid state to form the high molecular weight matrix. SEM, FTIR spectra, short‐beam shear stress test, flexural strength test, impact strength test, and the intrinsic viscosity measurement were used to investigate the wetting and interfacial adhesion, the mechanical properties of the composite, and the molecular weight of matrix resin in the composite. The results showed that the molecular weight of PET in the matrix resin and mechanical properties could be adjusted by controlling the SSP time and that the high level of interfacial adhesion between reinforcing fibers and matrix resin could be achieved by this novel INSITU SSP process, which are attributed to the good wetting of reinforcing fibers with low molecular weight oligomer melt as the impregnation fluid, the in situ formation of chemical grafting of oligomer chains onto the reinforcing fiber surface, and the in situ formation of the high molecular weight PET chains in the interphase regions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3959–3965, 2004     

Interfacial evaluation of epoxy/carbon nanofiber nanocomposite reinforced with glycidyl methacrylate treated UHMWPE fiber

Interface interactions of fiber–matrix play a crucial role in final performance of polymer composites. Herein, in situ polymerization of glycidyl methacrylate (GMA) on the ultrahigh molecular weight polyethylene (UHMWPE) fibers surface was proposed for improving the surface activity and adhesion property of UHMWPE fibers towards carbon nanofibers (CNF)‐epoxy nanocomposites. Chemical treatment of UHMWPE fibers was characterized by FTIR, XPS analysis, SEM, and microdroplet tests, confirming that the grafting of poly (GMA) chains on the surface alongside a significant synergy in the interfacial properties. SEM evaluations also exhibited cohesive type of failure for the samples when both GMA‐treated UHMWPE fiber and CNF were used to reinforce epoxy matrix. Compared with unmodified composite, a ～319% increase in interfacial shear strength was observed for the samples reinforced with both 5 wt % GMA‐grafted UHMWPE and 0.5 wt % of CNF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43751.     

Improvement of interfacial properties in bismaleimide composites using functionalized graphene oxide grafted carbon fiber

A hierarchical reinforcement, which was used to improve the interfacial properties of bismaleimide (BMI) composites, was prepared by grafting functionalized graphene oxide (GO) onto a carbon fiber surface. The GO and carbon fibers were first functionalized separately to create interactional functional groups on their surfaces. The grafting process was then realized by an amidation reaction of the amine and acyl chloride function groups formed on GO and carbon fibers, respectively. The surface groups of functionalized GO and carbon fibers were identified by an X‐ray photoelectron spectroscopy (XPS). The resulting reinforcement was further characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and dynamic contact angle analysis. Experimental results showed that the functionalized GO were successfully grafted onto the carbon fibers surfaces and significantly increased the surface energy of carbon fibers. The study also indicated that the prepared hierarchical reinforcement could significantly improve the interfacial adhesion of resulting BMI composite. POLYM. ENG. SCI., 58:886–893, 2018. © 2017 Society of Plastics Engineers     

Development and evaluation of surface treatments to enhance the fiber-matrix adhesion in PAN-based carbon fiber/liquid crystal polymer composites. Part I: Coupling agent and amine surface treatments

Several surface treatments, using both commercially available coupling agents and reagents containing multiple amines, were applied to commingled continuous as-received AS4 carbon reinforcing fiber/liquid crystal polymer (LCP) matrix fibers. Unidirectional composites (normally 60 vol% carbon fiber) were prepared from as-received and treated commingled fibers and characterized. To estimate the effect the effect of the treatments on fiber-matrix adhesion, short beam shear (SBS) tests were conducted, the failure surfaces were examined, and spectroscopic studies wee performed. The mean SBS strength of the as-received unidirectional AS4 carbon fiber/LCP matrix composite system was 49 MPa. The best coupling agent and amine treatments yielded increases in composite shear strength of ∼ 10 to 20%, relative to the as-received AS4/LCP system. For the amine treatments, ESCA and FTIR analyses suggested of both the carbon and LCP fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers (both with coupling agents and amines) showed that strong fiber-matrix adhesion was present. That is, failure occurred in the LCP matrix material.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 1. Interfacial adhesion study

