Kinetics of strain-induced crystallization during injection molding of short fiber composites of poly(ether ether ketone)

Crystallization kinetics of short glass and carbon fiber composites of poly(ether ether ketone) (PEEK) under melt-strain conditions have been obtained for the first time, using in-situ wide angle X-ray scattering, and have been correlated to a model based on the Avrami equation in order to enable minimization of the processing time for injection molding of these materials. It has been demonstrated that increased flow rate of the melt in the mold and, consequently, increased shear rate accelerates the crystallization process of PEEK composites, analogous to similar trends observed previously in PEEK resin. Short glass fiber composites of PEEK crystallize slower than the resin under identical processing conditions, while short carbon fiber composites crystallize faster than the resin, except at the highest mold temperatures and the lowest flow rates. A model based on the Avrami equation has been proposed to fit the kinetics data obtained experimentally. The Avrami coefficient has been calculated and Arrhenius plots have been used to predict the crystallization kinetics at temperatures lower than those at which experimental data have been obtained here. Fiber orientation, flexural elastic modulus, and flexural fracture toughness of the composites have also been evaluated.     

Development of crystallinity in NEW-TPI polyimide

Development of crystallinity in NEW-TPI semicrystalline polyimide has been studied using differential scanning calorimetry (DSC), wide (WAXS), and small angle X-ray scattering (SAXS). Crystallinity of the fully imidized powder, pellet, or film processed NEW-TPI can occur from the melt, and depends upon the holding temperature of the melt. Repetitive exposure to elevated temperatures supresses the development of crystallinity from the melt state. In amorphous pellets and film, crystallinity can also develop by cold crystallization from the rubbery amorphous state. SAXS results show that during cold crystallization, NEW-TPI develops a periodic structure consistent with formation of alternating crystalamorphous stacks, but with crystals only a few molecular repeat units thick. Kinetics of nonisothermal crystallization were studied as a function of heating rate and could be described using the Ozawa analysis. Non-isothermal crystallization proceeds at a slower rate in NEW-TPI than in other high temperature thermoplastics such as PEEK, and with a much narrower processing window. The maximum degree of crystallinity that could develop during heating was 0.34, which occurred at a rate of 5°C/min. Similar degrees of crystallinity could be introduced by heating amorphous NEW-TPI film in N-methylpyrrolidone.     

工艺参数对聚丙烯/聚酰胺6共混物水辅助共注塑管件壁厚及性能的影响

基于自行搭建的水辅助共注塑实验平台,通过正交实验制备了系列水辅助共注塑管件,探究工艺参数对各层壁厚、拉伸性能及各相结晶的影响。结果表明,外层壁厚随着外层熔体温度、注水压力、内层熔体注射压力、模具温度增大而逐渐减小,随着熔体注射切换延迟时间、注水延迟时间增大而逐渐增大;内层壁厚随着注水延迟时间、内层熔体注射压力增大而逐渐增大,随着注水压力、模具温度增大而逐渐减小;管件拉伸强度随着外层熔体温度增大而逐渐减小,随着熔体注射切换延迟时间、注水延迟时间增大而逐渐增大;工艺参数会影响到成型壁厚及冷却进程,进而影响各相结晶度,最终影响管件性能。     

Crystallization behavior and morphological characterization of poly(ether ether ketone)

The crystal structure and morphology of poly(ether ether ketone) (PEEK) was investigated using standard differential scanning calorimetry (DSC), flash DSC, optical microscopy, atomic force microscopy, and small angle X-ray scattering tools. The flash DSC results suggested that the double melting peaks phenomenon observed in conventional DSC work originated from the reorganization of PEEK crystals, which was due to the much faster recrystallization rate of PEEK than the DSC heating and cooling rate. A refined crystallization model to describe PEEK crystal structure formation was proposed. The refined crystallization model could help reconcile the discrepancy found between the bulk crystallinity measured by DSC and the linear crystallinity obtained from SAXS experiments by taking into account possible variation in crystal perfection within the lamellar structure. Simplified molecular dynamic modeling was carried out to support this model. Implications of the above findings to the fundamental understanding of structure–property relationships in PEEK were discussed.     

