Characteristics of nylon 6,6/nylon 6,6 grafted multi-walled carbon nanotube composites fabricated by reactive extrusion

Nylon 6,6 composites containing nylon 6,6 grafted multi-walled carbon nanotubes (nylon 6,6-g-MWCNT) were fabricated from nylon 6,6 and acyl chloride grafted MWCNT (MWCNT–COCl) by reactive extrusion. MWCNT–COCl was produced by reacting acid-treated MWCNTs with thionyl chloride. Formation of nylon 6,6-g-MWCNT by reactive extrusion was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and scanning electron microscopy. To quantify the interfacial adhesion energies of nylon 6,6 and pristine and functionalized MWCNTs, the contact angles of cylindrical drop-on-fiber systems were determined using the generalized droplet shape analysis. The interfacial adhesion energy of the nylon 6,6/nylon 6,6-g-MWCNT composite was twice that of the nylon 6,6/pristine MWCNT composite. Nylon 6,6-g-MWCNTs exhibited excellent dispersion in the composite, whereas pristine MWCNTs exhibited poor dispersion when composite films were prepared by solvent casting. The reinforcement level of the composite increased with increasing MWCNT content. Among the composites examined, the nylon 6,6/nylon-g-MWCNT composite with a fixed MWCNT content exhibited the highest level of reinforcement.     

Polymerization compounding composites of nylon‐6,6/short glass fiber

Nylon‐6,6 was grafted onto the surface of short glass fibers through the sequential reaction of adipoyl chloride and hexamethylenediamine onto the fiber surface. Grafted and unsized short glass fibers (USGF) were used to prepare composites with nylon‐6,6 via melt blending. The glass fibers were found to act as nucleating agents for the nylon‐6,6 matrix. Grafted glass fiber composites have higher crystallization temperatures than USGF composites, indicating that grafted nylon‐6,6 molecules further increase crystallization rate of composites. Grafted glass fiber composites were also found to have higher tensile strength, tensile modulus, dynamic storage modulus, and melt viscosity than USGF composites. Property enhancement is attributed to improved wetting and interactions between the nylon‐6,6 matrix and the modified surface of glass fibers, which is supported by scanning electron microscopy (SEM) analysis. The glass transition (tan δ) temperatures extracted from dynamic mechanical analysis (DMA) are found to be unchanged for USGF, while in the case of grafted glass fiber, tan δ increases with increasing glass fiber contents. Moreover, the peak values (i.e., intensity) of tan δ are slightly lower for grafted glass fiber composites than for USGF composites, further indicating improved interactions between the grafted glass fibers and nylon‐6,6 matrix. The Halpin‐Tsai and modified Kelly‐Tyson models were used to predict the tensile modulus and tensile strength, respectively.     

Adhesion of Polypropylene Fiber to Cement Matrix

Abstract

In this research, the adhesion of polypropylene (PP) fibers to cementitious matrix has been investigated and the chemical bonding and mechanical interlocking between PP fiber and hardened cement paste has been studied. Furthermore, thermodynamic work of adhesion and loss-function (dissipation energy) has been calculated in the PP-cement matrix model system. To investigate the work of adhesion, the pull-out test has been used. Also, the surface free energy and contact angle of the PP monofilaments and cement matrix have been measured using a tensiometer and the fiber–cement interfacial interactions and thermodynamic work of adhesion and loss-function were calculated. Scanning electron microscopy (SEM) analysis was used to study the fiber–cement matrix interfacial transition zone (ITZ). The results showed that the application of theories of polymer–polymer adhesion in fiber–cement matrix systems was feasible. To verify the accuracy of the method, the adhesion of two other fibers (nylon 6,6 and acrylic polymer) was studied.     

Adhesion of Graphite Fibers to Epoxy Matrices: I. The Role of Fiber Surface Treatment

Adhesion between graphite fibers and epoxy matrices is a necessary and sometimes controlling factor in achieving optimum performance. Manufacturers' proprietary fiber surface treatments promote adhesion without providing a basic understanding of the fiber surface properties altered through their use. This study has combined fiber surface chemistry, morphology, interfacial strength measurements and fracture characterization in order to elucidate the role of surface treatments. The results of this investigation lead to the conclusion that surface treatments designed to promote adhesion to epoxy matrix materials operate through a two-part mechanism. First, the treatments remove a weak outer fiber layer initially present on the fiber. Second surface chemical groups are added which increase the interaction with the matrix. Increases in fiber surface area are not an important factor in promoting fiber-matrix adhesion. In some cases the upper limit to fiber-matrix interfacial shear strength is the intrinsic shear strength of the fiber itself.     

