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.     

Crystallization kinetics of poly(phenylene sulfide) (PPS) and PPS/carbon fiber composites

The evolution of crystallinity of neat PPS and of the carbon fiber reinforced polymer under different processing conditions is studied. Crystallization from the amorphous state at low temperatures (cold crystallization), crystallization from the melt during cooling, and crystal melting processes are analyzed using calorimetric techniques under both isothermal and nonisothermal conditions. Cold and melt crystallization kinetics are described using an Avrami equation and an Arrhenius expression for the temperature dependence of the kinetic constant. Also, the melting kinetics of the, reinforced and of the unreinforced polymer are studied in this work. The effect of carbon fibers on the crystallization kinetics of PPS is analyzed, and a comparison of the crystallization behavior of PPS and other semicrystalline thermoplastic matrices, such as poly(etheretherketone) (PEEK), is presented.     

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.     

Influence of carbon nanotubes on the thermal, electrical and mechanical properties of poly(ether ether ketone)/glass fiber laminates

Novel poly(ether ether ketone) (PEEK)/single-walled carbon nanotube (SWCNT)/glass fiber laminates incorporating polysulfone as a compatibilizing agent were fabricated by melt-blending and hot-press processing. Their morphology, mechanical, thermal and electrical properties were investigated and compared with the behavior of similar non-compatibilized composites. Scanning electron micrographs demonstrated better SWCNT dispersion for samples with polysulfone. Thermogravimetric analysis indicated a remarkable improvement in the thermal stability of PEEK/glass fiber by the incorporation of SWCNTs wrapped in the compatibilizer, ascribed to a significant thermal conductivity enhancement. Differential scanning calorimetry showed a decrease in the crystallization temperature and crystallinity of the polymer with the addition of both wrapped and non-wrapped SWCNTs. The laminates exhibit anisotropic electrical behavior; their conductivity out-of-plane is lower than that in-plane. Dynamic mechanical studies revealed an increase in the storage modulus and glass transition temperature in the presence of polysulfone. Mechanical tests demonstrated significant enhancements in stiffness, strength and toughness by the incorporation of wrapped nanofillers, whilst the mechanical properties of non-compatibilized composites only improved marginally. Samples with laser-grown SWCNTs exhibit enhanced overall performance. This investigation confirms that SWCNT-reinforced PEEK/glass fiber compatibilized composites possess excellent potential to be used as multifunctional engineering materials in industrial applications.     

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.     

Material response of a semicrystalline thermoplastic polymer and composite in relation to process cooling history

A model capable of predicting the process-induced macroscopic in-plane material response of semicrystalline thermoplastic matrices and their composites was developed. Thi sinvestigation focused on the material response of a single layer or ply of neat PEEK matrix and its carbon fiber composite (APC-2) when subjected to various processing histories. Specifically, the response of the material moduli and processing strains as a function of temperature and the degree of crystallinity were studied. The kinetic-viscoelastic response of the matrix was determined from a modified form of the Standard Linear Solid model. A constitutive relation was proposed to quantify resign shrinkage as a function of thermal history, which incorporated crystallization. For a specific process history, the effective composite mechanical properties were determined from micromechanics models. Both neat and composite processing strains were evaluated to show the effect of fibers on the matrix dominated response (90° direction). In addition, comparisons of model moduli predictions with experimental measurements were performed. This study demonstrated that an increase in the degree of crystallinity results in an asymmetric shift of the modulus in the glass transition region to higher temperatures. Also, strains due to crystallization were predicted to be much smaller in comparison to the strains resulting from thermal contraction of the PEEK matrix.     