Crystallization and melting behavior of poly(ether ether ketone)/poly(aryl ether sulfone) blends

The crystallization and melting behavior of poly(ether ether ketone) (PEEK) in blends with poly(aryl ether sulfone) (PES) prepared by melt mixing are investigated by differential scanning calorimetry (DSC) and wide‐angle X‐ray scattering (WAXS). The presence of PES is found to have a notable influence on the crystallization behavior of PEEK, especially when present in low concentrations in the PEEK/PES blends. The PEEK crystallization kinetics is retarded in the presence of PES from the melt and in the rubbery state. An analysis of the melt crystallization exotherm shows a slower rate of nucleation and a wider crystallite size distribution of PEEK in the presence of PES, except at low concentrations of PES, where, because of higher miscibility and the tendency of PES to form ordered structures under suitable conditions, a significantly opposite result is observed. The cold crystallization temperature of the blends at low PES concentration is higher then that of pure PEEK, whereas at a higher PES concentration little change is observed. In addition, the decrease in heat of cold crystallization and melting, which is more prevalent in PEEK‐rich compositions than in pure PEEK, shows the reduction in the degree of crystallinity because of the dilution effect of PES. Isothermal cold crystallization studies show that the cold crystallization from the amorphous glass occurs in two stages, corresponding to the mobilization of the PEEK‐rich and PES‐rich phases. The slower rate of crystallization of the PEEK‐rich phase, even in compositions where a pure PEEK phase is observed, indicates that the presence of the immobile PES‐rich phase has a constraining influence on the crystallization of the PEEK‐rich phase, possibly because of the distribution of individual PEEK chains across the two phases. The various crystallization parameters obtained from WAXS analysis show that the basic crystal structure of PEEK remains unaffected in the blend. Further, the slight melting point depression of PEEK at low concentrations of PES, apart from several other morphological reasons, may be due to some specific interactions between the component homopolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2906–2918, 2003     

Crystallization and fiber/matrix interaction during the molding of PEEK/carbon composites

The objective of this work was to investigate the effects of molding conditions (molding temperature, residence time at melt temperature, and cooling rate) on the crystallization behavior and the fiber/matrix interaction in PEEK/carbon composites made from both prepreg and commingled forms. In order to investigate the crystallization behavior of the PEEK matrix, the molding process was simulated by differential scanning calorimetric analysis, DSC. The results show that the prepreg and commingled systems do not have the same matrix morphology; prepreg tape was found to be at its maximum of crystallinity, whereas the commingled system was found to be only partially crystalline. The results show that processing must be carried out at a temperature sufficiently high to destroy the previous thermal history of the PEEK matrix; this is an essential requirement to produce efficient fiber/matrix adhesion in the commingled fabric system. Optical microscopic observations also suggest that matrix morphology near the fibers is dependent on the melting conditions; a well-defined transcrystalline structure at the interface is observed only when the melt temperature is sufficiently high. However, the high temperature of molding can easily result in degradation of the PEEK matrix such as chain scission and crosslinking reactions. Thermal degradation of the matrix during processing is found to affect the crystallization behavior of the composites, the fiber/matrix adhesion, and the matrix properties. This effect is more important in the case of a commingled system containing sized carbon fibers because the sizing agent decomposes in the molding temperature range of PEEK/carbon composites. This produces a decrease of the matrix crystallinity and an elimination of the nucleating ability of the carbon fibers. A transition between cohesive and adhesive fracture is observed when the cooling rate increases from 30°C/min to 71°C/min for the composite made from the commingled fabric. This critical cooling rate is found to closely correspond to a change in the mechanism of crystallization of the PEEK matrix.     

