Molecular aggregation of PEEK with PES blends and the block copolymers composed of PEEK and PES components

Polymer blends of PEEK with PES were prepared by the solution blending method. Copolymers composed of PEEK and PES components were synthesized from these oligomers. The formation conditions exerted an influence over the molecular aggregation and the crystallization behaviors of the blend films and block copolymers which were examined by X-ray diffractometry and DSC analysis. As a result, phase-separation in the blend films was found when the formation temperature was high. The blend films formed at 340°C, quenched and annealed at 180°C, exhibited the same crystallization behavior as those of PEEK. In the case of the blend films formed at 300°C, the annealing of the films at 250°C was required to crystallize the blend films. The T_g of a copolymer with a PEEK component content of more than 50% tends to shift toward a higher temperature than the T_g of PEEK itself, and the T_m of the copolymer toward a lower temperature than that of PEEK ist.     

Effect of annealing and orientation on microstructures and mechanical properties of polylactic acid

Two types of polylactic acid (PLA) films (one amorphous and one semi‐crystalline) were produced by sheet extrusion. Talc was used as a nucleation agent for the semi‐crystalline PLA. The films were annealed above their T_g or were uniaxially orientated in two ways: (1) via a drawing system in front of the extruder and die or (2) via a three‐roller stretching system. The slower crystallization rate and lower melting stress of the PLA resulted in amorphous film using the drawing system. Annealing above T_g increased crystallinity and polymer chain relaxation, which resulted in increases in both strength and toughness. Stretching above T_g also produced simultaneous crystallization and chain relaxation, which resulted in increases in both modulus and toughness. Both modulus and tensile strength in the stretching direction were higher than in the crosswise direction. Talc acted not only as a rigid filler to reinforce the PLA, but also as a nucleation agent for the PLA, especially during annealing. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The temperature and strain-rate dependence of mechanical properties in polyoxymethylene

The computer aided design approach used in current applications of semicrystalline polyoxymethylene (POM) requires high strain-rate mechanical data. The primary aim of this work has been to measure the room temperature modulus and tensile strength of injection molded samples of POM of different molecular weights at cross-head speeds of between 10^?5 ms^?1. We observe no major transition in bulk mechanical behavior in this range of test speeds, the Young's modulus E, in particular, showing little strain rate dependence. This is rationalized on the basis of tensile tests over a range of temperatures, these indicating room temperature to correspond to the plateau in the E(T) curves (T_g for these materials is taken to be ?70°C, and the DSC melting onset occurs at ～ 170°C). The tensile strength increases as ～log(d?/dt) and the behavior is found to be highly nonlinear, strains to fail of the order of 1 being observed even at the highest strain rates, depending on the molecular weight. It is believed that the yield stress of th crystalline regions determines the tensile strength above T_g, the higher degree of crystallinity associated with lower molecular weights resulting in a slightly higher tensile strength. Nevertheless, failure is qualitatively brittle, with no necking and relatively little permanent deformation. This behavior is discussed in terms of morphological investigations of the fractured samples by optical and scanning electron microscopy (SEM). In attempting to relate ultimate failure to the molecular/crystalline structure of the samples, measurements of the critical stress intensity for crack initiation in mode I opening, K_IC, as a function of crystallization temperature T_c have been carried out using compact tension specimens machined from injection molded and compression molded plaques. K_IC increases with molecular weight and decreases with T_c at low test speeds (in spite of an increase in crystallinity with T_c). This is accounted for in terms of a crack shielding model for crack initiation and of molecular rearrangements occurring during crystallization which lead to a decrease in the effective entanglement density with T_c. The implications of this model are then compared with K_IC results over a range of cross-head speeds and temperatures.     

