Influence of new thermoplastic sizing agents on the mechanical behavior of poly(ether ketone ketone)/carbon fiber composites

In this study, unidirectional poly(ether ether ketone)/carbon fiber (CF) composite sheets were elaborated with unsized, epoxy‐sized, and thermoplastic‐sized CFs by hot‐press molding. The thermoplastic sizings that we used were poly(ether imide) (PEI) and poly(ether ketone ketone) oligomer aqueous dispersions. Scanning electron microscopy observation of the composites freeze fractures showed that unlike unsized or epoxy‐sized CFs, the thermoplastic sizings improved the interaction between the fibers and the matrix. A comparative study of the mechanical relaxations by dynamic mechanical analysis was carried out on the different composites before and after immersion in kerosene. At low temperature, the PEI sizing had a significant influence on the β relaxation, particularly after kerosene immersion. The thermoplastic sizings did not modify the glass‐transition temperature but improved the kerosene resistance on the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42550.     

Interfacial shear strength in carbon fiber‐reinforced poly(phthalazinone ether ketone) composites

We studied interfacial shear strength (IFSS) in carbon fiber (CF)‐reinforced poly (phthalazinone ether ketone) (PPEK) composites system, with emphasis on the influence of forming temperature of composite and sizing agent on CFs. To obtain apparent IFSS of CF‐reinforced PPEK composites shaped at various forming temperatures ranged from 20 up to 370°C, microbond test was carried out at single‐fiber composites. Results of microbond test showed that apparent IFSS was directly proportional to the difference between the matrix solidification temperature (forming temperature) and the test temperature and approximately 80% of the apparent IFSS in CF/PPEK composite system was attributed to residual radial compressive stress at the fiber/matrix interface. By sizing CF with sizing agent, the wettability of the fiber by the matrix was improved and the final apparent IFSS was also improved. POLYM. COMPOS., 34:1921–1926, 2013. © 2013 Society of Plastics Engineers     

Improved interfacial adhesion in carbon fiber/poly (ether ether ketone) composites with the sulfonated poly (ether ether ketone) sizing treatment

A water-soluble sulfonated poly (ether ether ketone) (SPEEK) sizing agent is prepared and applied to improve the interfacial adhesion of carbon fiber/poly (ether ether ketone) (CF/PEEK) composites. The surface morphology, surface roughness, surface chemistries, and surface free energy of SPEEK sized CF are obtained to understand the sizing effect. The results reveal the increased surface free energy and surface roughness of SPEEK sized CF. In addition, a chemical reaction between the CF surface and sizing layer is proved based on the results of XPS, IR, and ¹H NMR. The interfacial structure of CF/PEEK composites is further ascertained by AFM and the appearance of gradient interface could be verified for SPEEK sized CF/PEEK composites. The formation of the gradient interface is due to the chemical reaction between the CF and sizing agent as well as the improved compatibility between the sized CF and matrix, which benefits the improvement of interfacial adhesion.     

Effects of sizing materials on the properties of carbon fiber‐reinforced polyamide 6,6 composites

This article aims to study the effect of the sizing materials type on the mechanical, thermal, and morphological properties of carbon fiber (CF)‐reinforced polyamide 6,6 (PA 6,6) composites. For this purpose, unsized CF and sized CFs were used. Thermogravimetric analysis was performed, and it has been found that certain amounts of polyurethane (PU) and PA sizing agents decompose during processing. The effects of sizing agent type on the mechanical and thermomechanical properties of all the composites were investigated using tensile, Izod impact strength test, and dynamic mechanical analysis. Tensile strength values of sized CF‐reinforced composites were higher than that of unsized CF‐reinforced composites. PA and polyurethane sized CF‐reinforced composites exhibited the highest impact strength values among the other sized CF‐reinforced composites. PU and PA sized CF‐reinforced composites denoted higher storage modulus and better interfacial adhesion values among the other sizing materials. Scanning electron microscope studies indicated that CFs which were sized with PU and PA have better interfacial bonding with PA 6,6 matrix among the sized CFs. All the results confirmed that PA and PU were suitable for CF's sizing materials to be used for PA 6,6 matrix. POLYM. COMPOS., 34:1583–1590, 2013. © 2013 Society of Plastics Engineers     

