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.     

Effects of mechanical drawing on the structure and properties of peek

This study examines the effects of crystallinity and temperature on the mechanical properties of PEEK. Crystallinity in PEEK Increases with annealing temperature up to a maximum of 28 percent with a melting point at 335°C. A minor melting peak also occurs about 10°C above the annealing temperature. In cold drawing the samples exhibited a yield stress and necking followed by homogeneous drawing. The yield stress increases with crystallinity, but there is no change in the modulus. The extension in the necking process also increases with crystallinity, however there is only a slight increase in extension-to-break since necking is compensated by the final amount of homogeneous drawing. The yield stress of PEEK when drawn at T_g (145°C) is significantly lower than at room temperature indicating a reduction in mechanical properties at temperatures approaching T_g. After mechanical drawing the minor melting peak disappears and on heating the material undergoes cold crystallization near the onset of T_g. There is evidence that this minor crystalline component might contribute to the yield stress changes with annealing history. Cold drawing induces crystallization of amorphous PEEK but decreases crystallinity and generates microscopic voids in crystalline PEEK, The various effects of crystallinity on mechanical properties could be important in determining the stress response of PEEK as the matrix in composites.     

Effects of thermal history on mechanical behavior of PEEK and its short-fiber composites

The effect of crystallinity differences induced by mold wall temperature and annealing on mechanical behavior is evaluated for poly(etheretherketone) (PEEK) resin and its composites. The systems investigated were neat PEEK, glass fiber (GF) reinforced PEEK, and carbon fiber (CF) reinforced PEEK. Both composite systems were reinforced with 10, 20, and 30 wt% fiber. The degree of crystallinity (X_c) of PEEK was found to increase by processing at higher mold temperatures, by annealing, and by fiber length reductions, which appears to indicate the ability of short fibers to nucleate the crystallization of PEEK under favorable thermal conditions. Improvements in Young's modulus and strength together with ductility reductions are generally obtained as crystallinity increases in both neat PEEK and its composites. The contribution of crystallinity to mechanical behavior is significant only for neat PEEK and PEEK reinforced by 10% fiber. SEM micrographs reveal that this is due to a change in failure mode. When PEEK is reinforced by carbon fibers or by 20–30% glass fibers, a macroscopic brittle mode of failure is observed irrespective of matrix crystallinity, and mechanical behavior is principally determined by the nature and content of the reinforcing fibers.     

熔融共混PPS／PEEK中PPS组分的结晶行为

采用熔融共混法制备结晶／结晶共混体系ＰＰＳ／ＰＥＥＫ，并用差示扫描量热法研究了不同ＰＥＥＫ含量和不同ＰＥＥＫ粒径对ＰＰＳ／ＰＥＥＫ共混物中ＰＰＳ组分结晶行为的影响。随ＰＥＥＫ含量的增加ＰＰＳ的结晶温度提高，结晶峰宽增加。这是由于在降温过程中ＰＥＥＫ先结晶，可充当ＰＰＳ熔体结晶的异相晶核，使ＰＰＳ结晶温度提高，且随着ＰＥＥＫ含量增加，异相晶核密度增大，但ＰＥＥＫ晶区的存在阻碍了ＰＰＳ的结晶生长过程，     

Crystallinity of isothermally and nonisothermally crystallized poly(ether ether ketone) composites

PEEK/carbon fiber composites were prepared by a modified diaphragm forming machine under vacuum. The study of the degree of crystallinity versus the differential scanning calorimetry (DSC) heating rate indicated that 50°C/min was an optimal heating rate to suppress the reorganization of the specimens crystallized between 315°C and 255°C and to avoid superheating the specimens. A high volume of fibers constrained the spherulitic growth by an impingement mechanism, which depressed the crystallization rate and reduced the crystallinity. Thus the crystallization was still in process even after 240 min annealing at 300°C. The effect of the cooling rate on the degree of crystallinity was simulated and investigated in DSC at a heating rate of 50°C/min. The results indicated that the cooling rates ranging from 1°C/min to 100°C/min could be divided into five regions that were associated with a high volume of fiber and the crystallization regime. A Time-Temperature-Transformation diagram superposed on the Continuous-Cooling-Transformation curves allows us to predict the amount of crystallization in different regimes. The data points for the DSC method deviated from the prediction at the cooling rates above 60°C/min because of the recrystallization during DSC heating scans.     