Unsized AS-4 carbon fibers were etched by RF plasma and then coated via plasma polymerization in order to enhance their adhesion to vinyl ester resin. Gases utilized for plasma etching were Ar, N₂ and O₂, while monomers used in plasma polymerization coating were acetylene, butadiene and acrylonitrile. Plasma etchings were carried out as a function of plasma power (30–70 W), treatment time (1–10 min) and gas pressure (20–40 mtorr). Plasma polymerizations were performed by varying the treatment time (15–60 s), plasma power (10–30 W) and gas pressure (20-40 mtorr). The conditions for plasma etching and plasma polymerization were optimized by measuring interfacial adhesion with vinyl ester resin via micro-droplet tests. Plasma etched and plasma polymer coated carbon fibers were characterized by SEM, XPS, FT-IR and α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. In Part 1, interfacial adhesion of plasma etched and plasma polymer coated carbon fibers to vinyl ester resin is reported, while characterization results including tensile strength of carbon fibers are reported in Part 2. Among the treatment conditions, a combination of Ar plasma etching and acetylene plasma polymer coating provided greatly improved interfacial shear strength (IFSS) of 69 MPa, compared to 43 MPa obtained from as-received carbon fiber. Based on the SEM analysis of failure surfaces and load-displacement curves, the failure was found to occur at the interface between plasma polymer coating and vinyl ester resin.     

Interfacial adhesion of plasma‐treated carbon fiber/poly(phthalazinone ether sulfone ketone) composite

Interfacial adhesion between fiber and matrix has a strong influence on composite mechanical performance. To exploit the reinforcement potential of the fibers in advance composite, it is necessary to reach a deeper understanding on the relation between fiber surface treatment and interfacial adhesion. In this study, air plasma was applied to modify carbon fiber (CF) surface, and the capability of plasma grafting for improving the interfacial adhesion in CF/thermoplastic composite was discussed and also the mechanism for composite interfacial adhesion was analyzed. Results indicated that air plasma treatment was capable of increasing surface roughness as well as introducing surface polar groups onto CF; both chemical bonding and mechanical interaction were efficient in enhancements of interlaminate shear strength of CF/PPESK composite, while mechanical interaction has a dominant effect on composite interfacial adhesion than chemical bonding interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Characterization of coatings of poly(hexamethylene adipamide) deposited on carbon fibers by interfacial polymerization techniques

Polyamide coatings deposited on carbon fibers by means of an interfacial in situ polymerization technique have been examined. Two different coating processes were used, depending on the length of the carbon fibers (short or long). The effect of the concentration of the monomer reactants on the quantity of coating deposited on the fibers has been determined using thermogravimetric analysis (TGA). Characterization techniques used to identify the nature of the coating process product included Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). Using the above techniques, IR spectra were collected and identified, and important polymer properties, such as morphology, melting point, and the molecular weight of the polymer coating were determined. © 1995 John Wiley & Sons, Inc.     

Cellulose fiber/polymer adhesion: effects of fiber/matrix interfacial chemistry on the micromechanics of the interphase

The objective of this study was to examine the effects of interfacial chemistry on the interfacial micromechanics of cellulose fiber/polymer composites. Different interfacial chemistries were created by bonding polystyrene (a common amorphous polymer) to fibers whose surfaces contained different functional groups. The chemical compatibility within the interphase was evaluated by matching the solubility parameters (δ) between the polymer and the induced functional groups. The physico-chemical interactions within the interphase were determined using the Lifshitz–van der Waals work of adhesion (W _a ^LW) and the acid–base interaction parameter (I _a?b) based on inverse gas chromatography (IGC). The micromechanical properties of the fiber/polymer interphase were evaluated using a novel micro-Raman tensile test. The results show that the maximum interfacial shear stress, a manifestation of practical adhesion, can be increased by increasing the acid–base interaction (I _a?b) or by reducing the chemical incompatibility (Δδ) between the fibers and polymer. A modified diffusion model was employed to predict, with considerable success, the contribution of interfacial chemistry to the practical adhesion of cellulose-based fibers and amorphous polymers. The increased predictability, coupled with the existing knowledge of the bulk properties of both fibers and matrix polymer, should ultimately lead to a better engineering of composite properties.     