Properties of carbon fiber sized with poly(phthalazinone ether ketone) resin

We studied thermoplastic poly(phthalazinone ether ketone) (PPEK) resin as a sizing agent on carbon fiber, with emphasis on its thermal stability, surface energy, wetting performance, and interfacial shear strength (IFSS). X‐ray photoelectron spectroscopy characterization was carried out to study the chemical structure of sized/unsized carbon fibers. Scanning electron microscopy and atomic force microscopy were used to characterize surface topography. TGA was used to analyze the thermal stability. Meanwhile, contact angle measurement was applied to analyze the compatibility between the carbon fibers and PPEK and the surface energy of carbon fibers. IFSS of carbon fiber/PPEK composite was examined by microbond testing. It is found that carbon fibers uniformly coated with PPEK resin had better thermal stability and compatibility with PPEK resin than the uncoated fiber. The contact angle is 57.01° for sized fibers, corresponding to a surface energy of 49.96 mJ m^?2, much smaller than that for unsized ones with contact angle value of 97.05°. The value of IFSS for sized fibers is 51.49 MPa, which is higher than the unsized fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties of carbon nanotube/carbon fiber reinforced thermoplastic polymer composite

Carbon nanotube (CNT)/carbon fiber (CF) hybrid fiber was fabricated by sizing unsized CF tow with a sizing agent containing CNT. The hybrid fiber was used to reinforce a thermoplastic polymer to prepare multiscale composite. The mechanical properties of the multiscale composite were characterized. Compared with the base composite (traditional commercial CF), the multiscale composite reinforced by the CNT/CF hybrid fiber shows increases in interlaminar shear strength (ILSS) and impact toughness. Laminate containing CNTs showed a 115.4% increase in ILSS and 27.0% increase in impact toughness. The reinforcing mechanism was also discussed by observing the impact fracture morphology. POLYM. COMPOS., 38:2001–2008, 2017. © 2015 Society of Plastics Engineers     

Influence of carbon fiber surface treatments on the structure and properties of conductive carbon fiber/polyethylene films

Effects of carbon fiber (CF) surface modification on the crystalline structure and both electrical and mechanical properties of conductive CF/high‐density polyethylene (HDPE) films were studied. Three different types of surface‐treated CF, epoxy‐sized, unsized, and sized but thermally treated, were considered. It was found that the uniformity of the transcrystalline zone around CF and the overall crystallinity of the polyethylene matrix decreased when epoxy‐sized CF was used. Epoxy‐sized CF caused a significant reduction not only in electrical resistivity and temperature coefficient of resistivity (TCR) but also tensile strength and coefficient of linear thermal expansion (CLTE) of composite films compared with that of unsized or sized CF that was thermally treated. We observed the systematic changes of TCR and CLTE values in accordance with CF surface modification and CF content in composite films. It was concluded that thermal expansion of the polymer matrix is the main reason for the positive TCR of CF/HDPE films. As the most probable reasons for decreased resistivity and strength of the CF/HDPE films with epoxy‐sized CF, the diffusion of epoxy sizing agent into the polyethylene matrix and the formation of loosened semiconductive interphase structure in the film are considered. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2040–2048, 2002; DOI 10.1002/app.10500     

Morphology and dynamical mechanical properties of poly ether ketone ketone (PEKK) with meta phenyl links

Poly ether ketone ketone (PEKK) with different proportion of meta phenyl links were investigated by combining differential scanning calorimetry and dynamic mechanical analysis. The influence of the Terephthalyl/Isophthalyl isomers (T/I) ratio on the vitreous phase is mild, the shift of the glass transition is limited to a few degrees and the vitreous G′ is only sensitive to the content of the crystalline phase. Contrarily, the increase of meta isomers is responsible for a significant decrease of the melting temperature (T_m) by 60 °C, which considerably facilitates processing. The modification of interchain interactions in the crystalline phase might be implied. A series of thermal protocols evidenced that the difference of crystallization behavior is also dependent upon the T/I isomer ratio. A time and temperature dependence of annealing on the double melting behavior of PEKK was observed. Regarding the mechanical behavior, the observed reinforcing effect due to the crystalline phase was more prominent in the rubbery state than in the glassy state. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43396.     