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

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

Effect of polymer properties on the structure of injection-molded parts

In this study, the distributions of both molecular orientation and crystallinity along the flow direction as well as across the thickness direction of injection-molded specimens of poly(ethylene terephthalate) (PET) molded at different mold temperatures were investigated. The degree of molecular orientation at the surface of the specimens was compared with that of other injected materials (polystyrene, high density polyethylene, liquid crystal polymer) showing different thermal, rheological, and crystallization characteristics. It was found that the molecular orientation at the skin layer of the molding increases with the polymer relaxation time, the rigidity of the polymer molecules, and the crystallization rate of the polymer. Moreover, in the case of PET, it was found that the crystallinity at the skin layer and in the core of the molding depends on the mold temperature. For low mold temperatures, near the gate, the maximum of crystallinity was observed at the subskin layer because of the “shear-induced crystallization” generated during the filling stage. On increasing the mold temperature, the maximum of crystallinity was found to shift to the skin layer as a result of the decrease of the thickness of this layer. For low mold temperatures, the variation of the molecular orientation in the thickness direction was found to be much the same as for the crystallinity of the polymer. This result indicates that the shear-induced crystallization process improves the degree of molecular orientation in the flow direction since it inhibits the relaxation process of the polymer molecules.     

Influence of molecular weight on rheological,thermal, and mechanical properties of PEEK

This study focuses on the influence of molecular weight on the rheological, thermal, and mechanical behavior of poly(ether‐ether‐ketone) (PEEK), a semicrystalline high‐performance polymer. The results show that the molecular weight of PEEK has significant influence on its rheological, thermal, and mechanical behavior. It was found that PEEK has the unique characteristic of two shear‐thinning regions. The shear viscosity and the stress relaxation time of PEEK increase significantly as molecular weight increases. In general, the Cox‐Merz rule is valid for all grades of PEEK. As molecular weight increases, the melting temperature of PEEK decreases slightly, but its isothermal and nonisothermal crystallization temperatures drop dramatically. As molecular weight increases, the crystallinity, the crystallization rate, and the magnitude of crystallization activation energy decrease. The crystallization kinetics study indicates that PEEK tends to form spherical crystalline structures, regardless of its molecular weight. As molecular weight increases, the tensile strength at yield, the tensile modulus, and the flexural modulus of PEEK decrease slightly, whereas the tensile strength at break, the tensile strain at break, the modulus of toughness, and the impact strength of PEEK increase significantly. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

碳纤维增强聚醚醚酮的非等温结晶行为与力学性能

利用聚酰亚胺(PI)作为碳纤维(CF)界面改性剂,制备了界面改性碳纤维增强聚醚醚酮(MCF/PEEK)复合材料。采用差示扫描量热仪(DSC)讨论了CF及其界面改性对PEEK非等温结晶行为的影响机制与作用规律,并基于莫志深法研究了MCF/PEEK的非等温结晶动力学;借助DSC和小角X射线散射仪(SAXS)表征不同降温速率下PEEK基体的结晶结构,采用万能试验机评价了MCF/PEEK的力学性能。结果发现:CF对PEEK的结晶有较为明显的异相成核促进作用,经过PI界面改性之后成核作用有所下降,但结晶行为仍较纯PEEK更容易发生,整体结晶速率更快;随冷却速率的增大,基体结晶度、片晶厚度与长周期均减小,MCF/PEEK的拉伸强度与模量也显著减小,层间断裂韧性提高。     

Crystallization phenomena in the injection molding of poly ether ether ketone and its influence on mechanical properties

A basic experimental investigation of structure development in the injection molding of poly ether ether ketone (PEEK) is presented. It is shown that, dependent upon processing conditions, especially mold temperature, PEEK may be injection molded to form glassy or crystalline parts or parts consisting of intermediate structures such as a glassy surface and one with an internal crystalline link. In general, cold molds produce glassy parts and hot molds crystalline parts. This behavior is carefully characterized using optical microscopy, differential scanning calorimetry, and wide angle X-ray diffraction techniques. The mechanical properties of these injection molded parts is characterized as a function of the crystalline and glassy contents and types of structural gradients developed in the parts.     

