Hydroxyl terminated PEEK-toughened epoxy–amino novolac phthalonitrile blends – Synthesis,cure studies and adhesive properties

Self cure promoting, amine-containing novolac–phthalonitrile (APN) resins of varying compositions were synthesized and characterized. APN possessing amine functionalities reduced the cure initiation temperature from 310 °C (typical of pure phthalonitrile systems) to 180 °C. It showed excellent thermal stability up to 420 °C and high char residue of 77–79 %. Co-reaction of APN with diglicydyl ether of bisphenol A (DGEBA) led to a decrement in their thermal stability though improved their adhesive properties. Evidences were obtained for epoxy–amine, epoxy–phthalonitrile and amine–phthalonitrile reactions. The latter reactions led to formation of oxazoline, triazine and phthalocyanine groups in the network. These were rationalized by density functional theory studies on model compounds. The extents of epoxy–amine and epoxy–phthaonitrile reactions were quantified. Introduction of hydroxyl terminated poly ether ether ketone (PEEK) reduced the brittleness of the blends and improved their lap shear strength. Toughening of epoxy–amino novolac phthalonitrile networks occurred through phase separation of PEEK segments in cured matrix.     

Toughening of Diglycidyl Ether of Bisphenol-A Epoxy Resin Using Poly (Ether Ether Ketone) with Pendent Ditert-Butyl Groups

Poly(ether ether ketone) (PEEKDT), hydroxyl terminated poly(ether ether ketone) (PEEKDTOH) and fluorine terminated poly (ether ether ketone) (PEEKDTF) with pendent ditert-butyl groups were synthesized by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with 2,5-ditert-butylhydroquinone in N-methyl-2-pyrrolidone medium using anhydrous potassium carbonate as catalyst. Diglycidyl ether of bisphenol-A epoxy resin was blended with PEEKDT, PEEKDTOH, and PEEKDTF, and cured with 4,4′-diaminodiphenylsulfone (DDS). The polymers formed heterogeneous blends before curing, and upon curing the polymers got dispersed in the epoxy matrix. The mechanical properties of the cured blends were slightly lower than that of the unmodified resin. The fracture toughness increased with the addition of ditert-butyl PEEK into epoxy resin and the extent of improvement was dependent on the type of modifier used. Hydroxyl terminated polymers gave up to 40% increase in fracture toughness. The dynamic mechanical spectrum of the blends showed only a single T_g due to the proximity of the glass transition temperature of modified PEEK and DDS cured epoxy resin.     

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.     

Phenol‐containing phthalonitrile polymers – synthesis,cure characteristics and laminate properties

Novolac–phthalonitrile polymers bearing a controlled concentration of phthalonitrile groups were synthesized by condensation of novolac with 4‐nitrophthalonitrile. The cure characteristics monitored by DSC and rheometry indicated acceleration of the cure reaction by the phenolic groups. Fourier transform infrared analysis of the cured products indicated that the cure mechanism was dependent on the extent of phthalonitrile substitution. In phenol‐rich systems, evidence was obtained for the phenol‐mediated reaction of nitrile groups resulting in the formation of isoindoline groups. The phthalonitrile‐rich system underwent crosslinking through formation of triazine and phthalocyanine groups. The phenol groups in the phthalonitrile backbone were conducive to building a stronger interphase in their carbon composites, resulting in better mechanical properties. This was corroborated by morphological studies by SEM. However, these groups were detrimental to the thermal stability of the cured resins. The polymers exhibited very high flame retardancy which improved further on increasing the degree of phthalonitrilation. Copyright © 2012 Society of Chemical Industry     

Poly(ether ether ketone)/wrapped graphite nanosheets with poly(ether sulfone) composites: Preparation,mechanical properties,and tribological behavior

Antiwear composites with extraordinary tribological performances and good mechanical/thermal properties were developed by the dispersion of poly(ether sulfone) (PES) wrapped graphite nanosheets (GNSs) inside a poly(ether ether ketone) (PEEK) matrix via melt blending. The tribological behaviors and the mechanical/thermal properties of the composites were carefully investigated. Compared with pure PEEK and PEEK/GNS composites, the PEEK/wrapped GNS composites exhibited considerable enhancements in those performances; these were attributed to the eliminated layer of PES; this elimination not only eliminated the GNS aggregation inside the PEEK matrix for homogeneous distribution inside the PEEK matrix but also enhanced the interfacial adhesion between the PEEK and wrapped GNSs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41728.     

