Modified continuous carbon fiber‐reinforced poly(phthalazinone ether sulfone ketone) composites by blending polyetherimide and polyethersulfone

Poly(phthalazinone ether sulfone ketone) (PPESK) is a novel high performance thermoplastic with outstanding high temperature resistance and excellent mechanical properties and therefore, it is a very ideal candidate matrix for advanced composites. However, its high melting viscosity makes the melting process difficult. In this article, two well‐known high performance thermoplastics, polyetherimide (PEI) and polyethersulfone (PES) were introduced to PPESK in order to reduce the melting viscosity of PPESK and to improve the properties of composites. The effect of addition of PEI and PES on the resultant composites was studied. A series of unidirectional composites were made of PPESK and its PEI and PES blends as matrix and continuous carbon fiber (T700) as reinforcement. The solution prepregging method and hot‐press molding method were used in preparation of composites. The effects of polymer blends matrix on mechanical properties, interfacial adhesion, and fracture mode were studied by three points bending, interlaminar shearing, porosity, and scanning electron microscope test. The results show that the mechanical properties and interfacial adhesion increases, and the porosity decrease after blending PEI or PES in the matrix. Addition of PEI and PES to PPESK results in an obvious transition of fracture mode. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Improvement of interfacial properties of carbon fiber‐reinforced poly(phthalazinone ether ketone) composites by introducing carbon nanotube to the interphase

This article aims to improve interfacial properties of carbon fiber‐reinforced poly(phthalazinone ether ketone) (PPEK) composites by means of preparing carbon nanotube (CNT)/carbon fiber hybrid fiber. XPS was used to characterize the chemical structure of unsized carbon fiber and SEM was used to observe the surface topography of carbon fibers. Specific area measurement, dynamic contact angle, and interfacial shear strength (IFSS) testing were performed to examine the effect of CNT on the interfacial properties of carbon fiber/PPEK composites. By the introduction of CNT to the interphase of carbon fiber‐reinforced PPEK composites, an enhancement of IFSS by 55.52% was achieved. Meanwhile, the interfacial fracture topography was also observed and the reinforcing mechanism was discussed. POLYM. COMPOS., 36:26–33, 2015. © 2014 Society of Plastics Engineers     

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     

Influence of oxygen plasma treatment on interfacial properties of poly(p‐phenylene benzobisoxazole) fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite

The influence of oxygen plasma treatment on both surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fibers and interfacial properties of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated. Surface chemical composition, surface roughness, and surface morphologies of PBO fibers were analyzed by X‐ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. Surface free energy of the fibers was characterized by dynamic contact angle analysis (DCAA). The interlaminar shear strength (ILSS) and water absorption of PBO fiber‐reinforced PPESK composite were measured. Fracture mechanisms of the composite were examined by SEM. The results indicated that oxygen plasma treatment significantly improved the interfacial adhesion of PBO fiber‐reinforced PPESK composite by introducing some polar or oxygen‐containing groups to PBO fiber surfaces and by fiber surface roughening. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of functionalized carbon nanotubes/poly(phthalazinone ether sulfone ketone)s composites

Multiwalled carbon nanotubes (MWNT) were successfully functionalized with phthalazinone‐containing diamine (DHPZDA) groups by the amidation reaction. The morphologies and structures of the DHPZDA‐functionalized MWNT (MWNT‐DHPZDA) were characterized by scanning electron microscope, Fourier transform infrared, and Raman spectroscopy, revealing that the DHPZDA were covalently attached onto the surface of MWNT, and the weight gain due to the functionalization was determined by thermogravimetric analysis. The MWNT‐DHPZDA/poly(phthalazinone ether sulfone ketone)s (PPESK) composites with different filler content were prepared by the solution‐mixing method. MWNT‐DHPZDA can be uniformly dispersed in the matrix and the strong interfacial adhesion between two constituents was found, which resulted in obvious enhancements of the mechanical properties. For the composite with 1 wt% MWNT‐DHPZDA, the tensile strength and the Young's modulus are 102.1 and 1,974 MPa, about 1.65 and 1.72 times of the pure PPESK, respectively. Conductivity measurements indicate that a typical percolation transition behavior takes place for MWNT‐DHPZDA content in the range from 0.5 to 2 wt%. Additionally, introducing MWNT‐DHPZDA into PPESK is favorable to improvement of the thermal stability. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Isothermal crystallization and melting behavior of short carbon fiber reinforced poly(ether ether ketone) composites