Kinetics and thermal crystallinity of recycled PET. I. Dynamic cooling crystallization studies on blends recycled with engineering PET

The recycled poly(ethylene terephthalate) (R-PET) from the recovery of a blow-molded bottle is studied with its crystalline behavior in terms of glass transition temperature (T_g), crystallization temperature (T_c), melting temperature (T_m), and its dynamic crystallization kinetics. These crystalline behaviors offer an explanation of the better mechanical properties of the R-PET. Thermal cycles of the processes of the R-PET and its blending specimens with engineering PET (E-PET) show the importance of the thermal treatment of the plastic PET in the improvements of mechanical strength and increased crystallinity. Tenfold and fivefold increases, respectively, of elongation and impact strength are observed in the specimen of R-/E-PET of 20/80 weight ratio blend, better than that of E-PET alone. A nearly 20-fold increase of the crystallization rate constant (K) at 190°C for the same R-/E-20/80 blend is observed. The Avrami exponent (“n”) is found to be variable with temperature. The changing crystallization mechanisms are mainly the result of the competition between the nucleating and growing of crystallites in response to the temperature-controlling factor at the melt state. © 1996 John Wiley & Sons, Inc.     

Thermal behavior of transparent poly(etheretherketone)(PEEK) film

The thermal behavior of poly(etheretherketone)(PEEK) film heated in an open differential scanning calorimetry (DSC) pan at 20°C/min is distorted by relaxation of the strained film. PEEK film in a closed pan or quenched PEEK in open or closed pans shows a glass-transition temperature (T_g) around 144°C, cold crystallization (～22 J/g) at 177°C, melt-temperature (T_m) peaking at 335–340°C, with an enthalpy of fusion of 32–34 J/g, and recrystallization on cooling at 285°C, with a crystallization exotherm of about 40 J/g. The enthalpy of fusion decreases with increasing heating rate from 2–100°C/min and approaches the enthalpy of cold crystallization. With increasing heating rate, further crystallization of PEEK during the DSC scan is suppressed. With increasing cooling rate, PEEK melt crystallizes at larger supercoolings to a lesser extent. Crystallization on cooling the melt was more complete than cold crystallization and annealing on heating.     

Annealing effect on the microstructure of poly(vinyl chloride)

The effect of annealing on the microstructure of commercial grade poly(vinyl chloride) was investigated by calorimetric, X-ray and viscoelastic measurements. The degree of crystallinity increases with increasing annealing temperature from above the glass transition temperature up to 130°C, at which point the degree of crystallinity takes on a maximum value. Also, the crystal melting temperature increases with increasing annealing temperature. Thermal analysis and X-ray study suggest that the crystallite of poly (vinyl chloride) decomposes by thermal degradation when annealed, above 170°C. The isothermal crystallization process is analyzed using Avrami's equation employing the degree of crystallinity as a function of annealing time at various annealing temperatures. The crystallization rate has a maximum value at around 140°C. It is expected that the crystalline texture grows in the shape of a lineal-like habit, judging from the magnitude of Avrami's constant and from a study of the X-ray intensity distribution. The α_f-transition was observed to occur at temperatures 5 to 10°C lower than the crystalline melting temperatures for annealed specimens of poly(vinyl chloride) using a dynamic spring analysis. The α_f-transition may be attributed to thermal molecular motions with a long time scale, resulting from the cross-link points introduced by the small crystallites.     

Synthesis of multi‐block copolymer and its compatibilization to the blends of poly(ether ether ketone) with thermotropic liquid crystalline polymer

A multiblock copolymer (BCP) containing amorphous poly(aryl ether ketone) (PAEK) and thermotropic liquid crystalline polymer (TLCP) segments was synthesized. The chemical structure and properties of BCP were characterized by fourier‐transform infrared spectrometer (FTIR), differential scanning calorimeter (DSC), gel permeation chromatograms (GPC), thermogravimetry analysis, polar light microscope (PLM), and solubility test respectively. BCP can dissolve in chloroform because of soluble PAEK block bonded with TLCP block, which was insoluble. The peak of the original PAEK oligomer was no more present in the GPC traces of the block copolymer. These facts indicated that polymer synthesized should be copolymers of the two components rather than blends. A single T_g at 138.1°C and broad melting endotherm at 315.7°C can be observed. The liquid crystalline texture of BCP showed uniformity in the view after heat treated for 10 min above its T_m under PLM. Ternary blends of poly(ether ether ketone) (PEEK)/TLCP/BCP were prepared by extrusion and characterized by DSC. DSC results showed that the crystallization temperature of PEEK phase in the blends shifted higher with the addition of TLCP. Wide angle X‐ray diffraction investigations indicated that the crystalline structure of PEEK was not disturbed by blending or compatibilizing. Scanning electron microscope and mechanical tests confirmed the compatibilizing effect of BCP. Reduction in dispersed phase TLCP size was observed when 2 phr by weight of compatibilizer was added to the blend. Measurement of the tensile properties showed increased elongation as well as improved modulus and strength to some extent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of dihydroxydiphenyl ether on poly(ether ether ketone)