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.     

聚苯酯对聚醚醚酮结晶行为的影响

用模压法制备了聚苯酯(Ekonol)／聚醚醚酮(PEEK)复合材料，通过X射线衍射(XRD)、差示扫描量热分析(DSC)考察了PEEK的结晶行为，并测定了复合材料的熔点、结晶温度和玻璃化转变温度。结果表明：Ekonol含量的大小对PEEK的结晶行为产生了直接影响，PEEK的相对结晶度随着Ekonol含量的增加而提高；Ekonol含量小于30％时，对复合材料的熔点、结晶温度和玻璃化转变温度影响不大，但含量大于30％时，材料的结晶温度、熔融温度下降，玻璃化转变温度提高。     

熔融条件对聚醚醚酮结晶熔融行为的影响

用ＤＳＣ法研究了熔融温度和熔融时间对聚醚醚酮地晶熔融行为的影响。实验表明，聚醚醚酮的结晶峰随熔融延长向高温移动，且峰形变窄，峰的强度增大，继续延长熔融时间，结晶峰降低，峰形变宽；熔融时间延长时，聚醚醚酮的玻璃化转变温度和冷结晶峰温度均提高，熔融峰强度减弱。熔融温度升高时，聚醚醚酮的结晶峰强度减弱，峰宽增强；而冷结晶温度提高。     

Effect of thermal history on the crystallization behaviour of polyetheretherketone by the dynamic viscoelastometer

The effect of thermal history on the crystallization behaviour of PEEK is investigated by the dynamic viscoelastometer. The crystallization behaviour of PEEK shows significant influence on the α peak in the tan δ and the storage modulus. The α peak temperature is rapidly increased at shorter times with the annealing temperature at 160°C or higher, and is then constant. The storage modulus is more gently reduced in the α transition region as the annealing temperature is higher, and becomes then a constant value. It is suggested that the reduction in the storage modulus corresponds to some defect in the crystal structure of PEEK.     

Crystallization behavior of poly(lactic acid)/elastomer blends

Differential Scanning Calorimetry (DSC) was used to evaluate the crystallization behavior of poly(lactic acid) and its blends with elastomer. It has been observed that the cold crystallization temperature of the blends decreased as the weight fraction of elastomer increased as well as the onset temperature of cold crystallization also shifted to lower temperature. In non-isothermal crystallization experiments, the crystallinity of poly(lactic acid) increased with a decrease in the heating and cooling rate. The melt crystallization of poly(lactic acid) appeared in the low cooling rate (1, 5 and 7.5 °C/min). The presence of low elastomer tends also to increase the crystallinity of poly (lactic acid). The DSC thermogram at ramp of 10 °C/min showed the maximum crystallinity of poly(lactic acid) is 36.95% with 20 wt% elastomer contents in blends. In isothermal crystallization, the cold crystallization rate increased with increasing crystallization temperature in the blends. The Avrami analysis showed that the cold crystallization was in two stages process and it was clearly seen at low temperature. The Avrami exponent (n) at first stage was varying from 1.59 to 2 which described a one-dimensional crystallization growth with homogeneous nucleation, whereas at second stage was varying from 2.09 to 2.71 which described the transitional mechanism to three dimensional crystallization growth with heterogeneous nucleation mechanism. The equilibrium melting point of poly(lactic acid) was also evaluated at 176 °C.     

Flow-induced crystallization of linear polyethylene above its normal melting point

The phenomenon of flow-induced crystallization was investigated using a linear polyethylene above its normal melting point flowing continuously in a Biconical Rheometer. It was found that the resin crystallized in the superheated state at rates which increased with increasing shear rate and decreasing temperature. A method of analysis of the temperature dependence of the various stages of flow induced crystallization is proposed. It deals with and attempts to explain the experimental fact that a higher viscosity enhances the rate of flow-induced crystallization in contrast to the effect of viscosity on the rate of quiescent crystallization. Some of the flow-induced crystallization samples were transparent and exhibited a high DSC thermogram “tail”.     

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.     