Effect of polyurethane sizing on carbon fibers surface and interfacial adhesion of fiber/polyamide 6 composites

Commercial epoxy sized carbon fibers (CFs) or unsized CFs have poor interfacial adhesion with polyamide 6 (PA6). Here, CFs are coated with polyurethane (PU) and their surface properties in terms of surface chemistry, contact angle, roughness, and morphology, are investigated. The results of Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy demonstrate PU sizing evidently increases the quantity of polar functional groups on the CFs surface. The surface energy of the PU sized fiber is calculated according to the Owens–Wendt method. Compared with unsized fibers, the contact angle of PU sized fibers is decreased while their total surface energy is increased, indicating superior wettability. Moreover, transverse fiber bundle tests are performed to determine the interfacial adhesion between the CFs and PA6 matrix. The transverse fiber bundle strength of unsized CF is measured to be 12.57 MPa. For PU sized CFs processed with sizing concentration of 1.2%, this value is increased to 24.35 MPa, showing an increase of more than 90%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46111.     

Improvement of interfacial interactions in CF/PEEK composites by an s-PSF/graphene oxide compound sizing agent

The interfacial interactions of carbon fiber (CF)-reinforced polymer composites is a key factor affecting the overall performance of the material. In this work, we prepared a sulfonated poly(ether sulfone)–graphene oxide mixed sizing agent to modify the interface of CF/PEEK composites and improve the interfacial properties between the PEEK matrix and CF. Results showed that the mechanical and interfacial properties of CF/PEEK composites are improved by the sizing agent. Specifically, the flexural strength, flexural modulus and interlaminar shear strength of the materials reached 847.29 MPa, 63.77 GPa, and 73.17 MPa, respectively. Scanning electron microscopy confirmed markedly improved adhesion between the resin matrix and fibers. This work provides a simple and effective method for the preparation of high-performance CF/PEEK composites, which can improve the performance of composites without degrading the mechanical property of pristine CF.     

Enhancing resistance of poly(ether ketone ketone) to high-temperature steam through crosslinking and crystallization control

Poly(aryl ether ketone)s (PAEKs) are promising materials for harsh environments, such as in high-temperature steam applications. Here, the effect of high-temperature steam on the crystallinity and mechanical properties of existing poly(ether ether ketone) (PEEK) and PEKK(T/I) polymers is investigated. Differential scanning calorimetry (DSC), wide-angle X-ray scattering or diffraction (WAXD), and dynamic mechanical analysis experiments show these materials undergo significant crystallization and reorganization after prolonged exposure to steam and suffer from embrittlement. In addition, we show that xanthydrol-based crosslinks can provide the dimensional stability and stabilize the PEKK crystal structure. Mechanical tests demonstrate that the ductility is preserved for longer exposures to steam compared to neat PEKK, whereas DSC and WAXD data indicate xanthydrol crosslinks effectively stabilize the crystal structure against steam-assisted crystallization. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47727.     

High Porosity Poly(ether ketone ketone): Influence of Solvents on Foam Properties

Poly(ether ketone ketone) (PEKK) is a semicrystalline high-performance polymer with exceptional mechanical properties, high continuous operation temperature, and is insoluble in most common solvents. Porous PEKK, desired for biomedical applications, is produced by a high-temperature thermally induced phase separation process using PEKK solutions in two high boiling aprotic solvents, 4-phenylphenol and 9-fluorenone, with concentrations up to 20 wt.%. It is demonstrated that the solvent choice has a pronounced influence on the phase separation behavior, which determines the foam morphology, physical and mechanical properties of PEKK foams. Porous PEKK with porosities ranging from 70% to 90%, specific surface areas up to 194 m² g⁻¹ and elastic moduli ranging from 35 to 100 MPa are produced.     