A series of modified poly(ether ether ketone) (PEEK) polymers were synthesized by introduction of addition ether groups from dihydroxydiphenyl ether (DHDE) into the PEEK structure. The inherent viscosity of the DHDE-modified PEEK increased with reaction time at 320 °C. DSC thermograms showed the melting points of the obtained PEEK decreased with the increase of the DHDE content in the backbone. The degradation temperature (T_d) was slightly decreased by the introduction of DHDE. The crystallinity as measured via the X-ray diffraction (XRD) increases with the introduction of DHDE into the modified PEEK. The crystalline structure was identified as an orthorhombic structure with lattice constants a = 7.72 Å, b = 5.86 Å, and c = 10.24 Å. Due to the glass transition temperature (T_g) and the melting temperature (T_m) decreasing with the increase of the DHDE content in the reaction system. the processability of the resultant PEEK could be improved through this DHDE modification.     

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     

Transport and solubility of fluids into polyphenylene sulfide (PPS)

The solubility and transport of toluene and carbon disulfide into amorphous and crystalline polyphenylene sulfide (PPS) was investigated. The rates of sorption, desorption, and resorption of both fluids were measured as a function of temperature. The sorption of these fluids into amorphous PPS produces a semi‐crystalline material by solvent induced crystallinity (SIC). Although the rate of diffusion of carbon disulfide (CS₂) into crystalline PPS, (produced either thermally or by SIC), is several orders of magnitude slower than that observed in amorphous PPS, the solubility is only slightly reduced, by approximately 10%. The PPS films exhibit highly stressed surface regions that rapidly sorb the penetrant. Thermal annealing at temperatures as high as 100°C (note T_g of PPS is 85°C) has little or no effect on the surface stress, the diffusion process or the solubility of toluene into PPS. In addition to SIC, PPS undergoes cold crystallization at 130°–140°C; however, the degree of crystallinity induced by cold crystallization is approximately 60% of that formed by cooling from the melt. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 615–625, 2003     

Annealing effects on the crystallinity of polyetheretherketone (PEEK) and its carbon fiber composite

The degree of crystallinity of polyetheretherketone (PEEK) has been measured using both the density gradient technique (DGT) and differential scanning calorimetry (DSC). The difference in results between the methods was shown to depend on crystallization taking place during the heating scan in the DSC. By freezing the sample at different stages of the DSC thermogram and measuring its crystallinity in the density gradient column, the existence of induced crystallization for PEEK was established. Though this induced crystallization is not visible in the DSC thermogram, it must be taken into account when comparing the degree of crystallinity measured by the two methods. The induced crystallization was in turn interpreted as a result of an increase in crystal perfection that is also commonly observed during the initial stages of the annealing process. Accordingly, the effect of annealing on the crystallinity was also investigated. DSC scans on annealed samples exhibited a small endothermic peak at approximately 10°C above the annealing temperature. This peak was observed in both neat PEEK and its carbon fiber-reinforced composite. Annealed PEEK shows, therefore, two melting transitions, a low one which depends on the annealing temperature and a high one which is independent of annealing temperature conditions. Collectively, the results of this study demonstrate that processing conditions and morphological features must be considered in characterizing semicrystalline-based matrix polymers for high performance composites.     