Effects of sorbed caprolactam on the crystallinity,morphology, and deformation behavior of polyetheretherketone and poly(phenylene sulfide)

Studies on the high temperature sorption of caprolactam by polymer resins and their composites have been conducted. The systems investigated were glass fiber reinforced (GFR) poly(phenylene sulfide) (PPS), polyetheretherketone (PEEK) neat resin, GFR PEEK and carbon fiber reinforced (CFR) PEEK. To measure changes of caprolactam sorption, melting behavior, mechanical properties, and fracture surface morphology were determined. Absorption of caprolactam by the PEEK composites was 30 to 40 percent less than by the neat resin. This is attributed to the fibers, which acted to constrain the matrix and thus limit its swellability. Reductions in melt temperature, percent crystallinity, ultimate tensile strength, and modulus were observed following exposure to the chemical environment. The loss of strength and stiffness was a consequence of the degradation of the matrix/fiber interface by the sorbed caprolactam.     

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。     

Fluid sorption characterization of PEEK matrices and composites

Neat poly(ether-ether-ketone) (PEEK) and carbon fiber reinforced PEEK (APC-2) specimens were prepared using a variety of cooling rates to achieve a range of crystallinities. Amorphous specimens were exposed to a variety of fluids to determine the penetrant types which are able to strongly influence the material. This allowed the estimation of the solubility parameter and hydrogen bonding index for PEEK to be 9.5 and 3.1, respectively. Methylene chloride was used to investigate the kinetics of penetrant sorption. The data demonstrated Case II behavior, with the initial crystallinity having a pronounced effect on both the kinetic and equilibrium data. Accordingly, a model was proposed capable of describing the sorption level and penetration depth as a function of time given the sample crystallinity and sorption temperature. With Case II behavior there was no difference in the sorption kinetics of neat and fiber reinforced PEEK. Finally, the dynamic mechanical properties measured during sorption were found to be dependent on the sorption process.     

Crystallization of poly(etheretherketone) (PEEK) in carbon fiber composites

The tendency of carbon fiber to nucleate the zation of poly(etherettterlcetone) (PEEK) has been evaluated by DSC and other techniques. As the carbon fiber content was increased, the supercooling necessary for PEEK crystallization decreased. The repeated melting (at 396°C) of the same PEEK sample results in a decrease of the number of nuclei for crystallization. At equivalent thermal histories, PEEK with carbon fiber was found to have a higher nucleation density than PEEK itself. The surface of carbon fibers and nuclei in the PEEK matrix compete for crystallization growth. As the holding time in melt was increased, the number of matrix spherulites formed on cooling decreased, hence a more pronounced transcrystalline region was developed. Correspondingly, the composites preheated in the melt for 100 min showed about two times the transverse tensile strength and strain-to-failure of those preheated for only 30 min. Corresponding fracture surface produced in tension showed that the former samples had a greater matrix adhesion to the carbon fiber than the latter. A strong interfacial bond is thus developed by crystallization on carbon fiber surface. Destroying nuclei in the PEEK matrix by long preheating enhances crystallization on the carbon fiber.     

Adhesion at copper- polyamide 11- copper and aluminum-poly amide 11-aluminum laminate interfaces: influence of metal surface oxidation

Adhesion at copper-polyamide 11-copper and at aluminum-polyamide 11-aluminum laminate interfaces was studied. Metal-polymer-metal laminates were prepared by compression molding using processing conditions similar to the normal melt processing of polyamide 11. The results show that the time of contact at the molding temperature required to reach a constant level of adhesion is significant. Mild oxidation of the metal prior to molding improves the adhesion of polyamide 11 to aluminum; with copper, a monotonic slow decrease in adhesion with the oxidation time is observed. The presence of a metal surface affects the crystallization behavior of polyamide. With a cooling rate of 40-50°C/min, an approximately 15 μm transcrystalline polymer layer is formed with a degree of crystallinity that is almost 10% higher than the material away from the interface. The metal substrate surface oxidation prior to molding does not change the crystallinity profile of the polymer in the bulk. The polymer surface crystallinity is also a function of the time of contact with the metal substrate. The cooling rate and the metal substrate structure and its nucleating activity are responsible for the surface/bulk crystallinity ratio. Although the highly-crystalline polymer surface layer improves the adhesion to some extent, the formation of active species on the polymer surface which are able to react with the metal surface is mostly responsible for the increase of adhesion with time and its ultimate strength.     