Interfacial stress transfer in nylon‐6/E‐Glass microcomposites: Effect of temperature and strain rate

In this study, the interfacial properties between E‐glass fibers with different commercial sizings have been investigated on model composites with a nylon‐6 matrix. In particular, the fiber critical length was measured by means of the single‐fiber fragmentation test over a wide range of temperatures (from 25 to 175°C) and strain rates (from 0.0008 to 4 min⁻¹). The general trend observed is that the fiber critical aspect ratio increases as the temperature increases and it decreases as strain rate is increased. The fiber critical aspect ratio for unsized fibers resulted to be reasonably well linearly related to the square root of the fiber to matrix modulus ratio. This results is in accordance with the Cox's shear‐lag theoretical model and the Termonia's numerical simulations. Sized fibers display an higher deviation from the theoretical prevision probably because of the presence of interphases whose properties are different from the bulk matrix. As a consequence, the interfacial shear strength values resulted to be dependent on the fiber sizing. In particular, the fibers coated with an epoxy sizing showed a superior thermal stability of the fiber matrix‐interface with respect to the unsized or nylon compatible sized fibers.     

Synthesis and properties of copolymers of poly(ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

Poly(aryl ether ketone)s (PAEKs) are a class of high‐performance engineering thermoplastics known for their excellent combination of chemical, physical and mechanical properties, and the synthesis of semicrystalline PAEKs with increased glass transition temperatures (T_g) is of much interest. In the work reported, a series of novel copolymers of poly(ether ketone ketone) (PEKK) and poly(ether amide ether amide ether ketone ketone) were synthesized by electrophilic solution polycondensation of terephthaloyl chloride with a mixture of diphenyl ether and N,N′‐bis(4‐phenoxybenzoyl)‐4,4′‐diaminodiphenyl ether (BPBDAE) under mild conditions. The copolymers obtained were characterized using various physicochemical techniques. The copolymers with 10–35 mol% BPBDAE are semicrystalline and have markedly increased T_g over commercially available poly(ether ether ketone) and PEKK due to the incorporation of amide linkages in the main chain. The copolymers with 30–35 mol% BPBDAE not only have high T_g of 178–186 °C, but also moderate melting temperatures of 335–339 °C, having good potential for melt processing. The copolymers with 30–35 mol% BPBDAE have tensile strengths of 102.4–103.8 MPa, Young's moduli of 2.33–2.45 GPa and elongations at break of 11.7–13.2%, and exhibit high thermal stability and good resistance to organic solvents. Copyright © 2010 Society of Chemical Industry     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

Interfacial properties in commingled yarn thermoplastic composites. Part I: Characterization of the fiber/matrix adhesion

The paper aims to assess the fiber/matrix interface and adhesion quality in commingled GF/PP composites by means of complementary experimental methods. For this purpose, different interfacial qualities were obtained by a modification of the sizing of the fiber reinforcement (polypropylene specific sizing, non-specific sizing and no sizing), and of the matrix (with or without coupling agent). Transverse tensile stress-strain curves have been recorded while monitoring acoustic emissions. An analysis of acoustic emission data associated with fracture surface examinations has helped explain the differences observed in mechanical properties and damage mechanisms, emphasizing the importance of the interphase in the performance of these new composites. Thus it has been shown that the association of three experimental investigation methods (transverse tension, acoustic emission, and fracture surface analysis) makes it possible to characterize both the glass/silane bond (so-called fiber/matrix interface) and the global fiber/matrix adhesion (addition of several different zones and interfaces). Polym. Compos. 25:577–588, 2004. © 2004 Society of Plastics Engineers.     

