Crystallization behavior and mechanical properties of poly(aryl ether ether ketone)/poly(ether imide) blends

Crystallinity and mechanical properties of blends with different amounts of semicrystalline poly(aryl/ ether ether ketone) (PEEK) and amorphous poly(ether imide) (PEI) polymers have been studied. The blends, prepared by melt mixing, have been investigated by differential scanning calorimeter (DSC) to analyze the miscibility between the components and the final crystalline content. Moreover, for the 20/80 PEEK/PEI blend, crystallization in dynamic and isothermal conditions has been carefully investigated in order to find proper conditions for maximum development of crystallinity. Mechanical tests (static and dynamic) have been performed to evaluate the properties of the as-molded and crystallized blends and to compare them with those of crystalline PEEK and amorphous PEI neat resins. Finally, a few SEM observations have been performed to compare the fractured surface of the blend with those of the pure constituents.     

聚醚醚酮共混改性研究进展

综述了聚醚醚酮（PEEK）、聚醚酰亚胺（PEI）、聚四氟乙烯（PTFE）、热致液晶（TLCP）和聚醚砜（PES）等高性能工程塑料的共混改性研究进展,详细探讨了各种PEEK共混物的相容性、结晶行为、微观结构、热行为和力学性能等性能特征。PEEK与PEI在熔融和无定形状态下完全相容,常用于PEEK的结晶行为和微观结构的基础研究;与PTFE、TLCP、PES共混分别是提高PEEK的摩擦磨损性能、加工性能和热稳定性的有效手段。各种共混物的相容性好坏对其结晶行为和微观结构有重要影响,从而影响了共混物的力学性能。在此基础上,对PEEK共混改性领域进一步的研究方向和内容进行了讨论。     

Phase and crystallization behavior of solution-blended poly(ether ether ketone) and poly(ether imide)

Results on solution-blended poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) blends are reported. Dichloroacetic acid was used as the cosolvent for blending. PEEK and PEI are confirmed to be miscible in the melt. The glass transition, T_g, behavior obeys the simple Fox equation or the Gordon-Taylor equation with the adjustable coefficient k = 0.86. This agrees with prior data on melt-blended PEEK/PEI blends. The T_g width of the amorphous PEEK/PEI blends was found to be broader than that of the pure components. The maximum broadening is about 10°C. The specific volume of the amorphous PEEK/PEI blends shows a slight negative deviation from linearity, indicating favorable interaction between PEEK and PEI. The spherulitic growth and resultant blend morphology at 270°C were studied by a cross-polarized optical microscope. The radial growth rate of PEEK spherulites formed from the miscible melt at 270°C decreases from 3.04 μm/min for PEEK/PEI 90/10 blend to 0.77 μm/min for PEEK/PEI 70/30 blend. The decrease in crystalization rate of PEEK from PEEK/PEI blends is attributable to the increase in blend T_g. A linear growth was observed for PEEK spherulites formed from miscible melt at 270°C in the early growth stage. The spherulitic growth deviated from linearity in the late stage of growth. PEEK spherulites formed from the miscible PEEK/PEI melt at 270°C are essentially volume-filling. The branches of the spherulites become more clear for PEEK spherulites formed from the blend than that formed from pure PEEK melt.     

Miscibility and mechanical properties of poly(ether imide)/poly(ether ether ketone)/liquid crystalline polymer ternary blends

This paper is concerned with a novel ternary blend composed of poly(ether imide) (PEI), poly(ether ether ketone) (PEEK) and a liquid crystalline polymer (LCP; HX4000, Du Pont). Different compositions were prepared by extrusion and injection moulding. Dynamic mechanical thermal analysis and the observation of the fracture surfaces, before and after annealing, allowed determination of the cold crystallization temperatures and miscibility behaviour of these systems. PEEK/PEI blends are known from previous studies to be miscible at all compositions. In this case it was observed that the PEEK/HX4000 blend was miscible up to 50 wt% HX4000 but partially miscible above this value. The PEI/HX4000 blends were found to be partially miscible in the whole concentration range. As a result, some ternary blend compositions exhibited only one phase, while others exhibited two phases. The measurement of the tensile properties showed that ternary blends with high modulus can be obtained at high LCP loadings, while compositions with high ultimate tensile strength can be obtained with high loadings of PEI or PEEK.     