Thermal Aging Properties of Graphite Fiber Reinforced Peek and Graphite Fiber Reinforced Bmi Composites

Graphite fiber reinforced poly(ether ether ketone) (PEEK) and graphite fiber reinforced bismaleimide (BMI) composite materials are two kinds of advanced fiber-reinforced polymer matrix composites with good thermal stability and excellent mechanical properties at high temperature. They are currently receiving considerable attention. the main limitation on their application is the lack of knowledge regarding their behaviors during extended use at high temperature. Thermal aging properties are the main parameters for new polymer matrix composites that will be used in advanced spacecraft structural components. From the results of thermal aging effects on the properties—including interlaminar shear strength, drop-weight impact strength, and impact energy—of graphite/PEEK and graphite/BMI composites, it is found that unidirectional graphite fiber reinforced composites retain higher strength compared to multidirectional, and that multidirectional graphite/PEEK composites keep higher property retentions than multidirectional graphite/BMI composites after thermal aging at 190°C. From scanning electron photomicrographs, it is also found that graphite/PEEK composites have better fiber/resin adhesion, intraply adhesion, and microcrack resistance compared to graphite/BMI composites after thermal aging.     

Phthalonitrile‐epoxy blends: Cure behavior and copolymer properties

Binary blends composed of 4,4′‐bis(3,4‐dicyanophenoxy)biphenyl (biphenyl PN) and diglycidyl ether of bisphenol A (epoxy resin) and oligomeric n = 4 phthalonitrile (n = 4 PN) and epoxy resin were prepared. The cure behavior of the blends was studied under dynamic and isothermal curing conditions using differential scanning calorimetry, simultaneous thermogravimetric/differential thermal analysis, infrared spectroscopy, and rheological analysis. The studies revealed that phthalonitrile‐epoxy blends exhibited good processability and that they copolymerized with or without the addition of curing additive. In the absence of curing additive, the blends required higher temperatures and longer cure times. The thermal and dynamic viscoelastic properties of amine‐cured phthalonitrile‐epoxy copolymers were examined and compared with those of the neat epoxy resin. The properties of the epoxy resin improved with increasing biphenyl PN content and with n = 4 PN addition. Specifically, the copolymers exhibited higher glass transition temperatures, increased thermal and thermo‐oxidative stabililty, and enhanced dynamic mechanical properties relative to the commercially available epoxy resin. The results showed that the phthalonitrile‐epoxy blends and copolymers have an attractive combination of processability and high temperature properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties of poly(ether ether ketone)/poly(ether ketone) blends: Use of simple models relating normalized tensile parameters

In this study, mechanical properties such as tensile properties, flexural properties, and Izod impact strength of poly(ether ether ketone) (PEEK) and poly(ether ketone) (PEK) blends at PEK concentration from 0 to 0.42 volume fraction were studied. The blends of PEEK and PEK of different compositions were prepared by extrusion in a single‐screw extruder. With increase in the PEK concentrations, the tensile strength, flexural strength, and modulus increased whereas the tensile modulus and the impact strength decreased. Homogeneous dispersion and adhesion of PEK in PEEK was shown by the morphological studies. Crystallinity of blends influenced the tensile modulus and the impact strength. Using simple models to relate normalized tensile parameters where the data were divided by the crystallinity of the blends and of the PEEK matrix, respectively, supported the experimental results. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(ether ether ketone)/poly(aryl ether sulfone) blends: Relationships between morphology and mechanical properties

