The effect of physical ageing on the properties of amorphous PEEK

Physical ageing rates of poly(aryl-ether-ether-ketone) have been measured, and interpreted as a kinetic effect associated with the glass formation process. The extent of ageing achieved at equilibrium as measured by differential scanning calorimetry is equal to the product of the super-cooling from the quenched glass transition, and the heat capacity difference between the glass and liquid at the transition temperature. Heat capacities of amorphous and crystalline PEEK have been measured. The activation energy of physical ageing is similar in magnitude to that observed for temperature dependence of crystallization under conditions of viscosity control. Ageing is accompanied by a change in mechanical properties, increased tensile yield stress and drawing stress, more localized yielding and a decrease in impact strength. Fracture surfaces show evidence of mixed modes of fracture.     

Effect of physical aging on the properties of films of amorphous poly(ether ether ketone) (PEEK)

Physical aging of films of poly(ether ether ketone) kept for 2 months at 120°C was studied. The extent of aging was evaluated with different techniques. Aged samples show different thermal behavior and exhibit different mechanical, transport, and viscoelastic properties. An attempt was made to establish the accuracy of different techniques and their reliability in detecting the extent of physical aging. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2635–2641, 1997     

The effect of physical aging on properties of rigid polyvinyl chloride

This paper describes the effects of physical aging on properties of rigid PVC, such as tensile strength, tensile modulus, Izod impact, coefficient of thermal expansion, specific gravity, differential scanning calorimetry, and heat deflection temperature.     

Physical aging of amorphous poly(etheretherketone) (PEEK)

Thermal treatment of amorphous poly(aryl-ether-ether ketone) below the glass transition temperature has been studied. The extent of aging was measured by differential scanning calorimetry. X-ray and Fourier transform infrared spectra were used to study both melt-cast and annealed samples. The effect of the thermal treatment of viscoelastic response was evaluated using creep tests. Aging has been shown to be accompanied by a marked change in the transport properties of the material.     

The effect of fusion and physical aging on the toughness of poly(vinyl chloride)

It is well known that during aging or annealing, materials become stiffer and more brittle, and creep and stress relaxation rates decrease. Research in this area is very important because physical aging (annealing) plays a large role in the production of products, and it also occurs during the use of the objects or products. The decrease of free volume with time is unavoidable even at ambient temperatures. The influence of fusion and physical aging on the toughness of extruded PVC profiles was investigated. It is known that the toughness of PVC is influenced by secondary crystallization—after primary particles of PVC are partially melted. Recrystallization upon cooling or annealing forms a three-dimensional structure tying together the primary particles. This three-dimensional structure normally produces a tougher PVC product. The density of glassy PVC can be changed by changing the quenching rate. The density can be further changed by annealing below T_g. The densification of a glassy polymer normally leads to a less tough PVC product. This study uses density measurements and differential scanning calorimetry scans to measure the amount of enthalpy relaxation (related to densification) and crystalline melting energy (related to the amount of crystallinity) for various annealed samples. These are related to toughness as measured by notched Izod and droppeddart impact tests.     

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.     

The physical properties of sulfonated graphene/poly(vinyl alcohol) composites

Composites of poly(vinyl alcohol) (PVA) with sulfonated graphene (SG) show fibrillar, dendritic and rod like structures for SG1, SG3 and SG5 samples, respectively, where the number indicates weight percent of SG. Differential scanning calorimetry shows a new peak in addition to that of PVA arising from the supramolecular organization of the components in SG1 and SG3. Seventeen percent and 36% increases of PVA crystalline thickness and 77% and 79% increases in amorphous overlayer thickness for SG1 and SG3 over PVA are evident from small angle X-ray scattering results but SG5 does not show any change. Atomic force microscopy results of SG suggest aggregation at higher concentration and the composites exhibit composition dependent mechanical properties with the highest increase of stress (177%), strain at break (45%) and toughness (657%) in SG3 over PVA. Young’s modulus increases with increasing SG concentration with a maximum 180% increase in the SG5 sample. The storage modulus of SG3 shows the highest increase (1005%) over PVA. A 10 orders of magnitude increase of dc conductivity over PVA and a 10-fold increase in the dendritic SG3 to that of other composites are observed. SG1 is semiconducting, SG3 shows an electronic memory and SG5 exhibits a rectification property.     