Intermolecular interaction and conformation in poly(ether ether ketone)/poly(ether imide) blends — An infrared spectroscopic investigation

The intermolecular interaction and the conformation in miscible blends of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) have been investigated by Fourier-transform infrared (FTIR) spectroscopy. The intensity of the C=O out-of-phase stretching (1725 cm^–1) of PEI shows a minimum at 70 wt% PEI, whereas that of the C=O in-phase stretching (1778 cm^–1) is not perturbed by blending. These intensity variations have been attributed to the effect of blending on the coplanarity of the two imide rings bridged by the phenylene group. Change in coplanarity of these two imide rings alters the intensity of the C=O out-of-phase stretching, but it can not affect the intensity of the C=O in-phase stretching. When the two imide rings are perpendicular to each other, the intensity of the C=O out-of-phase stretching is shown to reach the minimum, corresponding to the observation at 70 wt% PEI. The difference spectra (blend - PEEK - PEI) reveal that the bands associated with the diphenyl ether groups in PEEK are modified by blending with PEI. It is proposed that the favorable interaction takes place between the oxygen lone-pair electrons of the ether group in PEEK and the electron-deficient imide rings in PEI.     

Morphology profiles obtained by reaction‐induced phase separation in epoxy/polysulfone/poly(ether imide) systems

The reaction‐induced phase separation in epoxy/aromatic diamine formulations simultaneously modified with two immiscible thermoplastics (TPs), poly(ether imide) (PEI) and polysulfone (PSF), has been studied. The epoxy monomer was based on the diglycidyl ether of bisphenol A (DGEBA) and the aromatic diamine was 4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline) (MCDEA). Phase‐separation conversions are reported for various PSF/PEI proportions for blends containing 10 wt% total TP. On the basis of phase‐separation results, a conversion–composition phase diagram at 200 °C was compiled. This diagram was used to design particular cure cycles in order to generate different morphologies during the phase‐separation process. It was found that, depending on the PSF/PEI ratio employed, a particulate or a morphology characterized by a distribution of irregular PEI‐rich domains dispersed in an epoxy‐rich phase was obtained for initially miscible blends. Scanning electron microscopy (SEM) characterization revealed that the PEI‐rich phase exhibits a phase‐inverted structure and the epoxy‐rich matrix presents a bimodal size distribution of TP‐rich particles. For PSF/PEI ratios near the miscibility limit, slight temperature change result in morphology profiles. Copyright © 2005 Society of Chemical Industry     

Permeation resistance of poly(ether ether ketone) to hydrogen,nitrogen, and oxygen gases

We studied the gas permeation properties of poly(ether ether ketone) (PEEK) and compared it with two other polymers commonly used in the construction of semiconductor microenvironments, polycarbonate (PC), and poly(ether imide) (PEI). The PEEK specimens consisted of extruded films as well as compression‐ and injection‐molded specimens. The compression‐molded specimens were prepared to achieve the highest crystallinity. Injection‐molded disks, representing products, were milled to a prescribed thickness. Permeation, diffusion, and solubility coefficients were measured on these various PEEK specimens for hydrogen, nitrogen, and oxygen gases. It was found that PEEK generally has better permeation resistance than PC or PEI; showing up to five times lower permeation rates than PC or PEI, depending on grade, crystallinity, and gas. The superior permeation resistance of injection‐molded or extruded PEEK, when compared with similarly processed PC or PEI, comes from its crystallinity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal properties and morphology of blends of poly(ether imide) and polycarbonate

Blends of poly(ether imide) (PEI) and bisphenol-A polycarbonate (PC) have been investigated by differential scanning calorimetry, dynamic mechanical thermal analyzer, scanning electron microscopy, and transmission electron microscopy. Three different molecular weights of polycarbonate have been used in the PEI-PC blends. Blends were prepared by screw extrusion and solution casting with weight fractions of PEI in the blends varying from 0.90 to 0.10. From the measured glass transition temperature (T_g), the maximum decrease of T_g(PEI) is observed for 0.9 weight fraction PEI in the PEI-PC blends. In the study of the morphology, the size of minor component domains (about 0.1 to 0.3 µm) in the 90/10 PEI-PC blend is small compared to the size of minor component domains (about 0.2 to 2.0 µm) in the 10/90 PEI-PC blend. This morphological behavior is attributed mainly to the difference of viscosity ratio between the dispersed phase and continuous phase. No considerable differences in the thermal behavior and morphologies have been observed among the blends of PEI and PC having different molecular weights.     