Characterization of the surface energies of functionalized multi-walled carbon nanotubes and their interfacial adhesion energies with various polymers

The surface energies of pristine multi-walled carbon nanotubes (MWCNTs) and MWCNTs functionalized with carboxylic acid (MWCNT-COOH), acyl chloride and ethyl amine were characterized, and the effects of the changes in MWCNT surface energies on the interfacial adhesion and reinforcement of the composites were explored. When the surface energy of pristine MWCNTs was compared to that of functionalized MWCNTs, a decrease in the dispersive surface energy and an increase in the polar surface energy were observed. Interfacial adhesion energies between MWCNTs and various polymers were estimated from surface energy values of MWCNTs and various polymers. Among the MWCNTs, polyethylene, polystyrene and bisphenol-A polycarbonate (PC) had the highest interfacial energy with pristine MWCNTs, while nylon 6,6 and polyacrylamine exhibited the highest interfacial energy with MWCNT-COOH. When tensile properties and adhesion at the interface of PC and nylon 6,6 composites containing MWCNTs were examined, composites having high interfacial adhesion energy exhibited greater adhesion at the interface and reinforcement.     

The Effect of Nitric Acid Oxidization Treatment on the Interface of Carbon Fiber-Reinforced Thermoplastic Polystyrene Composite

The quality of interfacial interaction is dictated by the surface chemistry of the carbon fibers and the composition of the matrix. The composition of polystyrene was modified by the addition of maleic anhydride (MAH) grafted polystyrene. The surface properties of the various matrix formulations were characterised by contact angle. Carbon fibers were modified by oxidation in nitric acid. The surface composition of the carbon fibers was characterized. The interaction between modified polystyrene and the carbon fibers was studied by single fiber pull-out tests. The best adhesion behavior was achieved between polystyrene containing grafted MAH and nitric acid oxidation carbon fibers. The addition of MAH-grafted polystyrene to the unmodified polystyrene caused the interfacial shear strength to increase. The apparent interfacial shear strength of this fiber-matrix combination allowed for the utilisation of 100% of the yield tensile strength of polystyrene.     

Debond behavior of copper fibers in thermoset matrices and their effect on fracture toughening

Single fiber pullout experiments were conducted to determine the adhesion quality, debond behavior and subsequent matrix fracture behavior for a variety of end-modified copper fibers. The matrices were: two different epoxy resins, polyester and polyurethane; the end-modified copper fibers were: straight, flat end-impacted, flat end-impacted with release agent applied and straight end-oxidized. The goal was to determine how the bonding and debonding behavior as well as the pullout behavior of the various fiber-matrix combinations affected the composite fracture toughness increment (ΔG). Results indicate that the greatest improvement in the calculated ΔG occurred with a fiber-matrix combination that had a moderate interface bond strength with an interfacial bond failure, minor matrix damage during fiber pullout and moderate post-debond interface friction. Selective oxidation of the fiber end was performed to determine if chemical anchoring of the fiber end could be as effective as mechanical (end-shaping) anchoring of the fiber into the matrix. Improvement in the adhesion bond strength as a result of the chemical anchoring resulted in a significantly lower ΔG compared to the end-impacted fibers because interfacial failure was not possible. This indicates that for the materials tested, mechanical anchoring of the fiber was better than chemical anchoring in improving ΔG. To decrease the adhesion bond strength and allow the fibers to debond, a release agent was applied to the flat end-impacted fiber prior to embedment into the matrix. This resulted in a significantly lower ΔG compared to straight and flat end-impacted fibers for all matrices tested, because the resulting debonding force and friction were significantly reduced. Pullout curves showed that with release agent applied, the end-shape did not effectively anchor the fiber into the matrix. The reduction in the pullout work indicates that the friction at the fiber-matrix interface plays a crucial role in actively anchoring the end-shaped fiber into the matrix after debonding.     

