The absorption of organic liquids in poly(aryl-ether-ether-ketone) [PEEK]

The absorption and subsequent desorption of benzene, toluene, carbon disulfide, and chloroform in amorphous and 27% crystalline poly (aryl-ether-ether-ketone) (PEEK) were determined. At 35°C, the equilibrium weight gain (solubility) of benzene, toluene, chloroform, and CS₂ are 23.5, 19.8, 51.2, and 21.2 wt%, respectively. The initial weight gain is linear with root-time and pseudodiffusion constants for absorption into amorphous PEEK ranging from 0.35 to 9.85 x 10^-12m²/s were calculated. The desorption processes are two-step and are controlled by the T_g of the penetrant-resin mixture. The rate of diffussion into the crystalline material is extremely slow; crystalline PEEK reaches saturation (12.5 wt%) after immersion in CS₂ (35°C) for several hundred hours but, even after 1300 h immersion, the other fluids do not reach saturation.     

Solvent-induced crystallinity in poly(aryl-ether-ether-ketone) [PEEK]

The amount and structure of the crystals formed by the solvent-induced crystallization (SIC) following a sorption-desorption cycle of five fluids (benzene, toluene, chloroform, methylene chloride, and carbon disulfide) in amorphous PEEK was determined by wideangle x-ray scattering (WAXS). The SIC crystal structure was compared with that produced by thermal methods, both those formed at low temperature by heating the amorphous material 10–20°C above T_g or by cooling from the melt. Although smaller in size, the SIC crystals are tighter and more organized than those produced thermally. The WAXS data indicates that all five fluids produce approximately 35% crystallinity in PEEK. Gravimetric data suggest that a low-density region, consisting of either microvoids or highly disordered amorphous region, surrounds the crystals.     

Stress-enhanced transport of toluene in poly aryl ether ether ketone (PEEK)

The transport of fluids in the semicrystalline polymer, poly(aryl ether ether ketone) (PEEK), was investigated. Both solubility and rate of penetration of toluene into PEEK are markedly increased by the application of an external stress. The induction period (i.e., the time for the sorption to begin) is a function of applied stress as well as temperature and crystallinity. At 22°C in 29% crystalline PEEK the induction period was reduced from more than 2000 h to approximately 10 h whereas the solubility of toluene was increased from 9 to 44 wt % upon the application of an external tensile stress of 30 MPa. A critical stress (i.e., a stress value below which the stress-enhanced effects are not observed) was determined. The critical stress is a strong function of crystallinity and temperature. © 1996 John Wiley & Sons, Inc.     

Transport behavior of carbon disulfide into poly aryl ether ether ketone

The sorption/desorption of carbon disulfide into/from PEEK as a function of crystallinity and temperature was investigated. The sorption curves of carbon disulfide into PEEK show only two major regions: (a) an increase of penetrant weight with time, and (b) a limiting equilibrium value (solubility). This is in contrast to the sorption of toluene into PEEK which shows three regions. The solubility of carbon disulfide decreases with increasing crystallinity, but temperature has little effect on the solubility in the temperature range of 25–40°C. An acceleration in penetration rate at the later stage of diffusion is observed for PEEK films whose crystallinity is greater than 13.4%, suggesting Supercase II diffusion. Carbon disulfide can be desorbed completely from PEEK in contrast to other fluids, such as toluene or methylene chloride, which are difficult to desorb. The normalized weight loss of carbon disulfide during desorption is an exponential function of square-root time. Solvent-induced crystallization was observed. Crystallinity was estimated from both the measured density and microhardness of the desorbed polymer and polymer which had undergone a sorption/desorption/resorption/desorption cycle. © 1996 John Wiley & Sons, Inc.     

Effects of methylene chloride sorption on the properties of poly(ether ether ketone)

Sorption of methylene chloride by poly(ether ether ketone) (PEEK) has been studied for both amorphous and highly crystalline polymer. After the determination of sorption and desorption curves, the crystallinity of the two materials after desorption was determined both by density and X-ray measurements. The experimental results indicate the existence of solvent-induced crystallization in initially amorphous PEEK and a virtual lack of this process in highly crystalline PEEK. In the latter case, the observed density increase is attributed to solvent compression and a decrease in free volume. The mechanical behavior of both PEEKs is consistent with their crystallinity levels. The mechanical behavior of both PEEKs before and after sorption allows us to discern the separate effects of the two processes to which the presence of methylene chloride in PEEK gives rise, i.e., plasticization and solvent-induced crystallization. © 1994 John Wiley & Sons, Inc.     