Thermal properties of melt‐blended poly(ether ether ketone) and poly(ether imide)

The thermal properties of blends of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) prepared by screw extrusion were investigated by differential scanning calorimetry. From the thermal analysis of amorphous PEEK–PEI blends which were obtained by quenching in liquid nitrogen, a single glass transition temperature (T_g) and negative excess heat capacities of mixing were observed with the blend composition. These results indicate that there is a favorable interaction between the PEEK and PEI in the blends and that there is miscibility between the two components. From the Lu and Weiss equation and a modified equation from this work, the polymer–polymer interaction parameter (χ₁₂) of the amorphous PEEK–PEI blends was calculated and found to range from −0.058 to −0.196 for the extruded blends with the compositions. The χ₁₂ values calculated from this work appear to be lower than the χ₁₂ values calculated from the Lu and Weiss equation. The χ₁₂ values calculated from the T_g method both ways decreased with increase of the PEI weight fraction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 733–739, 1999     

Characteristics of poly(ether ether ketone) microporous membranes prepared via thermally induced phase separation (TIPS)

The morphology and bulk properties of microporous membranes based on poly (ether ether ketone) (PEEK) have been investigated as a function of initial casting composition and thermal and mechanical processing history. Membranes were prepared via solid—liquid phase separation of miscible blends of PEEK and polyetherimide (PEI), with subsequent extraction of the PEI diluent. Scanning electron microscopy studies revealed a microporous morphology with two distinct pore size scales corresponding to diluent extraction from interfibrillar and interspherulitic regions, respectively. The membrane structure was sensitive to both initial blend composition and crystallization temperature, with the resulting pore size distribution reflecting the kinetics of phase separation. For membranes prepared with lower initial diluent content or at lower crystallization temperatures, mercury intrusion porosimetry indicated a relatively narrow distribution of fine interfibrillar pores, with an average pore size of approximately 0.04 microns. Membranes prepared at higher diluent content or at higher crystallization temperatures displayed a broad pore distribution, with a sizeable population of coarse, interspherulitic pores (0.1 to 1 μm in size). Uniaxial drawing led to a fibrillated network structure with markedly higher water flux characteristics compared to the as-cast membranes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2347–2355, 1997     

Reinforcing and toughening on poly(ether imide) by a novel thermo tropic liquid crystalline poly(ester‐imide‐ketone) with low content

Reinforcing and toughening effects on the thermoplastic poly(ether imide) (PEI) by a novel thermo tropic liquid crystalline poly(ester‐imide‐ketone) (TLCPEIK) with low content were studied in this work. The novel TLCPEIK with kink naphthalene structure in the backbone was synthesized in our laboratory. A series of in‐situ composites (TLCPEIK/PEI) with a low concentration of TLCPEIK(≤5 wt%) were prepared by direct extrusion. Tensile strength, flexural strength, and flexural modulus of the composites increased with increasing TLCPEIK content. Impact strength and elongation at break of the composites were enhanced greatly when compared with that of pure PEI. To explain the simultaneously reinforcing and toughening effects on PEI by TLCPEIK, miscibility and morphology of the composites were studied by differential scanning calorimetry (DSC) and scanning electron microscopy. The experimental results suggest that good compatibility of the components is beneficial to improve the ultimate properties of TLCPEIK/PEI in‐situ composites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers.     