Synthesis of a new compatibilisant agent PVC‐g‐MA and its use in the PVC/alfa composites

The main objective of this research was to synthesize a new compatibilisant agent (PVC‐g‐MA), which was grafted from the maleic anhydride on the PVC chains. The presence of maleic anhydride grafting on PVC was made evident by infrared analysis. PVC‐g‐MA was used like compatibilisant to solve the problem of the incompatibility between the hydrophobic polymeric matrix (PVC) and hydrophilic fiber (alfa). Composites samples were prepared with different alfa fiber loading (10, 20, and 30 wt %) and incorporating PVC‐g‐MA (1, 3, and 5 wt %) or PP‐g‐MA (3 wt %). The tensile properties, the thermal stability and the morphology of the composites were investigated. The result indicated that the PVC‐g‐MA increased the interfacial adhesion between the fibers and the polymer matrix and this effect was better than that obtained for the maleated‐polypropylene‐coupled composites. Microstructure analysis of the fractured surfaces of MAPP modified composites confirmed improved interfacial bonding. The addition of alfa and PVC‐g‐MA increased the thermal stability of the composites. The temperature of degradation of the polymer matrix increased about 16°C in comparison to the noncoupled composite, indicating that PVC‐g‐MA improved the thermal stability of the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of polycaprolactone/polyglycolide blended electrospun fibers on the morphology and mechanical properties of polycaprolactone

Polycaprolactone (PCL) and polyglycolide (PGA) are two biopolymers that have been used as in situ biomedical devices for various applications. The obstacle of creating a composite that captures the benefit of PCL's long degradation time, while acquiring the strength from PGA is overcoming the lack of surface adhesion between the two biopolymers for stress transfer to occur. This study investigates the use of miscible PCL‐PGA blended fibers, created by electrospinning, to increase the interfacial bonding of fibers to the PCL matrix of the polymer–polymer composite. The use of the blended fibers will thereby create the ability of load transfer from the long‐term PCL matrix to the stronger PCL‐PGA fiber reinforcement. The incorporation of the PCL‐PGA fibers was able to increase the tensile yield strength and Young's modulus over that of the bulk PCL, while decreasing the percent elongation at break. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40224.     

Grafted carbon fibers and their physicochemical properties. I. Grafting of methacrylic acid onto carbon fibers

A simple, reproducible method for grafting different carbon fibers (modified and unmodified, high‐modulus, and high‐tensile) with methacrylic acid is presented. The grafted carbon fibers were characterized by wetting measurements and electrokinetic studies. Scanning electron microscopy micrographs showed grafted polymer chains on all carbon fiber surfaces. The success of the grafting procedure depends on a suitable modification of the fiber surface. The amount and size of the grafted polymer chains on modified carbon fibers depend on the amount of initiator used. Contact angle measurements indicate an increase of the contact angle versus water and a decrease versus diiodomethane. The surface polarity calculated from the surface tensions obtained from contact angle values decreases for all systems under investigation. Zeta (ζ) potential measurements confirmed these results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1175–1185, 1999     

Thermal bonding of nonwovens as simulated by polypropylene films: Effect of time,temperature, and molecular weight