Dynamic relaxation behavior of solvent-crystallized poly(ether ether ketone)

The dynamic relaxation behavior of solvent-crystallized poly(ether ether ketone) (PEEK) has been investigated in the region of the glass-rubber (α) relaxation using dynamic mechanical and dielectric methods. Amorphous PEEK films were exposed to saturated methylene chloride and acetone vapor, with solvent-induced crystallization observed for both penetrants. Sample desorption at elevated temperatures (under vacuum) resulted in virtually complete removal of residual penetrant, thus providing for the measurement of relaxation characteristics independent of plasticization. Both dynamic mechanical and dielectric studies indicated a marked positive offset in the isochronal relaxation temperatures of the solvent-crystallized samples relative to thermally crystallized specimens of comparable bulk crystallinity, and a higher apparent activation energy in the solvent-crystallized case. These results are consistent with the evolution of a tighter crystalline morphology (i.e., smaller crystal long spacing) in the solvent-crystallized samples, the crystallites imposing a greater degree of constraint on the long-range motions of the amorphous chains inherent to the glass-rubber relaxation. © 1994 John Wiley & Sons, Inc.     

Effect of nitrogen plasma treatment on the crystallinity and self‐bonding of polyetheretherketone (PEEK) for biomedical applications

Polyetheretherketone (PEEK) is a thermoplastic material with outstanding properties and high potential for biomedical applications, including hermetic encapsulation of active implantable devices. Different biomedical grade PEEK films with initial degree of crystallinity ranging from 8% to 32% (with or without mineral filling) were inspected. PEEK surfaces were treated with nitrogen RF plasma and the effects on materials crystallinity and self‐bonding were evaluated. In particular, the relationship between auto‐adhesive properties and crystalline content of PEEK before and after plasma treatment was examined. PEEK samples showed different bonding strength depending on their degree of crystallinity, with higher self‐bonding performance of mineral‐filled semi‐crystalline films. XRD did not show any modification of the PEEK microstructure as a result of plasma treatment, excluding a significant influence of crystallinity on the self‐bonding mechanisms. Nevertheless, plasma surface treatment successfully improved the self‐bonding strength of all the PEEK films tested, with larger increase in the case of semi‐crystalline unfilled materials. This could be interpreted to the increase in chain mobility that led to interfacial interpenetration of the amorphous phase.     

聚醚醚酮及其碳纤维复合材料——恒温结晶动力学的研究

本文研究了聚醚醚酮(PEEK)和以PEEK树脂为基体的碳纤维复合材料(APC-2)在恒温条件下的结晶行为。采用差示扫描量热仪(DSC)测定从熔体和橡胶体结晶过程中热焓的变化。利用Avrami方程分析了PEEK和APC-2试样的恒温结晶动力学。PEEK从熔体和橡胶体结晶的活化能分别为532.1和531.7KJ/mol,Avrami指数的平均值分别为5.0和3.9;而APC-2则分别为444.2和432.5KJ/mol,3.5和2.3。这些实验结果表明,APC-2试样中碳纤维表面对PEEK树脂基体具有显著的成核作用,能降低其结晶活化能,因而导致PEEK树脂基体结晶速率加快和促进其结晶更加完整。     

Transparency enhancement in semicrystalline PEEK through variation of polymer morphology

We report a processing window in which transparent semicrystalline poly(ether ether ketone) (PEEK) can be produced. The transparent PEEK film reported is 100 μm in thickness and has light transmittance of 54%; while ordinary semicrystalline PEEK film of the same thickness and degree of crystallinity, but produced outside the processing window, is virtually opaque (with the light transmittance close to 0%). First processing conditions for producing the transparent PEEK film are discussed, and second characterization of the transparent PEEK film is detailed. Results suggest that the main processing condition for developing the transparent PEEK film is forming temperature, defined as the highest temperature that the film is exposed to during thermal treatment. Using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and small-angle x-ray scattering (SAXS), we characterized morphology of the PEEK films. TEM shows that the morphology in the transparent PEEK film has a locally oriented lamellar structure, instead of the commonly observed spherulites or sheaves. DSC results suggest that the new morphology is formed in the melt with a high density of residual crystals that act as nucleating agents during the crystallization process, which is known as a self-seeding effect. SAXS spectra show that specimens with higher forming temperature produce broader diffraction peak at larger Q value that is defined as 4π sin θ/λ. We conclude from the study that the light transmittance enhancement is morphology related, and can be achieved through control of processing conditions. © 1996 John Wiley & Sons, Inc.     