注射成型工艺参数对PP制品结晶度影响的实验研究

利用5因素4水平正交试验表安排16组实验,通过对注射成型参数进行调节,研究了聚丙烯制品结晶度随成型工艺参数发生变化的规律。结果表明,对结晶度影响较显著的因素是保压压力,影响较大的因素是模具温度,熔体温度、保压时间和注射速度的影响较小。成型工艺参数对结晶度的影响主要是使分子在应力诱导下发生结晶,在成型过程中降低熵。     

Nonisothermal crystallization of poly(ethylene terephthalate) and its blends in the injection-molding process

We investigated the nonisothermal crystallization during the cooling process of injection molding of poly(ethylene terephthalate) (PET), PET/talc, and PET/Surlyn blends. We applied the isothermal crystallization parameters obtained by the Hoffman–Lauritzen theory to the kinetics of nonisothermal crystallization and then calculated the relative crystallinity χ/χ_c as a function of the mold temperature. χ/χ_c were nicely interpreted by calculation without effect of the pressure history on crystallization in PET and PET/talc (1 wt %) blends. In contrast, in the PET/Surlyn (3 wt %) blend, crystallization occurred at a lower mold temperature than predicted by our calculation. The transmission electron micrograph near the surface of the injection-molded PET/Surlyn blend showed deformation and stretching of dispersed Surlyn particles, suggesting that orientation of the PET matrix proceeds with the flow in processing. The orientation of the PET matrix resulted in acceleration of the crystallization in the injection molding. © 1995 John Wiley & Sons, Inc.     

Manipulation of thick-walled PEEK bushing crystallinity and modulus via instrumented compression molding

An instrumented hot compression molding apparatus was fabricated to allow real-time monitoring and precise temperature control during the compaction and consolidation of large polyether ether ketone (PEEK) products. The objective was to determine the impact of controlled variables on the properties of the molded article. Four different strategies were designed to control the mold thermal profiles. The average crystallinity in a commercial molding process is restricted due to large thermal masses with low thermal conductivity. In contrast, this research was able to reduce the crystallinity range from 33% to 6% by developing a special controlled apparatus and implementing new processing methodologies. In this study, PEEK showed a significant increase in the modulus compared to typical values measured on commercially produced analogs, and a higher degree of property uniformity. In a single commercially molded PEEK billet, compressive modulus variability was 13% at room temperature, and 21% at 225°C. Properties of billets produced using the laboratory apparatus showed a reduction in variability to 2%.     

Preparation and characterization of high‐performance poly(ether ether ketone) fibers with improved spinnability based on thermotropic liquid crystalline poly(aryl ether ketone) copolymer

High‐performance poly(ether ether ketone) (PEEK) fibers were prepared by melt‐spinning in the presence of thermotropic liquid crystalline poly(aryl ether ketone) copolymer (FPAEKLCP). The rheological and mechanical properties, birefringence, orientation, and crystallization of the resulting PEEK/FPAEKLCP fibers were characterized by using a melt flow indexer, capillary rheometer, single fiber electronic tensile strength tester, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD), respectively. The results indicate that the melt viscosity of PEEK significantly reduced by introducing FPAEKLCP, followed by the improvements in the spinnability and the quality of as‐spun fibers. The tensile properties of PEEK/FPAEKLCP fibers mainly depend on the content of FPAEKLCP, drawing temperature, drawing ratio, and annealing processes. Moreover, the tensile strength and modulus of PEEK/FPAEKLCP fibers are obviously higher than those of neat PEEK fibers under the same processing conditions. This should be attributed to an enhancement in the orientation and crystallization of PEEK compounded with FPAEKLCP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1406‐1414, 2013     

Rheological and crystallization enhancement in polyphenylenesulfide and polyetheretherketone POSS nanocomposites

