The phase transformation toughening and synergism in poly(butylene terephthalate)/poly(tetramethyleneglycol) copolymer-modified epoxies

The toughening of epoxy modified with poly(butylene terephthalate)/poly(tetra-methylene glycol) (PBT–PTMG) copolymers of various chemical composition was investigated. The fracture toughness of the brittle epoxy was highly enhanced by the inclusion of PBT–PTMG copolymer without loss of other intrinsic mechanical properties, such as modulus and yield stress. These modified epoxies also exhibited synergism in toughening. The remarkable enhancement and the synergism in fracture toughness of PBT/PTMG-modified epoxies is possibly due to the enhancement of the degree of phase transformation toughening, which is a result of the enhancement of the degree of perfectness of PBT spherulites in the presence of PTMG segments. The changes in micro-morphology of PBT/PTMG phases induced by the different chemical composition of copolymer is the most important cause of the dependency of the fracture energy on the processing variables, such as the relative PBT/PTMG composition and total amount of modifiers. Other toughening mechanisms, such as crack bifurcation, ductile fracture of PBT/PTMG phases, main crack-path alteration, and crack bridging, also contributed to toughness enhancement of the modified epoxies. © 1998 Chapman & Hall     

Possible phase transformation toughening of thermoset polymers by poly(butylene terephthalate)

Mechanisms were explored by which particles of poly(butylene terephthalate) (PBT) are able to toughen a brittle epoxy. The epoxy studied was an aromatic amine-cured diglycidyl ether of bisphenol-A, which was toughened at about twice the rate with particles of poly(butylene terephthalate) as with particles of nylon 6, poly(vinylidene fluoride), or CTBN rubber. Many of the mechanisms of toughening are visible on the fracture surface of the PBT-epoxy blend, but a mechanism suggested to account for perhaps half of the increased toughness with PBT, phase transformation toughening, is not. The two types of experiment performed to detect phase transformation toughening were: (1) measurements of the rubber cavitation zone in PBT-CTBN rubber-epoxy ternary blends, which would detect an expansion of the PBT particles during fracture if it occurred, and (2) measurements of the fracture energy in PBT-epoxy blends in which the various mechanisms of toughening were selectively suppressed. Both types of experiment indicated the occurrence of phase transformation toughening in these PBT-epoxy blends.     

The toughness of epoxy-poly(butylene terephthalate) blends

Blends containing 5% poly(butylene terephthalate) (PBT) in an anhydride-cured epoxy with three different PBT morphologies were studied. The three morphologies were a dispersion of spherulites, a structureless gel and a gel with spherulites. The average fracture toughnesses, K _Ic, and fracture energies, G _Ic, for those morphologies were 0.83, 2.3 and 1.8 MPa m^1/2 and 240, 2000 and 1150 J m^–2, respectively. These values should be compared with the values of 0.72 MPa m^1/2 and 180 J m^–2, respectively, for the cured epoxy without PBT. The elastic moduli and yield strengths in compression for all three blend morphologies remained essentially unchanged from those of the cured epoxy without PBT, namely, 2.9 GPa for the modulus and 115 MPa for the yield strength. The fracture surfaces of the cured spherulitic dispersion blends indicate the absorption of fracture energy by crack bifurcation induced by the spherulites. The fracture surfaces of the cured structureless gel blends indicate that fracture energy was absorbed by matrix and PBT plastic deformation and by spontaneous crack bifurcation. But phase transformation of the PBT and anelastic strain of the matrix below the fracture surfaces may account for most of the large fracture energy of the cured structureless gel blends.     

Mechanical and thermal properties of poly(butylene terephthalate)/poly(ethylene naphthalate), and Nylon66/poly(ethylene naphthalate) blends

The tensile modulus, tensile strength and impact strength of melt blends of (a) poly(ethylene naphthalate) (PEN) and poly(butylene terephalate) (PBT) with 30, 40, 50, 60 and 70 wt% PEN, (b) Nylon66 and PEN with 30, 50 and 70 wt% Nylon66 were measured, and thermal/thermomechanical properties were analysed by differential scanning calorimetry and dynamic mechanical thermal analysis. Scanning electron microscopy was used for examination of the fracture surfaces of the blends.All PBT/PEN blends show two glass transitions corresponding to the presence of two phases: the glass transition temperature, T _g, of the phase with the lower T _g increases with increasing PEN content, and T _g for the phase with higher T _g decreases with increasing PBT content. The implication is that the two polymers are partially miscible, and scanning electron microscopy of fracture surfaces reveals a very small (sub-micron) domain size. Nylon66/PEN blends also show two phases, but the domain size is of the order of m and there is no evidence of partial miscibility.Up to 50 weight proportions PBT does not lower the tensile strength of PBT/PEN blends, and the tensile strength lies between values predicted by the rule of mixtures and a modified rule of mixtures. Incorporation of at least 40% PEN in PBT increases impact strength, but blending with smaller proportions of PEN decreases impact strength. By contrast, blending of Ny66 and PEN results in reduction of tensile strength for all blend compositions.     