Ionic interphase of glass fiber/polyamide 6,6 composites

Interfacial polymerization to polyamide 6, 6 followed by introduction of ionic groups was performed on the surface of short glass fibers. The ionic interphase-modified fibers were used with poly(ethylene-co-methacrylic acid) (DuPont Surlyn) to prepare composites with specific fiber-matrix interactions. Fiber treatment increased composite tensile and bending properties. An increase in the average fiber length was observed, which was attributed to a decrease in the fiber attrition during mixing. The effect of increasing temperature on the composite mechanical properties was studied. Different behavior was observed before and after the glass transition temperature, T_g, of the matrix. The dynamic mechanical measurements showed an increase in the T_g of the matrix after the treatments, which is attributed to a decrease in chain mobility at the interface resulting from increased interactions of the treated fiber surface with the polymer. Scanning electron microscopy of fractured composites after tensile tests revealed a smooth fiber surface with no polymer at the surface for the untreated composites. Adhered polymer was clearly observed on the surface of treated fibers, indicating better fiber wetting by the matrix. This improved adhesion was attributed to the grafted nylon molecules at the glass fiber surface.     

Nylon/Kevlar composites. I: Mechanical properties

This paper deals with the characterization of the mechanical properties of Kevlar/nylon composites. It has been shown that addition of up to 5 % Kevlar to nylon matrices (nylon-6, nylon- 11, and nylon-6,6) is possible by melt blending, and results in improved mechanical properties as compared to the pure matrix. In order to increase the interfacial adhesion of the fibers and the matrix, various chemical treatments were performed on the fibers: surface hydrolysis, succinyl chloride reactions and suberoyl chloride reactions. These were shown to affect significantly the mechanical properties, and depending on the treatment Of the fiber, improvement or deterioration of the mechanical properties could be observed. The effect of humidity has also been investigated, and it was shown that the addition of Kevlar greatly reduced the susceptibility of the tensile modulus to humidity.     

Compatibilization of nylon 6/liquid crystalline polymer blends with three types of compatibilizers

Polyblends of nylon 6 and liquid crystalline polymer (LCP) (Vectra A 950) are immiscible and highly incompatible, with resultant poor interfacial adhesion, large phase domains, and poor mechanical properties. In the present work, compatibilizing strategies are put forward for blends containing nylon and LCP. Effects of three types of compatibilizers, including ionomer Zn–sulfonated polystyrene (SPS), reactive copolymer styrene–maleic anhydride (SMA), functional grafted copolymers—polypropylene grafted glycidyl methacrylate (PP‐g‐GMA) and polypropylene grafted maleic anhydride (PP‐g‐MAH)—are studied in the aspects of morphology and dynamic mechanical behavior. The addition of compatibilizers decreases the domain size of the dispersed phase and results in improved interfacial adhesion between LCP and matrix. The compatibilization mechanism is discussed by way of diffuse reflectance Fourier transform spectroscopy (DRIFT), showing the reaction between compatibilizers and matrix nylon 6. Mechanical properties are improved by good interfacial adhesion. The contribution of SMA to mechanical properties is more obvious than that of Zn‐SPS and grafted PPs used. The blending procedure is correlated with the improvement of mechanical properties by the addition of compatibilizer. Two‐step blending is demonstrated as an optimum method to obtain composites with better mechanical properties as a result of a greater chance for LCP to contact the compatibilizer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1452–1461, 2003     

Catalytic grafting: A new technique for polymer/fiber composites. II. Plasma treated UHMPE fibers/polyethylene composites

In this paper, the catalytic grafting technique for preparation of polymer/fiber composites is extended to plasma treated ultra-high modulus polyethylene (UHMPE) fiber/high density polyethylene (HDPE) system. The OH groups introduced on the UHMPE fiber surface by oxygen plasma treatment were used to chemically anchor Ziegler-Natta catalyst which then was followed by ethylene polymerization on the fiber surface. The morphology and interfacial behavior, as well as the mechanical properties, of the HDPE composites reinforced by catalytic grafted or ungrafted UHMPE fibers were investigated by SEM, DSC, polarized light optical microscopy, and tensile testing. The experimental results show that the polyethylene grafted on the fibers acted as a transition layer between the reinforcing UHMPE fibers and a commercial HDPE matrix. The interfacial adhesion was also significantly improved. Compared with the composite reinforced by ungrafted UHMPE fibers, the composite reinforced by catalytic grafted UHMPE fibers exhibits much better mechanical properties.     