A comparison of the strength of autohesion of plasma treated amorphous and semi‐crystalline PEEK films

Polyether ether ketone (PEEK) is a promising material for the encapsulation of electronic components for medical implants but a strong and hermetic joining technology is required. Autohesion is a self‐bonding method that avoids the need for adhesives. The strengths of autohesive joins using amorphous and semi‐crystalline PEEK films after surface activation using RF plasma were compared. Both types of PEEK films showed successful autohesion after activation with the bond strength of the amorphous sample being twice as high as the bond strength of the semi‐crystalline sample. Plasma treatment increased the autohesion strength of PEEK with no observed change in surface roughness (as measured by profilometer). The water contact angle was reduced by the treatment. X‐ray photoelectron spectroscopy (XPS) was carried out to determine surface chemistry. In the case of the semi‐crystalline surface, plasma treatment increased the relative percentage of C? O functional groups compared to the untreated surface. For treated surfaces nitrogen concentration correlated positively with bond strength while oxygen concentration correlated negatively with the semi‐crystalline PEEK samples and positively with the amorphous PEEK samples. The oxygen groups most likely are formed after the treatment by ambient oxidation are not conducive to bond formation, possibly because of the quenching of radicals that would otherwise form links. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of proton irradiation on the melting and isothermal crystallization of poly(ether‐ether‐ketone)

Amorphous poly(ether‐ether‐ketone) (PEEK) progressively crosslinks on irradiation with 11.0 MeV protons, and this has a marked effect on the extent of crystallinity that subsequently develops and on the kinetics of the high temperature isothermal crystallization. The extent of crystallinity with time was analyzed using the Avrami equation, and the temperature dependence of the rate constants was analyzed in terms of nucleation theory. While irradiation inhibits the overall rates of crystallization by the reduction in the mobility of the chain segments as observed by the progressive increase in the glass transition temperature, it also alters the fold surface free energy. The observed melting points were consistent with depression of the equilibrium melting point by the crosslinks produced by irradiation. These two effects alone are sufficient to account for the inhibition of crystallization on irradiation of PEEK by protons. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1094–1103, 2008     

热处理对聚醚醚酮晶体结构参数及结晶度的影响

采用广角Ｘ射线衍射（ＷＡＸＤ）方法研究了不同热处理温度下聚醚醚酮（ＰＥＥＫ）的晶胞参数、微晶尺寸及结晶度的变化。根据Ｘ射线散射强度理论，运用图解多重峰方法导出了以ＷＡＸＤ方法计算ＰＥＥＫ结晶度的公式；用此公式对经不同热处理的ＰＥＥＫ样品进行计算，结果与由密度法及量热法测定的结果具有较好的可比性。     

Quantitative nanoscale measurements of the thermomechanical properties of poly-ether-ether-ketone (PEEK)

Understanding the internal structure and organization of semicrystalline polymers, especially at the nanoscale, has many challenges for researchers to date. In this article, we demonstrate a quantitative method for investigating the local viscoelastic properties (i.e., storage and loss moduli, as well as loss tangent) of semicrystalline polyether-ether ketone (PEEK) through the combination of contact resonance atomic force microscopy (CR-AFM) and in situ local heating with a thermal probe. Furthermore, the local viscoelastic properties of the crystalline and amorphous phases were decoupled by performing thermal CR-AFM array mapping near the glass transition temperature of PEEK (T_g, 143 °C). A distinct bimodal distribution of tip-sample interaction was observed for PEEK near its T_g, providing a means to estimate the T_g and the degree of crystallinity of PEEK.     

The solubility and diffusion of water in poly(aryl-ether-ether-ketone) (PEEK)

The transport properties of water in neat poly(aryl-ether-ether-ketone) (PEEK) coupons (2 to 6 mm thick) were investigated by gravimetric and mass spectrometric methods. The solubility of water increases from 0.44 wt.% at 35°C to 0.55 wt.% at 95°C; the temperature coefficient is 8 kJ/mol (1.9 kcal/mol). The diffusion processes for sorption, desorption, and resorption at 35°, 50°, 65°, 80°, and 95°C are, within experimental error, the same. The activation energy for diffusion is 42.7 kJ/mol (10.2 kcal/mol). The diffusion process is classical Case I Fickian in the temperature region investigated.     