Fracture toughness and fracture mechanisms of polybutylene-terephthalate/polycarbonate/ impact-modifier blends

A series of polybutylene-terephthalate/polycarbonate (PBT/PC) blends with different compositions were prepared using a twin-screw extruder. The morphologies of the blends were revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that a 50/50 PBT/PC blend possessed a bicontinuous structure and the other blends had a dispersed phase of either PBT or PC depending on which was the minor component. A relatively strong interface was observed in the blends with 20%, 40% and 50% PBT; but poor interfacial adhesion was found in the blends with 60% and 80% PBT. The strength of the interfacial boundary was believed to depend on the composition and blending conditions of the individual blend. Fracture experiments showed that the sharp-notch fracture toughness of PC could be significantly increased by mixing with up to 50% PBT without losing its modulus and yield stress. The toughening mechanisms involved in the fracture processes of the blends were studied using both SEM and TEM together with single-edge-double-notched-bend (SEDNB) specimens. It was found that in the toughened blends the growing crazes initiated by the triaxial stress in front of the crack tip were stabilized by the PC domains. The debonding-cavitation mechanism occurred at the PBT/PC interface, which relieved the plane-strain constraint and promoted shear deformation in both PBT and PC. This plastic deformation absorbed a tremendous amount of energy. Crack-interface bridging by the PC domains was clearly verified by the TEM study. Thus, the PC domains not only stabilized the growing crazes they also bridged crack surfaces after the crack has passed by. This effect definitely caused a large plastic-damage zone and hence a high crack resistance. Poor crack resistances of the blends rich in PBT was caused by the poor interfacial adhesion between PBT and PC. In these polymer blends, the growing crazes easily developed into cracks, which subsequently passed through the weak interface of PBT/PC and finally produced fast unstable fracture.     

Viscoelastic properties of poly(butylene terephthalate)/poly(ethylene naphthalate) blends

Melt blends of poly(butylene terephalate) (PBT) and poly(ethylene naphthalate) (PEN) with 30 and 60 wt% PEN were prepared using a single screw extruder and an injection moulding machine. Stress relaxation tests for the specimens of PBT/PEN blends and the homopolymers were carried out using an Instron testing machine in an Instron environmental chamber. The Taguchi method of experimental design analysed how different levels of temperature, PEN content and initial stress affected the relaxation behaviour of PBT/PEN blends and homopolymers. From the response tables and analyses of main and interaction effects, it was shown that the most significant factor was temperature, followed by PEN content and then the initial stress. Consequently, high temperature, low PEN content and high initial stress speeded up stress relaxation rate of specimens. Interaction effects between factors were insignificant. To fit the relaxation curves of the PBT/PEN blends and the homopolymers at different temperatures, PEN contents and the initial stresses, four different equations were attempted with Matlab™, which determined the coefficients of these functions using the experimental data of stress change with time. The simulated curves from the most suitable function among them were shown using the calculated coefficients to predict the relaxation behaviour of PBT/PEN blends (50% PEN) at temperatures of 30 and 60°C with an initial stress of 7 MPa.     

Super-tough poly(butylene terephthalate) based blends by modification with core-shell structured polyacrylic nanoparticles

Core-shell structured polyacrylic nanoparticles (named CSPN) impact modifiers consisting of a rubbery poly(n-butyl acrylate) core and a rigid poly(methyl methacrylate) shell with a size of about 352 nm were synthesized by seed emulsion polymerization. The CSPN modifier with core-shell weight ratio 80/20 was used to toughen poly(butylene terephthalate) (PBT) by melt blending. With an increase in CSPN content, the impact strength and the elongation at break of PBT/CSPN blends increased significantly compared with those of PBT; however, the tensile strength decreased. It was found that the polymerization had a very high instantaneous conversion (> 93%) and overall conversion (99%). The core-shell structure of CSPN was examined by means of transmission electron microscope. Scanning electron microscope was used to observe the morphology of CSPN particle and fractured surfaces of the blends. The dynamic mechanical analyses of PBT/CSPN blends showed two merged transition peaks of PBT matrix, with the presence of CSPN modifier, which was responsible for the improvement of PBT toughness. The results indicated that the notched impact strength of PBT/CSPN blend with a weight ratio of 80/20 was 8.61 times greater than that of pure PBT where the brittle-ductile transition point appeared.     