PPS／PEEK熔融共混物DSC多次扫描研究

借助ＤＳＣ研究ＰＰＳ／ＰＥＥＫ共混物熔融时间，ＰＥＥＫ粒径及ＰＰＳ组分对共混物中ＰＥＥＫ结晶熔融行为的影响，结果表明，ＰＥＥＫ粒径由５００～１０００μｍ减小至２００～５００μｍ时，ＰＥＥＫ与ＰＰＳ相互作用增大，ＰＥＥＫ的结晶峰由单峰分裂为双峰，其高温结晶峰向高温移动，峰强随熔融时间延长而减弱，低温结晶峰向低温移动，峰强随熔融时间延长而增大，熔融时间延长时，退火后ＰＥＥＫ的低温熔融峰强增大，而高温熔     

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     

超拉伸过程中UHMWPE纤维结构与性能的研究

利用密度梯度仪、声速取向仪、Instron材料强力仪、WAXD、DSC等手段 ,对超高相对分子质量聚乙烯 (UHMWPE)纤维在超拉伸过程中的结构和性能进行了测试研究。结果表明 ,不同拉伸倍数的UHMWPE纤维的结晶度、取向度、力学性能和熔融温度随着拉伸倍数的增大而增加 ;DSC图谱上的 Tm4 峰和WAXD分析证实了在超拉伸过程中UHMWPE纤维发生了正交晶相向六方晶相的转变 ,超拉伸后期结晶结构的变化对纤维的力学性能影响很大。     

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.     

Temperature modulated DSC studies of melting and recrystallization in poly (oxy‐1,4‐phenyleneoxy‐1,4‐phenylenecarbonyl‐1,4‐phenylene) (PEEK)

The thermal and crystal morphological properties of amorphous and melt crystallized poly(oxy‐1,4‐phenyleneoxy‐1,4‐phenylenecarbonyl‐1,4‐phenylene) (PEEK) were investigated. Two different molecular weights were studied by Temperature Modulated DSC (TMDSC) over a broad range of annealing times and temperatures. The lower molecular weight PEEK under all crystallization conditions was found to exhibit secondary crystal melting in the low endotherm region, followed by melting of primary crystals melting in the low endotherm region, followed by melting of primary crystals superimposed with a large recrystallization contribution. Primary crystal melting broadly overlapped with melting of the recrystallized species and contributed to the broad highest endotherm. Recrystallization contributions and the interpretation of TMDSC were partially confirmed by independent rapid heating rate melting point determinations and variable heating rate DSC. The higher molecular weight PEEK showed many similarities but generally had smaller levels of reorganization above the annealing temperature under most higher temperature crystallization conditions. TMDSC provides excellent resolution of recrystallization and related events compared to standard DSC. The broad and substantial exothermic recrystallization in amorphous samples was also examined, showing that recrystallization continues through the final melting region.     

Dynamic-mechanical and dielectric characterization of PEEK crystallization

Dynamic-mechanical and dielectric characterization of the cold crystallization of PEEK has been performed in order to develop a non-destructive evaluation method of crystallinity in thermoplastic matrices. The Avrami approach is applied here to describe the Poly(ether ether ketone) (PEEK) crystallization kinetics after an appropriate reduction of dynamic-mechanical and dielectric parameters. Avrami exponents obtained from dielectric characterization are comparable with those obtained with DSC measurements reported in literature, while the exponents obtained from the dynamic-mechanical characterization are higher, reflecting also changes in the aspect ratio of the growing crystals. Variations in the glass transition temperature detected during cold crystallization are analyzed and analogies between PEEK and PET are discussed.     

The influence of crystallinity on interfacial properties of carbon and SiC two‐fiber/polyetheretherketone (PEEK) composites

The influence of the degree of crystallinity on interfacial properties in carbon and SiC two‐fiber reinforced poly(etheretherketone) (PEEK) composites was investigated by the two‐fiber fragmentation test. This method provides a direct comparison of the same matrix conditions. The tensile strength of the PEEK matrix and the interfacial shear strength (IFSS) of carbon or SiC fiber/PEEK exhibited the maximum values at around 30% crystallinity, and then showed a decline. The tensile modulus increased continuously with an increase in the degree of crystallinity. Spherulite sizes in the PEEK matrix became larger as the cooling time from the crystallization temperature increased. Transcrystallinity of carbon fiber/PEEK was developed easily and more densely than with SiC fiber/PEEK. This might have occurred because the unit cell dimensions of the crystallite in the fiber axis direction on the carbon surface was more suitable for making nucleation sites. The IFSS of carbon fiber/PEEK was significantly higher than that of SiC fiber/PEEK because it formed transcrystallinity of IFSS more favorably.     

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。