Polyhedral oligomeric silsesquioxane (POSS) additives have been shown to increase melt‐flow and crystallization in thermoplastics. In this study, the effect of incorporation of trisilanolphenyl‐POSS molecules in polyphenylenesulfide (PPS) and polyetheretherketone (PEEK) on rheology, crystallization kinetics, and thermal and mechanical properties was evaluated. Parallel plate rheometry revealed a reduction in the viscosity of PPS and PEEK with the addition of POSS. The magnitude and concentration dependence of rheological modification were shown to depend on the polymer structure and POSS solubility. Isothermal crystallization kinetics were analyzed using the Avrami model and it was found that the addition of POSS accelerated the crystallization rate of PPS blends with no significant effect on PEEK blends. Interestingly, no statistical difference in degradation temperature, tensile modulus, or tensile strength of PPS or PEEK blends was observed. The findings indicate the potential for improvements in melt viscosity and crystallization of high temperature thermoplastics with tailored POSS/polymer interactions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44462.     

Phase behavior,crystallization, and morphology of poly(ether ether ketone)/polyarylate blends

The phase behavior, crystallization, and morphology of blends based on poly (ether ether ketone) [PEEK] and bisphenol-A polyarylate [PAr] are described. This system is partially miscible in the melt. Upon quenching to an amorphous glass the system displays two glass transitions corresponding to a nearly pure PEEK phase (T_g1) and a PAr-rich mixed phase (T_g2). The presence of the PAr has a strong retarding influence on the rate of crystallization of PEEK in the blends. Cold crystallization from the amorphous glass occurs in two stages with increasing temperature, corresponding to the mobilization of the PEEK-rich and PAr-rich phases, respectively. At lower cold-crystallization temperatures (below T_g2), the immobile PAr-rich phase constrains crystallization of the PEEK-rich phase, as manifested in both a decreased rate of crystallization and decreased bulk crystallinity. Dynamic relaxation studies of the crystallized blends reveal two glass-rubber relaxations originating from interlamellar amorphous populations in the PEEK-rich and PAr-rich phases. In the PAr-rich phase, there is no evidence of large-scale PAr exclusion to interfibrillar or interspherulitic regions.     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of semicrystalline polymers

A novel approach to predict anisotropic shrinkage of semicrystalline polymers in injection moldings was proposed using flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from amorphous and crystalline contributions. The amorphous contribution was based on the frozen‐in and intrinsic amorphous birefringence, whereas the crystalline contribution was based on the crystalline orientation function, which was determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with temperature‐ and crystallinity‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs on polypropylene of various molecular weights were carried out by varying the packing time, flow rate, melt temperature, and mold temperature. The anisotropic shrinkage of the moldings was measured. Comparison of the experimental and simulated results indicated a good predictive capability of the proposed approach. POLYM. ENG. SCI., 46:712–728, 2006. © 2006 Society of Plastics Engineers     

Thermal properties,structure and morphology of PEEK/thermotropic liquid crystalline polymer blends

The dynamic crystallization and subsequent melting behaviour of poly(aryl ether ether ketone), PEEK, and its blends with a thermotropic liquid crystalline polymer, Vectra^®, have been studied using differential scanning calorimetry, optical microscopy and wide‐angle and small‐angle X‐ray diffraction (WAXS and SAXS) techniques in a wide compositional range. Differences in crystallization rates and crystallinities were related to the structural and morphological characteristics of the blends measured by simultaneous real‐time WAXS and SAXS experiments using synchrotron radiation and optical microscopy. The crystallization process of PEEK in the blends takes place in the presence of the nematic phase of Vectra and leads to the formation of two different crystalline families. The addition of Vectra reduces the crystallization rate of PEEK, depending on composition, and more perfect crystals are formed. An increase in the long period of PEEK during heating was generally observed in the blends at all cooling rates. Copyright © 2003 Society of Chemical Industry