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.     

Molecular orientation of poly(ethylene terephthalate) and poly(butylene terephthalate) probed by polarized Raman spectra: a parallel study

Poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) samples uniaxially drawn above Tg and beyond the yield point exhibit significant differences in their molecular orientation behavior as probed by polarized Raman spectra. The quasi-amorphous PET samples, drawn close to the Tg, manifest considerable molecular orientation development; however, when drawn above Tg + 30 degrees C, they exhibit significant molecular orientation relaxation. The semi-crystalline PBT samples maintain prominent molecular orientation even when drawn 110 degrees C above Tg. The drawing process, in PET samples, when resulting in molecular orientation, is accompanied by a gauche-trans transformation of the glycol linkage and a concurrent initiation of crystallinity development. In PBT specimens, it gives rise to a coexistence of alpha- and beta-type crystalline phases. Phase alpha is predominant at high draw temperatures, i.e., Tg + 110 degrees C, while phase beta dominates at low draw temperatures, i.e., Tg + 10 degrees C. PBT samples, with beta-phase predominance, left at relevant draw temperatures without stress, exhibit a beta-alpha phase change though no molecular orientation relaxation occurs. A note is made of the fact that complete molecular orientation analysis of PBT segments utilizing the depol method gives more reliable results than the simplified analysis assuming a cylindrical tensor for the 1614 cm(-1) symmetric stretch of the para-disubstituted benzene ring of PBT. In this context, segments of PBT specimens rich in alpha-phase exhibit higher molecular orientation than those with beta-phase predominance.     

Fracture behaviour of liquid crystal epoxy resin systems based on diglycidyl ether of 4,4′-dihydroxy-α-methylstilbene: Part II Effect due to blending with TACTIX 556 epoxy resin and phenolic monomers

The mechanical behaviours of unoriented, poured resin castings based on formulated blends containing the diglycidyl ether of 4,4′-dihydroxy-α-methylstilbene monomer are studied. It is found that the mechanical and fracture behaviours of these liquid crystalline epoxy (LCE) blends vary significantly. In general, the LCE blends possess much higher fracture toughness and fatigue crack resistance than conventional epoxy resins. At low temperatures (−40°C), the KIC values of the LCE blends are slightly higher than those measured at room temperature. The common fracture mechanisms observed in the ductile LCE blends are crack segmentation, crack branching, crack bridging and crack blunting. The fracture surfaces of the tougher LCE blends only exhibit limited ductile drawing (furrow pattern) at the slow crack growth region; no signs of shear lips on the edges of the starter crack region are observed. The optical microscopy and transmission electron microscopy work suggests that orientation and/or transformation toughening may be the source for such high fracture toughness of the LCE blends. The possible cause(s) of the unusual fracture behaviour of the LCEs is discussed. Approaches for making high performance LCE blends are also addressed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Poly(ether ether ketone) with pendent methyl groups as a toughening agent for amine cured DGEBA epoxy resin

A diglycidyl ether of bisphenol-A (DGEBA) epoxy resin was modified with poly(ether ether ketone) with pendent methyl groups (PEEKM). PEEKM was synthesised from methyl hydroquinone and 4,4′-difluorobenzophenone and characterised. Blends of epoxy resin and PEEKM were prepared by melt blending. The blends were transparent in the uncured state and gave single composition dependent T _g. The T _g-composition behaviour of the uncured blends has been studied using Gordon–Taylor, Kelley–Bueche and Fox equations. The scanning electron micrographs of extracted fracture surfaces revealed that reaction induced phase separation occurred in the blends. Cocontinuous morphology was obtained in blends containing 15 phr PEEKM. Two glass transition peaks corresponding to epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum of the blends. The crosslink density of the blends calculated from dynamic mechanical analysis was less than that of unmodified epoxy resin. The tensile strength, flexural strength and modulus were comparable to that of the unmodified epoxy resin. It was found from fracture toughness measurements that PEEKM is an effective toughener for DDS cured epoxy resin. Fifteen phr PEEKM having cocontinuous morphology exhibited maximum increase in fracture toughness. The increase in fracture toughness was due to crack path deflection, crack pinning, crack bridging by dispersed PEEKM and local plastic deformation of the matrix. The exceptional increase in fracture toughness of 15 phr blend was attributed to the cocontinuous morphology of the blend. Finally it was observed that the thermal stability of epoxy resin was not affected by the addition of PEEKM.     