The influence of processing conditions on the mechanical properties of poly(aryl-ether-ketone)/polybenzimidazole blends

Interest in developing high-performance blends for niche applications has grown significantly in efforts to meet ever-increasing harsh environment demands. In this work, four model poly(aryl-ether-ketone)/polybenzimidazole (PAEK/PBI) blends were chosen to study the influence of premixing methods, processing, and matrix polymers, on their mechanical properties. Among the model poly(ether ether ketone) (PEEK) and PBI blends, mechanical properties are greatly enhanced by melt premixing. The molding process mainly affects the matrix crystallinity, which in turn greatly influences fracture toughness of the blend. Poly(ether ketone ketone) (PEKK) and PBI blend exhibits a slightly lower tensile strength and fracture toughness than PEEK/PBI due to the differences in inherent properties of PEEK and PEKK matrices and their interfacial interaction with PBI. The processing−structure–property relationship of PAEK/PBI blends is established to help guide optimal design of high-performance polymer blends for structural applications. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48966.     

Thermal conductivity and diffusivity of carbon-reinforced polyetherketoneketone composites

Heat transfer properties play an important role in processing of polyetherketoneketone (PEKK)/carbon fiber (CF) composites. Accordingly, thermal conductivity and diffusivity of PEKK, PEKK/glassy carbon (GC), and PEKK/CF composites have been studied. Observed increase in conductivity and diffusivity with carbon filler addition was analyzed using the Maxwell–Eucken model. PEKK/GC composites with low carbon fraction indicated good fitting experimental points of the model, indicating good dispersion of particles. For PEKK/CF composites, the thermal conductivity and diffusivity increase is a reflection of a decrease in porosity. Results as observed from the model points to a homogenous dispersion within the PEKK/CF composites as well. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47975.     

Morphologies,Mechanical Properties and Wear of Poly(ether ketone ketone) (PEKK) and its Composites Reinforced with Mica

Poly(ether ketone ketone) (PEKK) composites were developed using mica as a filler. Sulfonated poly(ether ketone ketone) (S‐PEKK), a possible interfacial modifier, was coated on the mica surface with ca. 50 nm thickness, as observed by contact atomic force microscope (AFM). The morphologies of these materials were examined by scanning electron microscopy (SEM). In comparison with PEKK, significantly improved mechanical properties were obtained for the composite materials. With increasing content of mica in the materials, tensile modulus of the materials increased and ultimate elongation decreased. The composites containing 30 wt.‐% of mica exhibited a maximum tensile strength of about 200 MPa while pure PEKK showed a tensile strength of 102 MPa. The composites filled with mica treated by S‐PEKK displayed somewhat higher values of tensile strength and ultimate elongation than those generated using pure mica. The glass transition behavior and thermal stability of PEKK were not affected by the composition of the materials. The amount of mica used in the composites showed some influence on the coefficient of friction and wearing rate of these materials.     

Mechanical properties,electrical resistivity and piezoresistivity of carbon fibre-based self-sensing cementitious composites

Carbon fibre (CF) is one of the most effective materials in improving the conductivity of the composites by developing a conductive network within the matrix, which also enhanced the piezoresistivity behaviour of the cementitious composites and has a potential application for structural health monitoring. A systematic study of the effect of sizing condition and fibre length on the piezoresistivity behaviour of cementitious composites by adopting unsized CF with the length of 3, 6 and 12 mm, and desized CF of 6 and 12 mm as functional fillers. Each type of CF was added at four different weight fractions of 0.1, 0.3, 0.5 and 0.7% to determine the optimal fibre content. Electrical resistivity and piezoresistivity tests were conducted for samples before and after drying treatment to evaluate the effect of water content on electrical properties. Besides, fresh properties of the fresh mixture, mechanical properties and microstructure of the composites were also investigated. Results showed that unsized CF is more effective in enhancing composites flexural strength and reducing the electrical resistivity, which also showed a stronger bonding with the cement matrix and also demonstrated a better dispersive ability. In terms of piezoresistivity behaviour, for a given fibre length, desized CF showed higher sensitivity and repeatability compared to unsized CF; however, the signals showed more noise. The best piezoresistivity behaviour was obtained for composites containing 3 mm CF at 0.7 wt%, which showed a fractional change in resistivity (FCR) value of approximately 70%. An equation was developed, which can successfully describe the relationship between the FCR of cementitious composites containing CF and the applied external stress.