Blends of a thermotropic liquid crystalline polymer and some flexible chain polymers and the determination of the polymer-polymer interaction parameter of the two polymers

Summary Blends of a thermotropic liquid crystalline polymer (LCP) with poly(ether imide) (PEI), poly(ether ether ketone) (PEEK), polysulfone (PSF) and polyarylsulfone (PAS) prepared by screw extrusion have been investigated by differential scanning calorimeter and dynamic mechanical thermal analysis. From the measured glass transition temperature (T_g) and specific heat increment (ΔC_p) at the T_g, it appears that the LCP dissolves more in the PEI- and PEEK-rich phases than does the PEI and PEEK in the LCP-rich phase. From the DSC study of PSF-LCP and PAS-LCP blends, the T_g(PSF) and T_g(PAS) of each blends are almost constant with blend composition. Therefore, it is concluded that PSF and PAS are immiscible with LCP. The polymer-polymer interaction parameter (χ₁₂) and the degree of disorder (y/x₁) of LCP have been investigated using the Flory lattice theory in which the anisotropy of LCP is considered. The χ₁₂ values have been calculated from the T_g data and found to be 0.181 ± 0.004 at 593 K for the PEI-LCP blends and 0.069 ± 0.006 at 623 K for the PEEK-LCP blends. Using the previously presented method, the χ₁₂ and y/x₁ in partially miscible systems have been determined. Received: 6 April 1998/Revised version: 8 June 1998/Accepted: 17 June 1998     

A Novel Quaternary Blend System of Poly(ethy1ene terephthalate), Poly(trimethy1ene terephthalate), Poly(butylene terephthalate), and Poly(ether imide)

Summary A quaternary blend system composed of three low-T_g semi-crystalline aryl-polyesters namely, [poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poli(butylene terephthalate) (PBT)] and an amorphous high-T_g poly(ether imide) (PEI) was prepared and investigated using thermal and morphology characterization techniques. This study, for the first time, demonstrated miscibility and phase behavior of a quaternary blend comprising four different polymers. A single and composition-dependent T_g was found for each of all quaternary blend samples. In addition, various thermal transition characteristics, single and composition-dependent T_c,c, increasingly suppressed ΔH_c,c at higher PEI contents, are also indication of phase miscibility of the quaternary blend. SEM morphology characterization (3000X) revealed no discernible domains and homogeneous phase morphology in the quaternary blends was also substantiated using optical and scanning electron microscopy results. Received: 14 November 2002/Revised version: 17 February 2003/ Accepted: 22 February 2003 Correspondence to Eamor M. Woo     

Tensile behaviour and fracture toughness of poly(ether ether ketone)/poly(ether imide) blends

Summary The bulk tensile behaviour of poly(ether ether ketone) and poly(ether imide) homopolymers and their blends has been investigated, and the temperature and strain rate dependence of the yield stress discussed in terms of simple Eyring rate theory. In fracture mechanics tests, the K_IC of PEEK was found to decrease significantly with increasing test speed, whereas the K_IC of PEI showed little rate sensitivity. Therefore, although a gradual increase in K_IC with increasing PEEK content was observed in the blends at low loading rates, this effect was anticipated to be less pronounced at higher loading rates.     

Spherulitic growth kinetics in miscible blends of poly(ether ether ketone) and poly(ether imide)

Growths of poly(ether ether ketone) (PEEK) spherulites from both pure melt and its miscible blends with poly(ether imide) (PEI) have been studied by polarized optical microscopy. The nucleation density of PEEK spherulites was depressed upon blending with PEI, which can be attributed to the reduction in degree of supercooling arising from equilibrium melting point depression. A modified Lauritzen-Hoffman (L-H) theory was adopted to analyze the growth kinetics. Regime III-II transition was observed with the transition temperature decreasing with increasing PEI composition. Assuming free rotations of the virtual bonds in PEEK molecule, the side surface free energy of 12.0 erg/cm² was calculated from the characteristic ratio. The fold surface free energy of 188 erg/cm² and work of chain folding of 12.3 kcal/mol were then obtained from the modified L-H analysis.     