Toughened blends of poly(butylene terephthalate) and BPA polycarbonate

The morphologies of melt blends of poly(butylene terephthalate) (PBT) and bisphenol A polycarbonate (PC) toughened with a core/shell impact modifier have been characterized by transmission and scanning electron microscopy. Selective staining with ruthenium and osmium tetroxide and etching with diethylene triamine have been used to assess the distribution of the various blend components and investigate the effects of thermal history on morphology. Strong evidence for partial melt miscibility of PC and PBT and rate-dependent segregation during cooling is presented.     

Toughening modification of polycarbonate/poly(butylene terephthalate) blends achieved by simultaneous addition of elastomer particles and carbon nanotubes

Small quantities of maleic anhydride grafted styrene-ethylene-butylene-styrene (SEBS-g-MAH) copolymer and carbon nanotubes (CNTs) were introduced into polycarbonate (PC)/poly(butylene terephthalate) (PBT) blends. The results demonstrated that simultaneously adding SEBS-g-MAH and CNTs greatly enhanced the fracture toughness of the samples and the impact strength increased with increasing CNT content. The morphologies, the dispersion of CNTs, the relaxation behaviors and the crystallization behaviors of samples were systematically investigated. SEBS-g-MAH formed the dispersed particles in the system. The particle diameter was decreased in the blend composites. CNTs exhibited homogeneous dispersion in the blend composites and they also formed a percolated network structure at relatively high content. The transesterification between PC and PBT components was suppressed by SEBS-g-MAH, and the crystallization ability of the PBT component was greatly enhanced. The toughening mechanisms were mainly related to the suppressed transesterification, the decreased elastomer particle size, and the formation of a CNT network structure.     

Fracture toughness and fracture mechanisms of PBT/PC/IM blends PART IV Impact toughness and failure mechanisms of PBT/PC blends without impact modifier

In this part of the series, the impact behaviour of the PBT and PC blends without impact modifier was studied. Failure mechanism of the blends under various conditions was discussed. It was found that the key toughening process, i.e. interfacial debonding-cavitation, was disabled when the blends were subjected to impact loading. Hence, the fracture of the thick PBT/PC specimens with strong interface occurred under plane-strain condition. Their impact toughness obeys the rule of mixtures and synergistic toughening could not be achieved. When thinner specimens were tested, the fracture took place under non-plane-strain condition. But, the toughness of the blends was much lower than the value predicted by the rule of mixtures. Negative blending effect was obtained. Study on the strain rate effect suggests that under impact loading, the PC domains in the blends are subjected to an additional plastic constraint imposed by the neighboring PBT matrix, which is more rigid at a higher strain rate. Since fracture of the PC is highly sensitive to the plastic constraint at the crack-tip, the PBT imposed high plastic constraint promotes brittle fracture of the PC, leading to a deteriorated impact resistance. Evidences from TEM, SEM and OM studies support the mechanism proposed. Based on this mechanism, some suggestions on the selection of polymer components and design of microstructure for rigid-rigid polymer blends are also given.     

Toughening of thermoset polymers by rigid crystalline particles

The toughening of an aromatic amine-cured diglycidyl ether of bisphenol-A epoxy with particles of crystalline polymers was studied. The crystalline polymers were poly (butylene terephthalate), nylon 6, and poly(vinylidene fluoride). Nylon 6 and poly(vinylidene fluoride) were found to toughen the epoxy about as well as did an equivalent amount of CTBN rubber. Poly(butylene terephthalate) was found to toughen the epoxy about twice as well as did the rubber. The toughness of poly(butylene terephthalate)-epoxy blends was independent of particle size for sizes in the range of tens of micrometres, but the toughness of the nylon 6-epoxy blends decreased with increasing particle size for sizes smaller than about 40 μm. There was no loss of either Young's modulus or yield strength of the epoxy with the inclusion of either nylon 6 or poly(butylene terephthalate) and less loss of these with the inclusion of poly(vinylidene fluoride) than with the inclusion of rubber. Toughness seems to have arisen from a combination of mechanisms. The poly(butylene terephthalate)-epoxy blends alone seem to have gained toughness from phase-transformation toughening. Crack path alteration and the formation of steps and welts and secondary crack bridging seem to have accounted for an especially large part of the fracture energy of the poly(vinylidene fluoride)-epoxy blends. Secondary crack nucleation contributed to the toughness of the nylon 6-epoxy blends.     