Polyetheretherketone (PEEK): Processing-structure and properties studies for a matrix in high performance composites

The processing, structure and properties of polyetheretherketone (PEEK) semicrystalline thermoplastic as matrix polymer for high performance composites has been investigated in this work. In processing PEEK samples with different crystallinities, a specially designed mold capable of cooling the polymer in excess of 115°C/s from its melt temperature was constructed. In addition, during processing studies, a reaction of PEEK in the presence of copper was discovered. Analysis of the samples in terms of their crystallinity values also provided a new method for measuring crystallinity of the matrix in the composite. Crystallization of low crystalline samples at room temperature in the presence of methylene chloride was also confirmed for the first time with polarized microscopy. However, at the same time, the excellent hygrothermal resistance of PEEK was also confirmed. Finally, dynamic mechanical and stress-strain experiments with samples of different crystallinities elucidated the dependence of these properties to crystallinity. However, this study also elucidated that under normal processing conditions for high performance composites, PEEK properties may not be strongly affected by different levels of crystallinity.     

Isothermal physical aging of PEEK and PPS investigated by fractional Maxwell model

Generalized fractional Maxwell model is applied to simulate the creep and the relaxation behavior of PEEK and PPS measured at different aging stages and different temperatures. Genetic algorithm and the conjugated gradient method are combined to optimize the model parameters. The results show that the fractional Maxwell model can describe both the creep and relaxation data very well when the model parameters are fitted properly. The momentary creep compliance and the relaxation modulus change with the time at an increasing rate; the fractional orders of the two fractional elements building up the model correspond to the creep or relaxation exponents at the initial glassy stage and the terminal fluid state. The relaxation time τ of the model, which corresponds to the characteristic time of α transition of the sample, shifts towards longer time with increasing the aging time and lowering the aging temperature. In the time domain scaled by the relaxation time τ, all the creep or relaxation curves measured at different aging times and temperatures superpose automatically, which means the time–aging time superposition and the time–temperature superposition present themselves. The shift rates and the temperature shift factors can be then obtained from the model parameters. Good simulation for the creep and relaxation behavior and optimum superposition of the experimental data achieved by the fractional model may offer reliable predictions for the long-term stress-strain response.     

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.     

The effect of long-term ambient aging on the mechanical properties of conducting polysiloxane-polypyrrole graft copolymers

The mechanical behavior of conducting polysiloxane-polypyrrole graft copolymers has been investigated as a function of ambient oxidative aging period. Graft copolymers of N-pyrrolyl-terminated polydimethylsiloxane (SPPy) with pyrrole were synthesized electrochemically at constant potential by using p -toluene sulfonic acid as the supporting electrolyte. Mechanical tests were performed on both unwashed and dichloromethane -washed copolymers after aging. An initial decrease followed by an increase in the tensile strength and strain values was observed with aging. The conductivities and mechanical properties of the films were determined to remain almost unchanged after 6 months of aging at about 46 S/cm.     

The effect of physical ageing on the properties of poly(ethylene terephthalate)

Physical ageing rates of poly(ethylene terephthalate) have been measured, and ageing is interpreted to be associated with the conventional glass formation process, which occurs at a more rapid rate at higher temperatures. Ageing is accompanied by a marked change in mechanical properties, increased tensile yield stress and drawing stress, more localized yielding of the polymer and a marked decrease in impact strength. The fracture results have been attributed to the increased yield stress and a change in contribution of plane stress and plane strain conditions in the samples. Fracture surfaces show evidence of mixed modes of fracture.     

Effect of physical aging on nano- and macroscopic properties of poly(methyl methacrylate) glass

Physical aging of amorphous poly(methyl methacrylate) has been studied by low frequency Raman scattering, broad-band dielectric spectroscopy, low frequency high resolution mechanical spectroscopy and differential scanning calorimetry. The material was subjected to different thermal histories by isothermal aging. A consistent relationship between the changes caused by the physical aging in nanostructure and molecular dynamics has been found. The aging makes the structure more homogeneous at a scale of few nanometers, bringing it to a structural state of lower energy. These structural changes affect mainly the -relaxation, however, some increase in the relaxation strength as well as an increase in the activation energy of the β-relaxation is also observed.     