Many nonwoven fabrics are made by melt spinning semicrystalline fibers followed by thermal bonding using heated calendar rolls. In this work, we have studied thermal bonding of polypropylene films to simulate bonding of nonwoven fibers. We have tried to relate the thermal bond strengths with the concepts of chain dynamics via interfacial adhesion development at symmetric polymer interfaces. This requires relating the microscopic dynamics of chains with macroscopic interfacial adhesion measurements. It was found that the interfacial bond strength was proportional to the fraction of the crystals melted. This required heating the interfacial region between the polymer layers into the melting region. Bond strengths were also related to process time as t^1/2. This dependence is consistent with the literature for reptation, but is also due to the required thermal diffusion to bring the interfacial region to the bonding temperature. Finally, the bond strength is also dependent on the polymer molecular weight as 1/M^1/2, which is consistent with forming the bonds via chain reptation, provided that the bonding time is less than the reptation time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrospinning of in situ and ex situ synthesized polyimide composites reinforced by titanate nanotubes

A colloidal dispersion of titanate nanotubes (TiNT) and polyamic acid (PAA) in dimethylformamide (DMF) was electrospun and chemically converted to polyimide (PI)–titanate nanotube (PI‐TiNT) composite nanofibers of 500–1000 nm diameter. The dispersion of nanotubes in the polymer was addressed by two different approaches, namely an in situ method (when TiNT was coated with one of the monomers) and an ex situ one (when TiNT reacted directly with PAA). SEM images showed bead formation on samples from the in situ approach, while ex situ samples showed the absence of such features. Good distribution and some alignment of TiNT within the polymer fibers from in situ or ex situ approaches were observed by TEM imaging. Addition of titanate nanotubes into the polyimide significantly decreased the viscosity of polyamic acid solution and increased the glass transition temperature of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44641.     

Supercritical carbon dioxide-assisted silanization of multi-walled carbon nanotubes and their effect on the thermo-mechanical properties of epoxy nanocomposites

Supercritical carbon dioxide was employed as the solvent for the functionalization of multi-walled carbon nanotubes (MWCNTs) with an epoxy-capped silane. The silanization protocol was found to be a suitable green alternative to traditional routes that rely on organic solvents for grafting nearly monolayers of silane molecules onto the nanotube surfaces. The addition of silanized MWCNTs to a model epoxy markedly increased its T_g, and measurements of the network cooperativity length scale linked this change to a reduction in polymer segment mobility. Composites filled with low loading levels of both pristine and silanized MWCNTs exhibited significantly higher strain at break and toughness than the neat epoxy, and the greatest improvements were observed at low loading levels. SEM analysis of the composite fracture surfaces revealed that nanotube pullout was the primary failure mechanism in epoxy loaded with pristine MWCNTs while crack bridging predominated in composites containing silanized MWCNTs as the result of strong interfacial bonding with the matrix. The elevated T_g and toughness achieved with small additions of silanized MWCNTs promise to extend the engineering applications of the epoxy resin.     

Interfacial improvement of carbon fiber/epoxy composites using a simple process for depositing commercially functionalized carbon nanotubes on the fibers

An aqueous suspension deposition method was used to coat the sized carbon fibers T700SC and T300B with commercially carboxylic acid-functionalized and hydroxyl-functionalized carbon nanotubes (CNTs). The CNTs on the fiber surfaces were expected to improve the interfacial strength between the fibers and the epoxy. The factors affecting the deposition, especially the fiber sizing, were studied. According to single fiber-composite fragmentation tests, the deposition process results in improved fiber/matrix interfacial adhesion. Using carboxylic acid-functionalized CNTs, the interfacial shear strength was increased 43% for the T700SC composite and 12% for the T300B composite. The relationship between surface functional groups of the CNTs and the interfacial improvement was discussed. The interfacial reinforcing mechanism was explored by analyzing the surface morphology of the carbon fibers, the wettability between the carbon fibers and the epoxy resin, the chemical bonding between the fiber sizing and the CNTs, and fractographic observation of cross-sections of the composites. Results indicate that interfacial friction, chemical bonding and resin toughening are responsible for the interfacial improvement of nanostructured carbon fiber/epoxy composites. The mechanical properties of the CNT-deposited composite laminate were further measured to confirm the effectiveness of this strategy.