聚对苯二甲酸丁二醇酯(PBT)抗水解性能的研究

聚对苯二甲酸丁二醇酯（PBT）处于玻璃化温度以上的潮湿环境中时,由于其自有端羧基催化的酸性水解过程具有自加速的特点,造成材料力学性能急剧下降,通过封闭PBT的端羧基,使端羧基浓度下降到10meq/kg以下,并且添加抗水解稳定剂,消耗水解过程新生的端羧基,以冲缓PBT的酸性水解速度,提高PBT树脂耐水解性。     

Fracture toughness and fracture mechanisms of PBT/PC/IM blends: Part V Effect of PBT-PC interfacial strength on the fracture and tensile properties of the PBT/PC blends

To investigate the effect of PBT-PC interfacial strength on the fracture toughness and toughening mechanisms of the PBT/PC system, a series of PBT/PC blends with different content of in situ formed PBT-PC copolymers were made by melt blending. The in situ copolymer was separately prepared via reactive blending of the PBT and PC in the presence of a transesterification catalyst in a twin-screw extruder for a few minutes. The reactive extrudate (RE) was studied using a DSC and the existence of the PBT-PC copolymer in the RE was confirmed. Microstructure characterizations of the PBT/PC/RE blends revealed that the domain sizes of the PBT and PC decrease and the PBT-PC interfacial strength increases with the RE content. Compared with the PBT/PC blend, all the PBT/PC/RE blends have higher yield strength, elongation at break as well as tensile modulus. The quasi-static fracture tests show that fracture toughness of the blends increases with the RE content. Since the highest toughness was obtained with the blend having the highest RE content (7.5%), it is not certain at this stage whether adding more than 7.5% RE will further improve the fracture toughness. The impact toughness of the PBT/PC/RE blends was found to decrease with the increase of the PBT-PC interfacial strength, which confirms the failure mechanisms proposed in the Part-4 of this series.     

Rheological and mechanical properties of poly(butylene terephthalate)-modified epoxy resins

Poly(butylene terephthalate) (PBT) was used as modifier for epoxy resin. With the incorporation of 7.5 wt% PBT, the resin became a gel as shown by rheological measurements in steady shear, thixotropic loop and dynamic shear mode. The gel was very stable on storage. An abrupt change of rheological properties occurred at the dissolution temperature of the PBT spherulites. The PBT modifier did not impair mechanical properties of the cured resins, yet a moderate improvement in toughness was achieved.     

Morphology and properties of acrylate styrene acrylonitrile/polybutylene terephthalate blends

The structure and mechanical properties of acrylate styrene acrylonitrile (ASA) and ASA/polybutylene terephthalate (PBT) blends have been studied. The morphology of ASA is found to conform to a previous model. 40/60 and 60/40 blends of ASA/PBT have a two-phase, dispersed morphology while the 50/50 blend is shown to have a co-continuous structure. As processing temperature is increased, the mechanical properties decrease, due to PBT degradation. The 60/40 ASA/PBT blend has very poor impact resistance because of the continuous, degraded PBT matrix. Better mechanical properties are observed for blends with a continuous ASA matrix, particularly in the 50/50 blend. Fracture surface analysis reveals a unique morphology of mushroom-like PBT fibrils for the low processing temperature samples near the crack tip. This is thought to occur due to the competition of cohesion and adhesion of the PBT with the ASA matrix.     

SMA增容ABS/PBT共混体系的形态和力学性能——共混过程对体系的影响

以苯乙烯-马来酸酐共聚物(SMA)为增容剂,研究了共混工艺对ABS/PBT共混物聚集态结构和力学性能的影响。结果表明,SMA先与ABS共混再与PBT共混,共混物的分散相尺寸最小、分布最均匀,优于SMA先与PBT共混再与ABS共混的方法。ABS与PBT共混物的相容性差,加入反应性相容剂SMA后,PBT分散相尺寸变小且均匀地分散于ABS中,显著改善了ABS/PBT共混物的冲击、拉伸性能。共混物的聚集态结构强烈地受共混工艺的影响。