Phase separation of poly(ether sulfone imide) modified epoxy resin

Poly(ether sulfone imide)s (PEI) with molecular weight M_n ∼ 10⁴ were synthesized from 3,3′,4,4′-benzophenone tetracarboxylic dianhydride and amine terminated poly(ether sulfone) having molecular weights ranging from M_n ∼ 400 to M_n ∼ 4000. Thus, the PEIs had the same molecular weight but various imide and ether sulfone contents. The PEIs were mixed with a stoichiometric mixture of diglycidyl ether bis-phenol-A (DGEBA)/diamino diphenyl sulfone (DDS). The effect of PEI on the curing reaction of DGEBA/DDS and the morphology of the polymer blend were studied by differential scanning calorimetry (DSC) and optical microscopy. In the DGEBA/DDS/PEI blend with a fixed PEI molecular weight and PEI concentration but with various imide content, the experimental data revealed the PEI with a higher content of ether sulfone had a lower T_g and a better compatibility with solvents and epoxy resins; the curing reaction rate of DGEBA/DDS/PEI was faster for PEI with a higher imide content; the DSC data of cured DGEBA/DDS/PEI showed two T_gs, indicating phase separation between PEI and cured epoxy resins; and the data of optical microscopy showed that the compatibility of PEI with epoxy resins increased with the content of ether sulfone in PEI. © 1996 John Wiley & Sons, Inc.     

Liquid-crystal polymer fiber production and reinforcing in ribbons of poly(ether imide)/vectra-B blends

Blends of poly(ether imide) (PEI) with a liquid-crystal polymer (Vectra-B950) were extruded into ribbon. Two PEI-rich compositions at three different draw ratios were obtained, and the miscibility and morphology of the blends analyzed. The tensile properties of the ribbons were determined, both in the processing and in the perpendicular direction and were compared with those of the pure PEI. Results showed that PEI/Vectra blends are immiscible and that complex structures were obtained as a consequence of extrusion. The blend composition and the draw ratio determined to a great extent the mechanical properties of the blends. The interfacial adhesion between blend components is low, but enough to break the LCP fibers when significant aspect ratios are attained.     

Synthesis,structural characterization and properties of novel functional poly(ether imide)/titania nanocomposite thin films

In this study, the synthesis, morphology, and thermal properties of new poly(ether imide)/titania nanohybrid films were investigated. The novel diamine containing functional nitrile groups was prepared in two steps by the nucleophilic substitution reaction and it was fully characterized by different techniques. Reaction of this diamine with pyromellitic dianhydride and 4-aminobenzoic acid gave poly(ether imide) with carboxylic acid end groups. This acid functionalized poly(ether imide) was condense with different amount of TiO₂ nanoparticles to provide organic-inorganic bonding, and the flexible films of these hybrid were prepared. The obtained materials were characterized by Fourier transform-infrared spectroscopy, thermogravimetry analysis (TGA), differential scanning calorimetry, X-ray powder diffraction, UV–Vis spectroscopy, field emission-scanning electron microscopy, and transmission electron microscopy (TEM) techniques. TEM of the nanohybrid films with 12% of TiO₂ contents confirms well dispersion of nanoparticles in the polymer matrix. TGA data indicated that the thermal behavior of the hybrid materials was increased with an increasing the content of TiO₂ nanoparticles. The tensile stress–strain of the hybrids was investigated and the resulting nanocomposites showed good mechanical properties. The permeability and selectivity of the PEI/TiO₂ membranes as a function of the titania weight percentage were study and the results indicated that the permeabilities of CO₂ and N₂ increase with increasing the titania content.     

Free volume and damping in a miscible high performance polymer blend: Positron annihilation lifetime and dynamic mechanical thermal analysis studies

High performance polymer blend of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) was examined for their free volume behavior at different compositions of PEI using positron annihilation lifetime spectroscopy (PALS). The damping property of the blend was studied using tan‐δ obtained from dynamic mechanical thermal analysis (DMTA). The dependence of tan‐δ on temperature revealed that the blend is miscible in all compositions, in agreement with earlier studies. The tan‐δ peak height is found to increase with increase in free volume fraction for the entire blend composition signifying that the free volume plays an imperative role in understanding the damping property. Using DMTA, master curves were obtained at a reference temperature T₀ by applying the time‐temperature‐superposition (TTS) using Williams‐Landel‐Ferry (WLF) relationship. From the shift factor a_T, the WLF coefficients and were evaluated, using which the free volume fraction was found. Both PALS and DMTA methods were found to give similar results for the dependence of free volume for various PEI contents studied in this blend. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42961.     

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