Mechanical properties such as the tensile modulus, yield (break) strength, and elongation to break (or yield) are measured for multiphase poly(ether ether ketone) (PEEK)/poly(aryl ether sulfone) (PES) blends. Specimens with three different levels of thermal histories (quenched, as‐molded, and annealed) are prepared in order to study their effects on the mechanical properties of PEEK/PES blends. Synergistic behavior is observed in the tensile modulus and tensile strength of the blends in almost the whole range of compositions. The ductility of quenched blends measured as the elongation to break (yield) shows an unexpected synergistic behavior in the blend containing 90 wt % PEEK, although a negative deviation from additive behavior is observed in the rest of the compositions. A ductile–brittle transition is observed between 50 and 75 wt % PEEK in the blend. The ductile–brittle transition in as‐molded blends shifts to 75–90 wt % PEEK. Annealed blends show predominantly brittle behavior in the whole composition range. The experimental data are further correlated with the theoretically predicted results based on various composite models. Although the prediction based on these equations fails to fit the experimental data in the whole composition range, the simplex equations that are normally used for blends showing synergistic behavior produced a reasonable fit to the experimental data. The mechanical properties obtained for different blend compositions are further correlated with their morphology as observed by scanning electron microscopy. Morphological observation shows a two‐phase morphology in PES‐rich blends, which is an interlocked morphology in which the disperse phase is not clearly visible in PEEK‐rich blends, and a cocontinuous type of morphology for a 50/50 composition. Considerable permanent deformation of both the disperse and matrix phase, especially in the case of quenched tensile specimens, demonstrates the remarkable adhesion present between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2887–2905, 2003     

Mechanical and Thermal Properties of Poly(phthalazinone biphenyl ether sulfone)/PEEK Blends

A series of blends with various compositions are prepared by melt extrusion on the basis of novel copoly(phthalazinone biphenyl ether sulfone) (PPBES) and poly(ether ether ketone) (PEEK). The melt flowability, mechanical and thermal properties of the blends are studied. The results show that the incorporated PEEK has a large influence on the melt viscosity and thermal stability of blends. The tensile strength of the blends remains at about 90 MPa at room temperature; PPBES improves the mechanical properties of PEEK at 150°C. The flexural strength and modulus of the PPBES/PEEK blends also increase with the addition of PEEK.     

Effect of the addition of silane coupling agents on the properties of wollastonite‐reinforced poly(ether ether ketone) composites

The wollastonite was grafted with different silane coupling agents, which could improve interface adhesion. Wollastonite and modified wollastonite‐reinforced poly(ether ether ketone) (PEEK) composites were prepared by melt blending. The mechanical properties, rheology behavior, and thermal properties of the composites were investigated. The modified wollastonite‐reinforced PEEK composites exhibited better mechanical properties than the unmodified wollastonite‐reinforced PEEK composites based on good interfacial adhesion. The composites had lower activation volume and complex shear viscosity. Furthermore, the modified wollastonite‐reinforced PEEK composites had higher crystallization peak temperature (T_c) and crystalline fraction (χ_c) compared with the unmodified wollastonite‐reinforced PEEK composites. This study shows that the traditional silane coupling agents could effectively improve the performance of PEEK composites. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis of poly(ether ether ketone)-block-polyimide copolymer and its compatibilization for poly(ether ether ketone)/thermoplastic polyimide blends

Novel poly(ether ether ketone)-block-polyimide copolymers (PEEK-b-PI) with different block length were prepared by the polycondensation of amino-terminated poly(ether ether ketone) oligomer and anhydride-terminated polyamic acid oligomer. As the compatibility agent, PEEK-b-PI was added to the poly(ether ether ketone)/thermoplastic polyimide (PEEK/TPI) blend, and blends of PEEK/TPI/PEEK-b-PI were prepared by melt extrusion. Morphology observation showed the domain size of the dispersed phase was significantly reduced with the addition of PEEK-b-PI having optimized block length, which suggested reduced interfacial tension and enhanced interfacial adhesion. The compatibilizing effect was further proven by the change of the glass transition temperature of PEEK and TPI, which shifted closer to each other. As a result, the mechanical properties of PEEK/TPI blends were significantly improved with the addition of the PEEK-b-PI. In particular, 5 wt% content of PEEK-b-PI can increase the elongation at break of the blend by about 200%.     

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.     