Conditions of homogeneous deformation of poly(ethylene terephthalate) films during uniaxially drawing

Amorphous poly(ethylene terephthalate) film was uniaxially drawn over a wide range of temperatures from below to above the T_g at a constant strain rate. The geometry of the deformation in macroscopic dimensions of the sample demonstrates that homogeneous deformation can be obtained when the drawing temperature (T_def) is not lower than 69°C. The change of the cold crystallization peak temperature (T_cc) and crystallinity determined by differential scanning calorimetry and density measurement, respectively, were studied in terms of the T_def and the draw ratio (λ). The orientation, relaxation, and crystallization during drawing were investigated as a function of T_def as well as of λ. The results suggest that 69°C is the critical temperature at which the sample with the highest orientation and the least slippage of the molecular chain and without obvious crystallization can be obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2044–2048, 2000     

Properties of high modulus PEEK yarns for aerospace applications

A study has been carried out on the influence of extrusion and drawing related process parameters with an object of obtaining high modulus poly ether ether ketone yarns that can be tailor made to meet critical requirements of aerospace applications. The influence of the interaction between rheological properties, spinning process variables, and drawing conditions has been given special attention to engineer a yarn that exhibit excellent structure property relationships. The wide angle X‐ray diffraction results suggest that drawing carried out above glass transition temperature (T_g) influences the structure that include unit cell parameters, density, and mechanical properties. The degree of orientation characterized in terms of sonic velocity measured as high as 3 km/s with sonic modulus of 105 gpd. With progressive increase in draw temperature, crystallinity was found to increase, and useful properties were observed at an optimum draw temperature of 200°C (may be region of maximum crystallization rate) primarily attributed to the maximum crystallization temperature and the heat setting effect. Thermal studies (TGA) indicate that these materials can be used in high temperature applications (up to 250°C) for long time exposure and 500°C for short term exposure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of thio‐containing poly(ether ether ketone)s

A series of thio‐containing poly(ether ether ketone) (PEESK) polymers was synthesized by the introduction of thio groups from 4,4′ thiodiphenol (TDP) into the poly(ether ether ketone) (PEEK) structure via reaction between the phenol and aromatic fluoride groups. The effect of the thio groups on the properties of the PEESK materials was investigated. Differential scanning calorimetry (DSC) analysis and X‐ray diffraction (XRD) patterns show a depression in the crystallinity of the PEESKs with incorporation of the content of thio groups in the backbones. The crystalline structure was identified as an orthorhombic structure with lattice constants of a = 7.52 Å, b = 5.86 Å and c = 10.24 Å for all crystallizable PEESKs. The crystalline structures of the thio‐containing PEEK polymers were the same as that of the neat PEEK, which means the thio‐containing block in the whole thio‐containing PEEK molecule is almost excluded from the crystalline structure and the crystals are completely formed by ‘non‐thio’ blocks only. Due to the glass transition temperature (T_g) and melting temperature (T_m) depression with increase in the TDP content in the reaction system, the processability of the resultant thio‐containing PEEKs could be effectively improved. Copyright © 2004 Society of Chemical Industry     

Crystallization kinetics,mechanical properties,and hydrolytic degradation of novel eco‐friendly poly(butylene diglycolate) containing ether linkages

The basic thermal properties, isothermal melt crystallization kinetics, spherulitic morphology, mechanical properties, and hydrolytic degradation behavior of a novel eco‐friendly polyester poly(butylene diglycolate) (PBDG) containing ether linkages were systematically studied with several techniques in this research. PBDG is an aliphatic polyester with high thermal stability. It had a glass transition temperature (T_g) of ?25.7 °C, a melting point temperature of 65.1 °C, and an equilibrium melting point of 73.2 °C. During the isothermal melt crystallization, PBDG crystallized slowly with increasing crystallization temperature, but the crystallization mechanism did not change. Negative spherulites were observed for PBDG. The mechanical properties of PBDG were investigated from the tensile testing. As a ductile polyester, PBDG possessed good mechanical properties. PBDG also showed a fast hydrolytic degradation rate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44186.     

The effect of annealing on the short and long term behavior of PEEK

Summary Short and long-term tensile tests have been done on injection-moulded poly-ether-etherketone (PEEK) in order to assess the effect of annealing on its mechanical behavior. In addition to the behavior reported before, namely increases in yield and drawing stress, the annealed specimens exhibit a distinct work hardening behavior in the beginning of the drawing phase at temperatures between 80°C and 160°C. Subsequent creep tests show that the annealing treatment also influences greatly the long-term static properties of PEEK with creep rates after annealing being considerably below those recorded on the standard injection.DSC thermograms of the samples annealed for more than 20 minutes exhibit similar curves as those reported before, two endothermic peaks: a major peak at 340°C and a minor one at 260°C which is 10 K higher than the annealing temperature.The experimental results support that a type of secondary crystallites grow in the material by the annealing treatment. The existance of those secondary crystallites enhances the mechanical properties of PEEK.     