Procedure effect on the physical and mechanical properties of the extruded wood plastic composites

This article investigates the effect of raw material preparation on the mechanical and physical properties in wood‐plastic composite (WPC) production. Four possible procedures in material preparation to obtain a determined level of wood content are: (i) to use and feed raw materials in the same ratio of the desired composition (single stage), (ii) to use the batch of granules of the same composition (two‐stage), (iii) to add wood to the batch of granules having a lower wood content, (iv) to add polymer to the batch of granules having a higher wood content. The main question then is that, while it is economically attractive to use granules of a fixed wood content in all productions, whether there are noticeable differences in final properties of the products. The examined compositions were 50, 60, and 70 wt% of wood content which are considered as highly filled WPCs and mainly used in the WPC markets. Thus, 12 sets of WPC profiles were manufactured and the processing conditions (temperature, pressure, and outlet velocity) recorded. The flexural properties, impact strength, density, and water uptake were measured. Results revealed that in the production of WPCs with 50 and 70 wt% of wood content, using the WPC granules with the same composition yields better physical and mechanical properties. However, for producing WPC with 60 wt% of wood content, using WPC granules with 70 wt% of wood and adding appropriate amount of polymer exhibit better results. POLYM. COMPOS. 34:1349–1356, 2013. © 2013 Society of Plastics Engineers     

Study on physical properties of multiwalled carbon nanotube/poly(phenylene sulfide) composites

The multiwalled carbon nanotubes were directly compounded with poly(phenylene sulfide) (PPS) via melt mixing. The morphology and physical properties, including viscoelasticity, electrical conductivity, and thermal and mechanical properties, of the obtained composites were investigated. The results show that the purified nanotubes can be fully dispersed in the PPS matrix especially at low loading levels because of their good affinity. The composites hence present relative low rheological and electrical percolation thresholds. The presence of nanotubes, on the one hand, shows good reinforcement effect because of the strong interfacial interactions with the PPS matrix, which is confirmed by the strain overshoot flow behavior, and, on the other hand, acts as a nucleation agent, promoting crystallization of the PPS matrix. Both contribute to evident improvement of tensile strength and dynamic mechanical properties of the composites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Fiber orientation and its effect upon thermoelastic properties of short carbon fiber reinforced poly(etheretherketone) (PEEK)

Experimental and analytical techniques are employed in the present study to investigate the influence of microstructure on thermoelastic properties of short carbon fiber reinforced poly(etheretherketone). The test specimen geometry is an edge gated, injection molded dogbone tensile bar. Typical of injection molded structures, three distinct layers of fiber orientation were discernable through the sample thickness. The thermoelastic properties of the surface layer (machined from the specimen) are measured for direct correlation with a micromechanics model. In addition to measuring the volume fractions and constituent properties, microstructural features such as fiber aspect ratio and the process-induced fiber orientation distribution are quantified. Correlation of experimental data with micromechanics model predictions is found to be quite good.     

Influence of cenosphere on tribological properties of short carbon fiber reinforced PEEK composites

This investigation focuses on the effects of cenosphere fillers on tribological properties of carbon fiber reinforced PEEK composites. Dry sliding wear behavior of 15 wt % short carbon fiber (SCF) reinforced PEEK composites filled with 5, 10, 15, and 20 wt % cenosphere was reported in this study, pure PEEK and 15 wt % SCF reinforced PEEK composites were also prepared for comparative analysis. Friction and wear experiments were conducted on a ring-on-block apparatus under different loads (100–400 N). The experimental results showed that all the composites exhibited lower coefficient of friction and better wear resistance than the matrix resin under different load conditions. It is noted that 10 wt % of the cenosphere particles filled SCF reinforced PEEK composites show superior tribological properties when compared to the other composites in this study. The morphologies of the worn surface and the fracture surface were analyzed by scanning electron microscopy and the transfer film was observed by optical microscope to understand the dominant wear mechanisms. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47245.     

Poly(lactic acid)/pulp fiber composites: The effect of fiber surface modification and hydrothermal aging on viscoelastic and strength properties

Poly(lactic acid) (PLA)/kraft pulp fiber (30 wt%) composites were prepared with and without a coupling agent (epoxidized linseed oil, ELO, 1.5 wt%) by injection molding. The non-annealed composite samples, along with lean PLA, were exposed to two hydro-thermal conditions: cyclic 50% RH/90% RH at 23 and 50°C, both up to 42 days. The aging effects were observed by size exclusion chromatography, differential scanning calorimetry, dynamic and tensile mechanical analysis, and fracture surface imaging. ELO temporarily accelerated the material's internal transition from viscous to an increasingly elastic response during the aging at 50°C. ELO also slowed down the tensile strength reduction of the composites at 50°C. These observations were explained with the hydrophobic ELO molecules' coupling and plasticizing effects at fiber/matrix interfaces. No effects were observed at 23°C.