Correlation between compounding sequence and the properties of glass fiber‐Reinforced nylon‐6,6 composite

The effects of the compounding sequence and addition of maleic anhydride grafted polypropylene (PP‐g‐MAH) as a sizing agent on the properties of glass fiber (GF)/nylon‐6,6 composite were investigated. Mechanical properties of tensile, impact, and flexural strength were measured. The fractured surface was analyzed to compare the variation of interfacial characteristics by different compounding sequences and addition of a sizing agent. It was found that mechanical and rheological properties of a composite are strongly affected by the compounding sequence and the addition of a sizing agent. In general, the addition of PP‐g‐MAH results in lowering the mechanical properties compared to GF/nylon‐6,6, while proper compounding sequence results in improved mechanical properties. Lowering melt viscosity of composites is achieved by addition of sizing agent and varied depending on the compounding sequence. POLYM. ENG. SCI., 59:155–161, 2019. © 2018 Society of Plastics Engineers     

Interfacial adhesion between ionic copolymers and high-modulus surface-treated carbon fibers

High-modulus carbon-fiber-reinforced thermoplastic composites typically fail at the interface due to poor adhesion between fiber and matrix. To increase interfacial strength, the research described herein focuses on modifying the fiber surface (via high-temperature acid treatment or zinc electrolysis) to facilitate chemical functional groups on the fiber that might increase fiber-matrix inter-actions. The thermoplastic matrix materials used in this study were random copolymers of ethylene and methacrylic acid in which the carboxyl groups in the methacrylic acid segments were neutralized with either sodium or zinc counterions. Mechanical tests were performed to determine the macroscopic effects of fiber pretreatment on the ultimate mechanical properties of the composites. Fabrication was designed such that fiber-matrix separation provides the dominant contribution to mechanical gracture. Composites containing fibers treated with nitric acid, or a mixture of nitric and sulfuric acids exhibit a 20 to 25 percent increase in transverse (tensile) fracture stress relative to composites fabricated with as-received fibers. Scanning electron microscopy of the fiber-matrix interface at fracture allows one to “zoom-in” and obtain qualitative details related to adhesion. Fracture surface micrographs of the above-mentioned acid-treated fiber-reinforced composites reveal an increase in the amount of matrix material that adhered to the fiber surface relative to the appearance of the fracture surface of composites fabricated with as-received fibers. The presence of acid functionality in the matrix, rather than the divalent nature of the zinc counterions, produces the largest relative enhancement of transverse (tensile) fracture stress in the above-mentioned composites containing surface-treated carbon fibers.     

Interfacial Characteristics of Sisal Fiber and Polymeric Matrices

Sisal-fiber-reinforced composites, as a class of eco-composites, have attracted much attention from materials scientists and engineers in recent years. In this article, the effects of fiber surface treatment on fiber tensile strength and fiber-matrix interface characteristics were determined by using tensile and single fiber pullout tests, respectively. The short beam shear test was also employed to evaluate the interlaminar shear strength of the composite laminates. Vinyl ester, epoxy, and high-density polyethylene (HDPE) were chosen as matrix materials. To enhance the interfacial strength, two kinds of fiber surface-treatment methods, namely, chemical bonding and oxidisation, were used. The results obtained showed that different fiber surface-treatment methods produced different effects on the tensile strength of the sisal fiber and fiber-matrix interfacial bonding characteristics. Hence, valuable information on the interface design of sisal fiber–polymer matrix composites can be obtained from this study.     

Plasma surface modification of carbon fibers: a review

The properties of the fiber/matrix interface in carbon fiber-reinforced composites play a dominant role in governing the overall performance of the composite materials. Understanding the surface characteristics of carbon fibers is a requirement for optimizing the fiber-matrix interfacial bond and for modifying fiber surfaces properly. Therefore, a variety of techniques for the surface treatment of carbon fibers have been developed to improve fiber-matrix adhesion as well as to enhance the processability and handling of these fibers. Many research groups have studied the effects of plasma treatments, correlating changes in surface chemistry with the interfacial shear strength. This article reviews the recent developments relative to the plasma surface modification of carbon fibers.     

Interfacial Characteristics of Sisal Fiber and Polymeric Matrices

Sisal-fiber-reinforced composites, as a class of eco-composites, have attracted much attention from materials scientists and engineers in recent years. In this article, the effects of fiber surface treatment on fiber tensile strength and fiber-matrix interface characteristics were determined by using tensile and single fiber pullout tests, respectively. The short beam shear test was also employed to evaluate the interlaminar shear strength of the composite laminates. Vinyl ester, epoxy, and high-density polyethylene (HDPE) were chosen as matrix materials. To enhance the interfacial strength, two kinds of fiber surface-treatment methods, namely, chemical bonding and oxidisation, were used. The results obtained showed that different fiber surface-treatment methods produced different effects on the tensile strength of the sisal fiber and fiber-matrix interfacial bonding characteristics. Hence, valuable information on the interface design of sisal fiber-polymer matrix composites can be obtained from this study.     