Characterization and exposure of polyetheretherketone (PEEK) to fluid environments

The sorption and desorption behaviour in fluids is described for polyetheretherketone (PEEK) films of different crystallinity. Water, Skydrol, and methylene chloride were used as fluid environments at two temperatures, and the weight gain of the films as a function of time was recorded. Density, thermomechanical, and dynamic mechanical measurements were made for the films before and after the fluid exposure. The results confirmed the general solvent resistance of PEEK. However, exposure to methylene chloride produced two significant effects: plasticization and additional crystallization for incompletely crystallized films. Exposure to different fluids was shown to suppress the exhibited thermomechanical transitions of these films. For the incompletely and fully crystallized films a comparison was made for crystallinity values obtained by the differential scanning calorimetric and density gradient techniques. Finally,dynamic mechanical and sorption in methylene chloride data obtained for PEEK reinforced with continuous carbon fibres are provided for comparison to the neat polymer results.     

The comparison of low‐velocity impact resistance of aluminum/carbon and glass fiber metal laminates

This article presents the low‐velocity impact response of fiber metal laminates, based on aluminum with a polymer composite, reinforced with carbon and glass fibers. The influence of fiber orientations as well as analysis of load‐time history, damage area and damage depth in relation to different energy levels is presented and discussed. The obtained results made it possible to determine characteristic points, which may be responsible for particular stages of the laminate structure degradation process: local microcracks and delaminations, leading to a decrease in the stiffness of the laminate, as well as further damage represented by laminate cracks and its perforation. The damage mechanism of fiber metal laminates is rather complex. In case of carbon fiber laminates, a higher tendency to perforation was observed in comparison to laminates containing glass fibers. Delaminations in composite interlayers and at the metal/composite interface constitute a significant damage form of fiber metal laminates resulting from dynamic loads. Fiber metal laminates with glass fibers absorb energy mainly through plastic deformation as well as through delamination initiation and propagation, whereas laminates containing carbon fibers absorb energy for penetration and perforation of the laminate. POLYM. COMPOS. 37:1056–1063, 2016. © 2014 Society of Plastics Engineers     

Thermoforming of advanced thermoplastic composites. I: Single curvature parts

Thermoforming has been studied for a single curvature part made from various advanced thermoplastic matrix composite prepregs. For parts with acceptable shape conformity, preheating of the composite laminates to a processing temperature of 350 to 400°C is necessary prior to forming with molds maintained at 200°C. However, only PEEK/carbon fiber prepreg tapes yielded parts with acceptable microstructural integrity and a matrix crystallinity level of about 30 percent. Amorphous matrix based PXM 8505/T500 fabric prepregs also result in lamination and void free parts, but fiber matrix distribution in this case was rather poor. Parts thermoformed from other prepreg laminates contained voids and/or were delaminated, thereby indicating the need for higher mold temperature and forming pressure than that afforded by the present study, in which a standard lab-scale thermoforming machine was used.     

Structural degradation and mechanical fracture of hybrid fabric reinforced composites

This investigation involves the study of accelerated environmental aging in two polymer composite laminates reinforced by hybrid fabrics based on carbon, Kevlar and glass fibers. Composite laminate configurations are defined as a laminate reinforced with E‐glass fiber and Kevlar 49 fiber hybrid fabric (GK) and another laminate reinforced with E‐glass fiber and AS4 carbon fiber hybrid fabric (GC). Both laminates were impregnated with epoxy vinyl ester thermosetting resin (Derakane 470‐300) consisting of four layers. Morphological studies (photo‐oxidation process and structural degradation) of environmental aging were conducted, in addition to comparative studies of the mechanical properties and fracture characteristics under the action of uniaxial tensile and three‐point bending tests in specimens in the original and aged conditions. With respect to uniaxial tensile tests for both laminates, good mechanical performance and little final damage (small loss of properties) was caused by the aging effect. However, for the three‐point bending tests, for both laminates, the influence of aging was slightly higher for all parameters studied. The low structural deterioration in the laminates is attributed to the high performance with the heat of the matrix (Derakane 470‐300) and the characteristics of the hybrid fabric, exhibiting fiber/matrix interface quality. POLYM. ENG. SCI., 56:657–668, 2016. © 2016 Society of Plastics Engineers     