Morphology and texture development of uniaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The texture development of PEN films with different semicrystalline morphologies have been studied by X‐ray diffraction. These different structures have been obtained by uniaxially stretching PEN amorphous films at 100 and 160°C (below and above T_g) at different drawing ratios. Samples have also been characterized by DSC to determine the crystallinity ratios, the crystallization, and melting temperatures. To define the orientation of crystallites in the oriented samples, pole figures have been constructed, as a function of temperature and drawing ratio (DR) in the range 1.5–4. In the range from DR = 2 to 4 the orientation is clearly uniplanar‐axial. At T_draw = 100°C the crystallinity shown by DSC analysis is higher than the sample stretched at 160°C. The orientation is also higher when samples are stretched at 100°C. The naphthalene rings mainly stay in the plane of the film with a lower fraction perpendicular to the plane of the film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 395–401, 2007     

Microstructural effects on hot drawing syndiotactic styrene P‐methyl styrene copolymer

Crystalline syndiotactic styrene/p‐methyl styrene copolymer (SPMS) has been oriented by tensile drawing at various temperatures between the glass transition and crystalline melting point. The microstructural changes resulting from drawing have been studied using differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). WIth increasing draw temperature, both melting temperature and crystalline dimensions of the oriented samples increase. The heat of fusion increases with increasing draw temperature up to ～200°C. It also increases with draw ratio and draw rate, while the crystalline width increases only with draw ratio. THe amorphous fraction shows a clear glass transition, the temperature of which (T_g) increases with draw ratio. However, T_g decreases somewhat with increasing draw temperature. This is interpreted in terms of the stretching of the randomly coiled amorphous phase molecules.     

Thermal properties of a tough,new semicrystalline polyimide

Thermal properties of a new semicrystalline polyimide synthesized from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride ( BTDA ) and 2,2-dimethyl-1,3-(4-aminophenoxy)propane ( DMDA ) have been studied. Heat capacities in the solid and liquid states of BTDA - DMDA have been measured. The heat capacity increase at the glass transition temperature (T_g = 230°C) is 145 J/°Cmol for amorphous BTDA - DMDA . The equilibrium heat of fusion of the BTDA - DMDA crystals has been obtained using wide-angle X-ray diffraction and differential scanning calorimetry measurements, and is 75.8 kj/mol. Based on the information on crystallinity and the heat capacity increase at T_g, a rigid amorphous fraction is identified in semicrystalline BTDA - DMDA samples, which represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample, which should be associated with crystal sizes, and therefore with crystal morphology. It has also been found that this polymer has a high-temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies of BTDA - DMDA in nitrogen and air are determined to be 154 and 150kJ/mol, respectively.     

Influence of copolymerisation on fracture behaviour of aliphatic polyketones

High strain rate tensile impact properties of aliphatic polyketone terpolymers were investigated and related to the polymer chain structure. Aliphatic polyketones were used as a model system, by changing the termonomer content and type. Aliphatic polyketone is a perfectly alternating copolymer and the structure was changed with the addition of a few mol% of termonomer: propylene, hexylene and dodecene. Studied were the thermal properties with DSC and DMTA, tensile behaviour, notched tensile impact behaviour, notched Izod properties and the temperature development during deformation. The perfectly alternating copolymer had a melting point of 257 °C, a T_g at 15 °C, a high crystallinity (48%), a high yield stress (77 MPa) and yield strain (31%) but a relatively low fracture strain (85%) and an impact strength (notched Izod) of 13 kJ/m². Increasing the propylene content to 6%, lowered the melting temperature to 224 °C, without changing the T_g. The modulus and yield stress were lowered but the impact strength improved. Increasing the length of the termonomer while keeping the T_m at 224 °C lowered the T_g, the modulus, the yield stress but strongly improved the impact resistance. The longer termonomers, with a lower yield stress, reduced the necking behaviour. The temperature increase in front of the notch was about 85 °C. By adding termonomers to aliphatic ketones, the notched impact behaviour improved significantly at the cost of modulus and yield stress.