Mechanical properties and morphology of polypropylene composites. III. Short glass fiber reinforced elastomer modified polypropylene

The impact strength and rigidity of polypropylene composites can be significantly improved by application of short glass fibers instead of mineral fillers in elastomer-modified polypropylene. The properties of such composites are strongly dependent on the adhesive forces at the fiber-matrix interface. Poor adhesion results in interfacial fracture solely by fiber-matrix debonding, as evidenced by scanning electron microscopy on the fracture surfaces. This is accompanied by relatively low impact strengths. By contrast, increased adhesion leads to fracture not only by fiber-matrix debonding, but also by crack propagation through the elastomeric phase at the fiber surface. This mechanism is thought to be responsible for a remarkable increase of the impact strength. Appropriate compositions of polypropylene, glass fiber, and elastomer resulted in composite properties similar to, or even better than, those of a typical acrylonitrile-butadiene-styrene copolymer. The lengths of the fibers recovered from the test specimens were somewhat smaller than the critical fiber lengths as calculated by simple shear lag theory. The properties of the present composites should thus be regarded as minima, rather than as potential maxima. This suggests that current composites may be suitable for engineering applications.     

Evaluation of interfacial adhesion in sheath/core composite fibers

Rayon/nylon sheath/core composite fibers were produced using a wire coating-type process. Fumaric acid (FA) was chosen as an adhesion promoter to pretreat the nylon core fiber before rayon coating to improve the adhesion between skin and core. Different FA pretreatment concentrations and times were used and the effects of the pretreatment conditions on the adhesion were evaluated. A fiber pull adhesion test technique was developed to determine the interfacial shear strength of the composite fibers. The results indicated that the interfacial adhesion in the rayon/nylon composite fibers was significantly improved for specific sets of FA application conditions. Adhesion results were confirmed with electron microscopy. © 1993 John Wiley & Sons, Inc.     

Grafting starch nanocrystals onto the surface of sisal fibers and consequent improvement of interfacial adhesion in sisal reinforced starch composite

Starch nanocrystals (SNCs) were obtained by the hydrolysis of waxy starch and used to improve the interfacial adhesion of a composite of sisal fibers and starch. Sisal fibers were first treated with acrylic acid (AA), and the modified fibers were then reacted with SNCs to form ester groups. The grafted fibers were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The FTIR and XPS results showed that the SNCs were successfully grafted onto the surface of SF-AA, and an ester linkage was formed during the reaction of AA with the SNCs. The SEM analysis showed that the SNCs were distributed over the fiber surface. Tensile tests and pull-out tests were also performed utilizing a two-parameter Weibull distribution analysis to study the effect of the grafted SNCs on the mechanical and interfacial properties. Compared to the untreated fibers, the interfacial shear strength of the grafted SNCs fibers increased by 79.3%. Therefore, the structural similarity between starch and the SNCs contributed towards their compatibility and improved interfacial properties, with the introduction of SNCs being used as an alternative material for fiber surface modification. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47202.     

Effect of moisture absorption on the dynamic mechanical properties of short carbon fiber reinforced nylon 6, 6

A study of hygrothermal aging in terms of the kinetics of moisture absorption by nylon 6,6 and its carbon fiber reinforced composites has been carried out. The single free phase model of absorption has been applied to the kinetic data and thereafter the values of diffusivity have been evaluted. The diffusivity was found to be dependent on the conditioning temperatures and the volume fraction of fibers. Dynamic mechanical properties of unaged and aged samples were studied using a free resonance torsion pendulum which covers a temperature range of 350°C. Incorporation of carbon fibers has led to an increase in structural rigidity of the nylon 6,6 matrix especially at higher temperatures. This was reflected by the sharp increase in the relative shear modulus as the glass transition temperature of nylon 6,6 is appoached. Absorbed moisture was observed to plasticize the polymer matrix and decreased the temperatures of all the transitions. For instance, the α-transition was shifted by almost 95°C. The intensities of the transition peaks of both unaged and aged samples were found to decrease with fiber volume fraction. Increasing the conditioning temperatures has resulted in a reduction of the shear storage modulus and this effect was found to be more pronounced in the reinforced nylon 6,6. This has been attributed to the increase in the extent of degradation at the fiber-matrix interface.