Films of short carbon fiber reinforced poly(ether ether ketone) (PEEK) composite were formed by compression molding pellets for 10 min at 380 °C under air. A heating stage was used to prepare isothermally treated PEEK composites before DSC scan. The dependence of degree of crystallinity on the heating rate (10–80 °C/min) was investigated for specimens crystallized at different temperatures. The results indicated that 50 °C/min was an optimum heating rate to suppress the reorganization and to avoid the superheating of high crystallinity specimens with the sample weight of 10 mg. The upper peak temperature of double-melting peaks continued to increase with crystallization temperature. This peak temperature was related to the transition from regime II to III. The phenomenon of lower crystallinity and higher melting temperature supports the interpretation that the upper melting peak corresponded to crystals growing during the earlier stage of isothermal crystallization.     

Interfacial contributions in lignocellulosic fiber‐reinforced polyurethane composites

Whereas lignocellulosic fibers have received considerable attention as a reinforcing agent in thermoplastic composites, their applicability to reactive polymer systems remains of considerable interest. The hydroxyl‐rich nature of natural lignocellulosic fibers suggests that they are particularly useful in thermosetting systems such as polyurethanes. To further this concept, urethane composites were prepared using both unused thermomechanical pulp and recycled newsprint fibers. In formulating the materials, the fibers were considered as a pseudo‐reactant, contributing to the network formation. A di‐functional and tri‐functional poly(propylene oxide)‐based polyol were investigated as the synthetic components with a polyol‐miscible isocyanate resin serving as a crosslinking agent. The mechanical properties of the composites were found to depend most strongly on the type of fiber, and specifically the accessibility of hydroxy functionality on the fiber. Dynamic mechanical analysis, swelling behavior, and scanning electron micrographs of failure surfaces all provided evidence of a substantial interphase in the composites that directly impacted performance properties. The functionality of the synthetic polyol further distinguished the behavior of the composite materials. Tri‐functional polyols generally increased strength and stiffness, regardless of fiber type. The data suggest that synthetic polyol functionality and relative accessibility of the internal polymer structure of the fiber wall are dominant factors in determining the extent of interphase development. Considerable opportunity exists to engineer the properties of this material system given the wide range of natural fibers and synthetic polyols available for formulation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 546–555, 2001     

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     

Synthesis and properties of novel poly(phthalazinone ether ketone ketone)

A novel poly(phthalazinone ether ketone ketone) was prepared via the nucleophilic substitution polycondensation of bis-1,4-(4-chlorobenzoyl)benzene and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one. The synthesized polymer exhibited high glass-transition temperature, excellent thermooxidative properties, and fair rheological properties. The polymer was soluble in some polar solvents. Electronic friction and membrane properties are also discussed. The results indicate that the polymer falls in the class of high temperature resistance engineering plastics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 823–826, 2001     

Synthesis and characterization of cross‐linkable poly(phthalazinone ether ketone)s

A novel class of crosslinkable poly(phthalazinone ether ketone)s with relative high molecular‐weight and good solubility were successfully synthesized by the copolymerization of bisphthalazinone containing monomer, 3,3′‐diallyl‐4,4′‐dihydroxybiphenyl and 4,4′‐di‐ fluorobenzophenone. The synthesized polymers with inherent viscosities in the range of 0.42 to 0.75 dL/g can form flexible and transparent membranes by casting from their solution. The crosslinking reaction of these polymers can be carried out by thermally curing of the virgin polymers in or without the presence of crosslinking agent. The experimental results demonstrated that the crosslinking reaction also occurred to some extent during the polymerization. The crosslinked polymers exhibited equivalent glass transition temperature (T_g) at lower crosslinking density, and showed higher T_g than virgin polymers at higher crosslinking density. The crosslinked high‐temperature polymer can be used as the base material for high temperature adhesive, coating, enamel material, and composite matrices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and properties of poly(ether ether ketone) composites reinforced by modified wollastonite grafting with silaneterminated poly(ether ether ketone) oligomers

Silane-terminated poly(ether ether ketone) oligomers were synthesized and grafted onto wollastonite (W) particles. The prepared grafted-wollastonite particles (g-W) were then incorporated into PEEK matrix via melt processing. Properties of the PEEK composites were investigated using differential scanning calorimetry (DSC), universal tester and rheometer. The researchers found the mechanical properties of the PEEK/g-W composites were markedly enhanced, complex viscosity of the PEEK/g-W composites increased, and both the peak crystallization temperature (T _c ) and crystalline fraction (χ _c ) of the PEEK composites with g-W were significant higher compared with those of the PEEK composites with W. It is our belief that these results are due to the strong interaction between the grafted-wollastonite particles and the PEEK matrix.     

Electrical conductivity and microwave absorbing properties of nickel‐coated multiwalled carbon nanotubes/poly(phthalazinone ether sulfone ketone)s composites

Nickel‐coated multiwalled carbon nanotubes (Ni‐MWNT) were prepared by electroless deposition with ultrasonic vibrations. The morphologies and components were characterized by scanning electron microscope and energy dispersive spectroscopy. Two types of fillers, multiwalled carbon nanotubes (MWNT) and Ni‐MWNT, were blended with poly(phthalazinone ether sulfone ketone)s (PPESK) by the solution‐mixing method, respectively. The electrical conductivity and microwave absorbing properties of the composites were investigated. The results show that Ni‐MWNT/PPESK composites have relatively lower electrical resistivity values than MWNT/PPESK, and in both cases the decrease in electrical resistivity indicates a similar percolation transition behavior in the same MWNT content region. Moreover, as MWNT loading is 5 parts per hundred parts of resin (phr), Ni‐MWNT/PPESK composite has the wider frequency region (9.5–13.5 GHz) of the reflection loss (RL) less than ?10 dB and the lower minimum value of RL (?27.5 dB) compared with MWNT/PPESK. The better microwave absorption properties can be attributed to the improved dielectric and magnetic properties of the fillers. A good correlation between electrical conductivity and microwave absorption was found for MWNT/PPESK composites. In addition, tensile test and thermogravimetric analysis indicate that introducing Ni‐MWNT into PPESK is favorable for the improvement of the mechanical properties and high temperature stability of the composites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Montmorillonite‐reinforced sulfonated poly(phthalazinone ether sulfone ketone) nanocomposite proton exchange membranes for direct methanol fuel cells

To produce a composite membrane with high conductivity and low permeability, SPPESK with a degree of sulfonation of 101% was carefully selected for the preparation of montmorillonite (MMT)‐reinforced SPPESK using solution intercalation. The fundamental characteristics such as water uptake, swelling ratio, proton conductivity, methanol permeability, and mechanical properties of the composite membranes were studied. Water uptake is improved when organic MMT (OMMT) loading increase. The composite membranes with CTAB‐MMT loading of 4–0.5% show 0.143–0.150 S cm^?1 proton conductivity at 80°C, which approaches the value of Nafion112. In addition, methanol permeability was decreased to 6.29 × 10^?8 cm² s^?1 by the addition of 6 wt % OMMT. As a result, the SPPESK‐MMT composite membrane is a good candidate for use in direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39852.     

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.     

Properties and crystallization kinetics of poly(ether ether ketone)‐co‐poly(ether ether ketone ketone) block copolymers

A series of block copolymers composed of poly(ether ether ketone) (PEEK) and poly(ether ether ketone ketone) (PEEKK) components were prepared from their corresponding oligomers via a nucleophlilic aromatic substitution reaction. Various properties of the copolymers were investigated with differential scanning calorimetry (DSC) and a tensile testing machine. The results show that the copolymers exhibited no phase separation and that the relationship between the glass‐transition temperature (T_g) and the compositions of the copolymers approximately followed the formula T_g = T_g1X₁ + T_g2X₂, where T_g1 and T_g2 are the glass‐transition‐temperature values of PEEK and PEEKK, respectively, and X₁ and X₂ are the corresponding molar fractions of the PEEK and PEEKK segments in the copolymers, respectively. These copolymers showed good tensile properties. The crystallization kinetics of the copolymers were studied. The Avrami equation was used to describe the isothermal crystallization process. The nonisothermal crystallization was described by modified Avrami analysis by Jeziorny and by a combination of the Avrami and Ozawa equations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1652–1658, 2005     

Preparation and characterization of carbon membranes made from poly(phthalazinone ether sulfone ketone)

Carbon membranes were prepared from a novel polymeric precursor of poly(phthalazinone ether sulfone ketone) (PPESK), of which the changes of microstructure and chemical compositions during pyrolysis from 500 °C to 950 °C were monitored by thermal gravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. It has been found that the weight loss of the PPESK precursor up to 800 °C is about 43.0 wt%. After the heat treatment, the typical chemical structure of the PPESK precursor disappears, at the same time a graphite-like structure with more aromatic rings is formed. The interlayer spacing (i.e., d value) decreases from 0.471 nm to 0.365 nm as the pyrolysis temperature increases. The gas permeation performance of carbon membranes has been tested using pure single gases including H₂, CO₂, O₂ and N₂. For the carbon membrane obtained by carbonizing the PPESK precursor at 800 °C, the maximum ideal permselectivities for H₂/N₂, CO₂/N₂ and O₂/N₂ gas pairs could reach 278.5, 213.8 and 27.5, respectively.     

Preparation and Characterization of high‐strength poly(ether ether ketone) films

High‐strength poly(ether ether ketone) (PEEK) films were prepared through melt extrusion followed by stretching. The tensile strength, orientation, and crystallization behaviors of PEEK films were characterized by universal testing machine, thermomechanical analysis, wide‐angle X‐ray diffraction, and differential scanning calorimetry. The results indicated that the tensile strength of PEEK films mainly depended on the stretching rate (ν), stretching temperature (T), and stretching ratio (λ_L). Moreover, the tensile strength of the stretched PEEK film (333 MPa) was almost four times higher than that of the unstretched PEEK film (87 MPa) under an optimized condition. This is attributed to a synergistic effect of orientation and crystallization in the stretching process, and the influence of orientation is stronger than that of the crystallization on the improvement of the tensile strength of PEEK films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40172.     

Chemical resistance of carbon fiber-reinforced poly(ether ether ketone) and poly(phenylene sulfide) composites

Studies have been conducted to investigate the aircraft fluid and chemical solvent resistance of the carbon fiber-reinforced poly(phenylene sulfide) (PPS) and poly(ether ether ketone) (PEEK) composites. The solvents and aircraft fluids utilized in this work include hydraulic fluid, paint stripper, JP-4 jet fuel, methyl ethyl ketone, and methylene chloride. The weight gain of the composites as a function of time is measured. Tensile and flexural strength, thermal behavior, and dynamic mechanical properties of the composites are examined. The alteration of crystallinity change of the composites is investigated by X-ray diffraction. It is found that paint stripper degraded the mechanical properties of the composites significantly. Furthermore, crystallization enhancement of the low crystallinity composites in the presence of solvents and aircraft fluids is also observed.     

Wear behavior of carbon fiber‐reinforced poly(phenylene sulfide)

On a pin‐on‐disc test rig, online measurements of the wear and friction of steel sliding against carbon fiber‐reinforced polyphenylene sulfide were done. Instead of the standard set‐up, a rotating composite disc and steel pin are used. The frictional behavior of this material pair results in a friction coefficient of 0.33, while a carbide film is formed in the wear track. This results in the lowering of the frictional behavior. The wear rate is rather low, but when the wear track is covered with a carbide film, suddenly the wear rate raises. This is not due to the wear of the composite material but only as a result of the start of terrible wear of the steel counter face. Moreover, the wear of the pin is strongly related to the wear track. The pin is flattened at the sides of the formed wear track, but in contact with the carbide film there is less wear, resulting in a pin with two flat sides, making contact with the original surface, and a rig in the middle of the pin following the roundness of the wear track. The frictional behavior is strongly dependent on the weft‐warp direction. POLYM. COMPOS., 27:92–98, 2006. © 2005 Society of Plastics Engineers     

Preparation and gas permeation of composite carbon membranes from poly(phthalazinone ether sulfone ketone)

Composite carbon membranes were prepared from poly(phthalazinone ether sulfone ketone) (PPESK) by incorporating with polyvinylpyrrolidone (PVP) or zeolite (ZSM-5) through stabilization and pyrolysis processes. The thermal stability of composite polymeric membranes was measured by thermal gravimetric analysis. The resultant composite carbon membranes were characterized by scanning electron microscopy, X-ray diffraction and gas permeation technique, respectively. The results illustrated that the thermal stability of composite polymeric membranes was enhanced by addition of ZSM-5 or reduced by PVP. For ZSM-5 or PVP composite carbon membranes prepared at 650 °C, the O₂ permeability is 199.70 Barrer or 124.89 Barrer, and the O₂/N₂ selectivity is 10.3 or 4.2, respectively. Compared with carbon membranes from pure PPESK, the O₂ permeability of ZSM-5 or PVP composite carbon membranes increases by 18.5 or 11.6 times, together with the O₂/N₂ selectivity decreasing by 35.2% or 73.6%, respectively. The gas separation mechanism of composite carbon membranes is molecular sieving. Adsorption effect also plays a significant role for CO₂ permeating through ZSM-5 composite carbon membranes.