Relationship between morphology and glass transition temperature in solvent-crystallized poly(aryl ether ketones)

The relationship between semicrystalline morphology and glass transition temperature has been investigated for solvent-crystallized poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK). Solvent-crystallized specimens of both PEEK and PEKK displayed a sizeable positive offset in T_g compared to quenched amorphous specimens as well as thermally crystallized specimens of comparable bulk crystallinity; the offset in T_g for the crystallized samples reflected the degree of constraint imposed on the amorphous segments by the crystallites. Small-angle X-ray scattering studies revealed markedly smaller crystal long periods (d) for the solvent-crystallized specimens compared to samples prepared by direct cold crystallization. The strong inverse correlation observed between T_g and interlamellar amorphous thickness (l_A) based on a simple two-phase model was in excellent agreement with data reported previously for PEEK, and indicated the existence of a unique relationship between glass transition temperature and morphology in these poly(aryl ether ketones) over a wider range of sample preparation history and lamellar structure than was previously reported. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 65–73, 1998     

The effect of morphology on the transport of dichloromethane in poly(aryl-ether-ether-ketone)

A study of the transport of the dichloromethane in neat poly(aryl-ether-ether-ketone) (PEEK) samples with thicknesses from 0.08 to 3.0 mm with different morphologies was conducted at 35°C. Both sorption and desorption of the solvent were studied. Thermal annealing was used to vary the sample morphology, and density measurements were used to determine the crystallinity of the samples. The equilibrium concentration of solvent and rate of solvent sorption were found to vary with sample morphology. The density of the dichloromethane when in the PEEK resin was found to be 1.65 g/cm³. Solvent desorption was independent of sample morphology or any previous sample treatment and depended only upon desorption temperature. Solvent sorption appears to alter the morphology of amorphous samples by increasing the crystallinity to about 20% after one sorption/desorption cycle. Small amounts of the solvent, less than 0.5 wt.%, remain trapped in fully desorbed samples. The micromorphology of solvent-induced crystallization appears to be different from that induced by thermal treatment.     

Preparation of high performance composites based on aluminum nitride/poly(ether-ether-ketone) and their properties

Novel high performance aluminum nitride (AlN)/poly(ether-ether-ketone) (PEEK) composites containing 0-50 wt.% fractions of AlN were prepared by solution blending method followed by hot pressing to evaluate their density, melting temperature, crystallization, thermal stability, morphological behavior and Vickers hardness by using different characterization techniques. Differential scanning calorimetry results indicated that the AlN particles are very effective nucleating agent, which results in increase in melting point, hot crystallization temperature and crystallinity of composites as the AlN content increases. Thermogravimetric analysis showed enhanced thermal stability of the composites with respect to PEEK. Density and X-ray diffraction techniques showed that crystallinity of the composites increases as the wt.% of AlN content increases in polymer matrix. Scanning electron microscopy revealed that AlN particles were well dispersed with no porosity in composites. Vickers hardness of the samples increased from 24 kg/mm² for the pure PEEK to 35 kg/mm² for AlN/PEEK composites.     

Surface Plasticization of Poly(ether ether ketone)

This paper describes a study of the surface plasticization and antiplasticization of an amorphous and a semicrystalline poly(ether ether ketone) (PEEK) in solvent environments using nanohardness method. A range of solvents (octane, chloroform, tetrachloroethane, acetone, dichlorobenzene, polyethyleneglycol (PEG), methanol and water) based on the Hilderbrand’s Solubility Parameter were selected as solvent environments. The results of the nanoindentation hardness experiments performed on the virgin and the solvent immersed polymeric surfaces are reported. The surface plasticization or antiplasticization is reported on the basis of the softening or the hardening of the near surface layers (?1 μm) after immersion of the polymeric surfaces in the solvent environments. Surface plasticization of the amorphous PEEK has been observed in organic solvents. The chlorine containing solvents have severely degraded the hardness of the amorphous polymer. A surface hardening of the amorphous PEEK has been observed after immersion in water. Semicrystalline PEEK was seen to exhibit a considerable inert behaviour to common organic solvents but chlorinated organic solvents and water have caused a decrease in the surface mechanical properties.     

Carbanion mechanisms : VIII. Metallation of arylmethanes by n-butyllithium. Spectrophotometric study of ion pairing

Results of a spectrophotometric study of the reaction of n-butyllithium are reported, in tetrahydrofuran (THF) medium, for triphenylmethane, diphenylmethane, di-p-tolylmethane, p-phenyltoluene and toluene. The temperature dependence of the absorption spectra for diphenylmethyllithium and di-p-tolylmethyllithium in THF gave evidence of an equilibrium between contact and solvent separated ion pair species, the latter predominating at low temperature. For di-p-tolylmethyllithium in THF this equilibrium is characterized by ΔH ?5.9 kcal/mol and ΔS ?18 e.u.     

Miscible blends of modified poly(aryl ether ketones) with aromatic polyimides

The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc.