Kinetics of structural evolution during crystallization of preoriented PET as followed by dual wavelength photometric birefringence technique

A two-color laser photometric measurement system was used to follow birefringence changes in annealing of prestretched PET films. This technique was shown to be capable of detecting large retardation (and thus birefringence) changes beyond one wavelength of the light. The use of green and red lasers in the photometric system allows the detection of the reversals in birefringence during the course of annealing. Unless critical orienialion/erystallinity levels are developed by stretching the films, heat setting the films at temperatures close to glass transition temper ature results in complete elimination of preferential orientation. At Intermediate stretch ratios, crystalline regions form and Ihe acl as anchor points establishing a network for the orienied amorphous chains. These Dims exhibit partial relaxation followed by rapid increase in birefringence due to the accelerating effect of orientation on crystallization. At high stretch ratios, where substantially oriented and strain crystallized structures are obtained, the initial relaxation stage disappears and birefringence continue to increase throughout the heat setting process even at temperatures very close to glass transition temperature. In these films, however, the total change of birefringence decreases as more of the chains are oriented and crystallized in the stretching stage, leaving a smaller fraction of polymer chains to rearrange during Ihe annealing stage. The kinetics of the structural change exhibit a complex behavior and the largest rates of structural changes were observed in films exhibiting intermidiate birefringence levels.     

Development of structural hierarchy during uniaxial drawing of PEEK/PEI blends from amorphous precursors

When poly(ether ether ketone)/poly(ether imide) (PEEK/PEI) blends are drawn in their rubbery region, prior to the critical draw ratio, they remain amorphous. Subsequent to the onset of strain hardening, the stress rises rapidly as a result of strain-induced crystallization of the chains highly oriented in the direction of strain. It is during this stage of deformation process that a highly structured physical network is formed where oriented crystallites act as nodes in the network structure. The wide angle X-ray scattering data indicate that chains in these ‘nodes’ are highly oriented and the three dimensional crystalline lattice is not well established due to poor axial registry of these highly oriented chains. This is evidenced by the absence of off-equatorial peaks. During this period, the effectiveness of drawing arises from the existence of the tie chains aligned in the direction of draw and forming the net between the crystallites. PEI, though a stiff and bulky chain, is found to delay the oriented crystallization rate of PEEK, but has little effect on its crystalline orientation in the composition range investigated.     

Influence of composition and annealing on the structure development in biaxially stretched PEN/PEI/PEEK ternary blends

The effect of biaxial stretching and annealing on the structure development in ternary blends of PEN/PEI/PEEK on mostly PEN-rich compositions has been investigated. Both PEN and PEEK are melt miscible with PEI. The addition of PEI greatly suppresses the crystallizability of the PEN while enhancing the glass transition temperature. The addition of PEEK to high PEI containing PEN/PEI recovers this crystallizability with the end result being the high T_g materials that can strain harden. The crystallization habit is mostly PEN at PEN-rich corner of the ternary diagram. The increase of PEI concentration beyond 20% eliminates the crystallizability of PEN and addition of as little as 10% PEEK causes these blends to crystallize upon stretching in the rubbery state.     

An analysis of the correlation between structural anisotropy and dimensional stability for drawn poly(lactic acid) films

The anisotropic structures found in drawn poly(lactic acid) films are strongly correlated to their overall dimensional stability. Several aspects of this relationship can be efficiently characterized by Raman spectroscopy. We determined the degree of orientation in these drawn films by measuring the relative intensity of the polarized and depolarized components and the shift in the relative band positions. The bandwidth and specific band frequency also correlated well with the degree of sample crystallinity. These aspects make the Raman method amenable for the online monitoring of orientation and crystallinity in commercial processes. A molecular understanding of heat setting to reduce film shrinkage is also proposed. Raman data from films that were heat-set while physically constrained suggest that amorphous-phase relaxation does not occur during heat setting. Rather, the level of crystallinity increases substantially, indicating that the cause of low shrinkage in the films was due to crystalline network formation rather than amorphous-phase relaxation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2497–2505, 2001     

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.     

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     

The suppression of strain induced crystallization in PET through sub micron TiO2 particle incorporation

The effects of TiO₂ particles on the crystallization and uniaxial stress-strain behavior of poly(ethyleneterephthalate) (PET) films from amorphous precursors were investigated. The addition of small fraction of sub micron sized TiO₂ particles were found to suppress the mechanical relaxation processes associated with high temperature side of the β relaxation while enhancing the low temperature relaxation. When crystallized from unoriented precursors, TiO₂ particles act as a nucleation agent and enhance the thermally induced crystallization of the PET chains. However, when stretched from the amorphous precursors in rubbery temperature range (T_g<T_p<T_cc), the TiO₂ concentration levels as low as 0.35 wt% was found to reduce the overall stress and retard strain hardening and accompanying stress induced crystallization. As a result, under the same stretching conditions, the films containing TiO₂ were found to possess lower crystallinity and orientation levels. This was attributed to suppression of stress induced crystallization as these particles act to disrupt the formation of crystalline lattice by their physical presence. This may be as a result of the reduction of chain entanglements in the presence of these sub micron sized TiO₂ particles in the structure of the polymers that retard the formation of physical network whose nodes are made up of entanglements and small crystalline domains. The development of this long range ‘connected’ network is primarily responsible for the rapid upturn in the stresses at the onset of strain hardening observed in stress strain curves.This method represent a unique way to apply ‘anti-nucleating agent’ effect to control the development of stress induced crystallization that will help control the film and fiber forming processes.     

Rapid structural changes that take place during constrained annealing of biaxially stretched pet films

The aim of this work is to study the structural changes that take place during the heat setting of simultaneously and sequentially biaxially stretched polyethylene terephthalate films. The rate of structural rearrangement, as detected by real‐time birefringence and off‐line Raman spectroscopy, DSC thermal analysis and X‐rays, was found to be dependent on the state of the orientation and crystallinity attained by the samples during the stretching step. This suggested that the annealing behavior can be categorized into three regimes according to the birefringence behavior of the samples. At low deformations, the films not crystallized by strain exhibit complete birefringence relaxation without showing any sign of crystallization. The intermediate ratio samples that were stretched to the onset of the strain‐induced crystallization exhibited the highest levels of birefringence increase after a short relaxation. The samples stretched well above the onset of the strain‐induced crystallization exhibited intermediate level of birefringence and crystallinity increase. Therefore, the classification of the three regimes was found to be related to the onset of the strain‐induced crystallization during the stretching step. POLYM. ENG. SCI., 57:550–562, 2017. © 2016 Society of Plastics Engineers     

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.     

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.     

热定型张力对PAN原丝结构与性能的影响

研究了热定型过程中的张力对PAN原丝结构与性能的影响。结果表明：热定型张力对PAN原丝的物理性能影响很大;随着热定型张力减小,PAN原丝的抗拉伸强度和初始模量随之减小,而断裂后伸长率逐渐增大;沸水收缩率和取向度也随着定型松弛幅度的增加而降低。     

Water sorption kinetics in poly(aryl ether ether ketone)

The kinetics of diffusion of water from different activity vapors and liquid phase have been investigated in glassy amorphous poly(aryl ether ether ketcne) (PEEK) films at the temperature of 60°C and in glassy semicrystalline PEEK sheets at different temperatures, respectively. In the case of the amorphous PEEK films (250 μm thick) the data at low activity levels were interpreted by means of a purely Fickian mechanism. At higher activity levels the material has shown the presence of a relaxation process; in this case the data have been interpreted using a model proposed by Berens and Hopfenberg. Equilibrium sorption isotherm is also reported. Liquid water sorption in semicrystalline (30%) PEEK sheets (2 mm thick) has been determined to follow the classical Fickian mechanism. The water uptake values obtained for both amorphous and semicrystalline PEEK, confirm the good moisture and liquid water resistance of this kind of high performance thermoplastic polymer.     

Polymer Film Heat Transfer Surfaces in Seawater Desalination: Fouling Layer Formation and Technology

The emerging polyether ether ketone (PEEK) films were evaluated as future heat exchanger materials in seawater thermal desalination processes. Fouling resistance curves were measured in a pilot plant for pure PEEK films, talcum-filled PEEK films, and stainless-steel films with artificial seawater, showing that pure PEEK films have the advantage of weaker forces of adhesion or cohesion between the scaling materials and the film surface. Increasing the flow rate from 18 to 24 L min⁻¹ results in decreases of both the fouling rate and the asymptotic values. This was attributed to the lower polarity of 10.4 %, the lower arithmetic average roughness of 0.06 μm, and the homogeneous topography of the PEEK film. This polymer film is adaptable to in situ cleaning in thermal seawater desalination processes.     

Structural and mechanical characterization of poly(ether ether ketone) (PEEK) and sulfonated PEEK films: Effects of thermal history,sulfonation, and preparation conditions

In this work, virgin and sulfonated poly(ether ether ketone) films (PEEK and SPEEK, respectively) have been studied by dynamic mechanical analysis, modulated differential scanning calorimetry, wide‐angle X‐ray diffraction, birefringence, and optical microscopy. The properties of the unmodified polymer have been addressed to assess the original morphological characteristics and the changes induced by sulfonation. In general, the introduction of ionic groups in the polymer backbone alters dramatically the intrinsic properties of the parent material. The particular thermomechanical response exhibited by PEEK and SPEEK samples, characterized by a hysteresis loop, can be explained by the reversible and irreversible relaxation–orientation of the microstructure, even in the sub‐T_g region. The results showed that the preparation conditions largely determine the nonequilibrium morphological features of both compression‐molded PEEK films and solvent‐cast SPEEK membranes. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 756–774, 2006     

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     

Nanocellular foams—cell structure difference between immiscible and miscible PEEK/PEI polymer blends

Plastic foam with a nanoscale cell structure was prepared from poly(ether ether ketone) (PEEK)/para‐diamine poly(ether imide) (p‐PEI) as well as PEEK/meta‐diamine poly(ether imide) (m‐PEI) blends by a temperature quench foaming method with CO₂. The difference in chemical configuration between m‐ and p‐PEI gave rise to a prominent change in the higher order blend morphology and cell structure of the respective foams. The bubble nucleation site and bubble size were controlled by templating the morphology of the PEEK/p‐PEI blend, which shows an immiscible and unique strip‐patterned crystalline morphology. The properties influenced by the immiscibility of the PEEK/p‐PEI blend were investigated using SEM, thermal analysis and rheology and compared with the properties of the miscible PEEK/m‐PEI blend. The bubble size and location were highly controlled in the PEI disperse domain that was aligned between the PEEK crystalline layers in the PEEK/p‐PEI blend. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

聚醚醚酮纤维的结构与性能

采用熔融纺丝法制得聚醚醚酮(PEEK)纤维,研究了纤维的结构与性能。结果表明:PEEK纤维纵向表面比较光滑,附着少量凝胶粒子,纤维断面近似圆形,内部致密无空洞;PEEK纤维经过热拉伸定型处理后,纤维结晶度和取向度提高,纤维聚集态结构更加完善稳定;其断裂强度大于3.5 cN/dtex,断裂伸长率为30%,干热收缩率为2%;PEEK纤维在300℃下连续使用7 d后,纤维的强度保留率大于70%;紫外光辐照6d后,其强度保留率为56.45%;PEEK纤维对化学溶剂具有很好的耐腐蚀性能。     

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.     

Flammability behavior of fiber–fiber hybrid fabrics and composites

The effect of heat flux levels on burning behavior and heat transmission properties of hybrid fabrics and composites has been investigated using cone calorimeter and heat transmission techniques. The hybrid fabric structures woven out of E‐glass (warp) and polyether ether ketone (PEEK) (weft) and E‐glass (warp) and polyester (weft) have been studied at high heat flux levels keeping in view the flame retardant requirements of structural composites. The performance of the glass–PEEK fabric even at high heat flux levels of 75 kW/m² was comparable with the performance of glass–polyester fabric evaluated at 50 kW/m². The results further demonstrate that glass–PEEK hybrid fabrics exhibit low peak heat release rate, low heat release rate, low heat of combustion, suggesting an excellent combination of materials and fall under the low‐risk category and are comparable with the performance of carbon fiber‐epoxy‐based systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of heat sealing temperature on the properties of OPP/CPP heat seal. I. Mechanical properties

The effect of heat sealing temperature on the mechanical properties and morphology of OPP/CPP laminate films was investigated. The laminated films were placed in an impulse type heat sealing machine with both CPP sides facing each other. The temperatures investigated ranged from 100 to 250°C. T‐peel and tensile tests in combination with SEM were used to characterize the heat seals. A minimum seal initiation temperature of 120°C was identified for OPP/CPP laminate heat sealing. Peel strength increased sharply from zero at 110°C to maximum at 120°C, after which a gradual decrease was observed. Tensile strength initially increased until 120°C, after which it gradually decreased until 170°C and assumed a constant value beyond that. The initial rise has been associated to cold crystallization, while the reduction between 120°C and 170°C was due to relaxation in molecular orientation. Beyond 170°C, all the orientation in the laminate has been lost so orientation effects are nullified. Morphological studies with SEM revealed that seals were partially formed at lower temperatures, while the laminates were totally fused together at high temperatures, with intermediate temperatures showing properties that lie in between. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 753–760, 2005