Thermal analysis of thermoplastic composites during processing

Unsteady two-dimensional thermal analysis has been performed on PEEK/AS-4 fiber thermoplastic composites. To calculate the crystallinity of the composite, a spherulite growth model was applied. A numerical analysis was carried out with variations in mold cooling rate, the prepreg lay-up, and the composite geometry. The effect of geometry and the cooling rate is significant in the temperature profiles. The degree of crystallinity varies with the cooling rate, but the gradient of crystallinity is small, with the exception of complex geometries at fast cooling rates. The results of numerical calculations are in excellent agreement with the experiments and offer validation of the numerical formulation.     

Instrumented thermoforming of advanced thermoplastic composites. II: Dynamics of double curvature part formation and structure development from PEEK/carbon fiber prepreg tapes

Poly(ether ether ketone) (PEEK) carbon fiber prepreg tapes (APC-2) have been thermoformed into a hemispherical double curvature part under a variety of processing conditions. Conventional matched die molding using aluminum molds (at 200°C) were not successful in thermoforming acceptable parts. Parts with severe wrinkling and folding were obtained. A novel three-piece (steel) mold with built-in sheet clamping arrangement was, therefore, designed and fabricated. This mold was used at 400°C temperature to thermoform parts from preheated preconsolidated laminates. More interestingly, using the above conditions, 8- and 16-ply unconsolidated laminates could be directly thermoformed into parts that were microstructurally sound and exhibited good shape conformity. Results suggest a cycle time of 15 min, with scope for further reduction, if mold cooling is employed. Notwithstanding the simplicity of the thermoforming process, such a short cycle time compares quite favorably with cycle times of several hours for conventional thermosetting resin based composites.     

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.     

Fluorescence monitoring of polymer injection molding: Model development

We have developed models to describe the behavior of an optical fiber sensor which was used to detect fluorescence from a polymer resin during the cooling phase of injection molding. The optical fiber sensor was positioned at the wall of the mold cavity by using the ejector pin channel as access to the cavity. The sources of fluorescence were dyes, which were chosen because of their sensitivity to temperature and which were mixed with the resin at dopant concentrations (parts per million by weight). The behaviors of a molecular rotor dye, dimethylamino diphenyl hexatriene, doped into polyethylene, and an excimer producing dye, bis-(pyrene) propane, doped into polystyrene were the subjects of the modeling calculations. The models consist of two modules: (a) a solution to the thermal diffusion equation for the resin cooling in the mold and (b) using temperature/time profiles and, in the case of polyethylene, crystallinity/time profiles obtained from the thermal diffusion equation, fluorescence intensity as a function of time was computed. Factors incorporated in the models are: adiabatic heating and cooling, light scattering due to microcrystals of polyethylene, crystallization kinetics, temperature and pressure shift factors for viscoelastic relaxation near the glass transition temperature of polystyrene, and the thermal resistance at the resin/mold interface.     

PEEK层间增韧碳纤维环氧树脂基复合材料的性能研究

为了改善碳纤维/环氧树脂(CF/EP)层合板层间断裂韧性较差的问题,采用预浸料层间涂层和模压工艺制备聚醚醚酮(PEEK)层间增韧CF/EP层合板。探究PEEK含量对CF/EP层合板Ⅱ型层间断裂韧性和冲击强度的影响。结果表明:PEEK的加入有效提高CF/EP层合板的Ⅱ型层间断裂韧性和冲击强度。当PEEK含量为2%,层合板的断裂韧性和冲击强度分别达到1 253 J/m²和259 kJ/m²,与纯层合板相比分别提高61.5%和32.8%。实验分析PEEK增韧机理,为研究高附加值复合材料产品提供参考。