Low‐viscosity and soluble phthalonitrile resin with improved thermostability for organic wave‐transparent composites

High processing viscosity and poor solubility limit the application of heterocyclic polymers for fabricating organic wave‐transparent composites for aerospace applications. In this paper, a novel resin, poly(phthalazinone ether bisphenol fluorene) encapped with phthalonitrile (PPEBF‐Ph), was synthesized and used as the matrix. Biphenol‐based phthalonitrile monomer BP‐Ph was also synthesized and blended with PPEBF‐Ph to further lower the processing viscosity. Solubility tests showed that the resin was soluble in dimethylformamide, N,N‐dimethyl acetamide, N‐methylpyrrolidone, dimethyl sulfoxide, chloroform, and other solvents. Differential scanning calorimetry and rheological studies revealed that the mixed resins exhibited low processing viscosity and a wide processing window below the gel temperature. Thermogravimetric analysis indicated that the cured resins were stable below 510–530 °C under nitrogen atmosphere after 6 h of curing (decreased by 40–60% compared with previous reports on phthalonitrile resin). In air, the char yields of the resins reached 20–30% when heated at 800 °C. The composites were reinforced by a quartz fiber cloth and exhibited a dielectric constant of 2.94–3.27 in an electromagnetic field with frequency ranging from 8 to 18 GHz. Retention of the bending modulus exceeded 70% at 400 °C according to dynamic mechanical analysis, indicating excellent mechanical stability was obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45976.     

PEEK/diatomite composites by in situ polymerization: Synthesis,characterization and fundamental properties

In this study, poly (ether ether ketone)/diatomite composites (PEEK/diatomite composites) were prepared by in situ polymerization. In contrast to the direct melt-compounding method, particles are produced with up to 25 wt % higher filler content by the in situ polymerization method. We found that filling with diatomite improved the mechanical properties of PEEK by about 15%. Scanning electron microscopy revealed that the diatomite particles are uniformly dispersed in the PEEK matrix. Furthermore, the PEEK resin penetrates into the diatomite channels to form interpenetrating organic–inorganic network structures. The thermal stabilities of the composites were studied by thermogravimetric analysis, which revealed that they possess excellent thermal stabilities; these PEEK/diatomite composites exhibit higher decomposition-onset temperatures than virgin PEEK and lower rates of decomposition. This is attributable to interactions between the diatomite and the matrix, with the diatomite acting as a physical barrier between the polymer and the superficial zone where polymer combustion takes place. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46983.     

Morphology,viscoelastic properties,and mechanical behavior of epoxy resin modified with hydroxyl‐terminated poly(ether ether ketone) oligomer with pendent tert‐butyl groups

Hydroxyl‐terminated poly (ether ether ketone) with pendent tert‐butyl groups (PEEKTOH) synthesized from 4,4′‐difluorobenzophenone and tert‐butyl hydroquinone was blended with diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin. A diamine, 4,4′‐diaminodiphenyl sulfone (DDS) was used as the curing agent. The thermal and mechanical properties, fracture toughness, and morphology of the blends were investigated. Morphological analysis of the blends revealed a particulate structure with PEEKTOH phase dispersed in the epoxy matrix. Unlike classical polymer blend systems, increase in concentration of PEEKTOH does not increase the domain size. Instead, a decrease is obtained. The fracture toughness increased with the addition of oligomer without much decrease in tensile and flexural strengths. Addition of 15 phr oligomer gave maximum toughness. The dispersed PEEKTOH initiated several mechanisms that improved the fracture toughness of the blends. The cross‐link density calculated from the storage modulus in the rubbery plateau region decreased with the increase in PEEKTOH. The thermal stability of epoxy resin remained unaffected even after blending with PEEKTOH. POLYM. ENG. SCI., 45:1645–1654, 2005. © 2005 Society of Plastics Engineers     

Sulphonated Biphenylated Poly(aryl ether ketone)s for Fuel Cell Applications

New series of fully aromatic poly(ether ketone)s with a biphenyl pendant groups were synthesised. A direct comparison of sulphonation reaction among monophenylated poly(ether ether ketone) (Ph‐PEEK), biphenylated poly(ether ether ketone) (BiPh‐PEEK) and PEEK (Victrex) was thoroughly investigated. Several advantages of the pendant‐phenyl poly(ether ketone)s compared with commercial PEEK were identified, including ready control over the site of sulphonation and degree of sulphonation (DS), and mild and rapid sulphonation. The basic membrane physical properties comprising of thermal and mechanical properties, dimensional stability and proton conductivity were studied. One new membrane, sulphonated biphenylated poly(ether ether ketone) (BiPh‐SPEEKDK) having a good combination of membrane properties was fabricated into a membrane electrode assembly (MEA), and it showed excellent direct methanol fuel cell (DMFC) performance.     

Preparation of novel semihomogeneous cation‐permeable membranes from blends of sulfonated poly(phenylene sulfide) and sulfonated phenolphthalein poly(ether ether ketone)

A series of semihomogeneous cation‐exchange membranes were prepared with binary blend systems, such as sulfonated phenolphthalein poly(ether ether ketone) (SPEEK‐C)/sulfonated poly(phenylene sulfide) (SPPS), or ternary blend systems, such as phenolphthalein poly(ether ether ketone) (PEEK‐C)/SPEEK‐C/SPPS, by solution blending and phase inversion, in which PEEK‐C and SPEEK‐C acted as binders and SPPS powder acted as a polyelectrolyte. Compared with homogeneous and heterogeneous membranes, the prepared semihomogeneous membranes had good electrochemical properties and mechanical strength as well as good dimensional stability. The fundamental properties of the membranes, such as the ion‐exchange capacity, water content, electrical resistance, transport number, diffusion coefficient of the electrolytes, and streaming potential, were largely dependent on both the loading of the SPPS resin and the sulfonation degree of PEEK‐C. Through the adjustment of these two important parameters, a series of semihomogeneous membranes with the desired conductivity and selectivity and the proper water content for different industrial purposes, such as electrodialysis, diffusional dialysis, and proton exchange, were achieved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1478–1485, 2004     

Dynamic mechanical analysis and morphological studies of fly ash/mica reinforced poly(ether‐ether‐ketone)‐based hybrid composites

Hybrid composites based on poly(ether‐ether‐ketone) (PEEK) were fabricated with fly ash and mica. Nearly 5, 10, and 15 wt% of fly ash were replaced by mica of the optimized fly ash reinforced composites and were subjected to dynamical mechanical analysis to determine the dynamic properties as a function of temperature. The storage modulus E′ was found to decrease with the increase of weight fraction of mica. Loss modulus was also found to decrease with loading while the damping property was found to increase marginally. Peak height of tan δ for hybrid composites were decreased by varying combinations of fly ash with mica. It is probably due to improved crystallinity of PEEK and strong interaction between the fillers and PEEK matrix. Cole–Cole analysis was made to understand the phase behavior of the composite samples. Kubat parameter was calculated to study the adhesion between matrix and filler of the fabricated composites. Without surface modification for inorganic fillers, the distribution of two different shape filler particles appears to be reasonably uniform. The use and limitation of various theoretical equations to predict the tan δ and storage modulus of filler reinforced composites have been discussed. Addition of both fillers opens up new opportunities for development of high‐performance multifunctional materials suitable for industrial applications. Scanning electron micrographs of tensile fracture surfaces of composites demonstrated filler–matrix bonding. POLYM. COMPOS., 35:68–78, 2014. © 2013 Society of Plastics Engineers     

High performance PEEK/AlN micro‐ and nanocomposites for tribological applications

The tribological properties of poly(ether–ether–ketone) (PEEK)/aluminum nitride (AlN) composites reinforced with micro‐ and nano‐AlN particles were evaluated under dry sliding conditions. The wear resistance of pure PEEK is 10‐fold higher than mild steel. It was further improved by 2‐fold at 20 wt % micro‐AlN and by more than 4‐fold at 30 wt % nano‐AlN composite compared with pure PEEK. The improvement in wear resistance was attributed to a thin and coherent transfer film. However, it was deteriorated on further increasing micro‐AlN. The coefficient of friction of the composites was increased. Scanning electron microscopy and optical microscopy of worn surfaces and transfer films have been explained in detail. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011