Crystallization behavior of PBT/ABS polymer blends

Poly(butylene terephthalate) (PBT) crystallization behavior is modified by blending it with acrylonitrile‐butadiene‐styrene copolymers (ABS). The effects of ABS on melting and crystallization of PBT/ABS blends have been examined. Most ABS copolymers of different rubber content and styrene/acrylonitrile ratios studied showed little effect on the melting behavior of PBT crystalline phase. However, ABS copolymer with high acrylonitrile content had a significant effect on the crystallization behavior of the PBT/ABS blends. The nucleation rate of the PBT crystalline phase decreased due to the presence of the high acrylonitrile content ABS, whereas the spherulitic growth rate increased significantly. These phenomena are attributed to changes in nucleation and growth mechanisms of PBT crystalline phase promoted by ABS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 423–430, 1999     

Crystallization kinetics of glass fiber reinforced PBT composites

The effect of glass fibers on the crystallization of poly(butylene terephthalate) (PBT) was investigated by crystallization kinetics analysis under isothermal and nonisothermal conditions. From the crosspolar optical micrographs of melt‐ and solvent‐crystallized PBT composites, the glass fibers were found to increase the number density and decrease the size of crystallites. The glass fibers provided heterogeneous nucleation sites, and thus enhanced the overall rate of PBT crystallization in isothermal experiments. However, the Avrami exponent and the regime transitions were not significantly affected by the presence of glass fibers. For the nonisothermal kinetics of PBT composites, the model prediction was excellent in most ranges of crystallization, but it deviated above 70% of crystallization especially at fast cooling rates (>40°C/min). This discrepancy of the model seemed to result from the growth regime transitions, which were clearly observed especially at high undercoolings. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 576–585, 2000     

TPP/PMMA复合物促进环氧树脂/酸酐体系的固化动力学研究

以三苯基膦(TPP)和甲基丙烯酸甲酯(MMA)为原料合成了TPP/PMMA复合物,用DSC研究了TPP/PMMA催化双酚A二缩水甘油醚(EP828)/甲基四氢苯酐(MTHPA)体系固化反应动力学。非等温固化动力学研究结果表明,转化率在20%～60%范围内,用Ozawa法能较好地描述环氧树脂/酸酐体系的固化反应过程。     

Dynamically cured PP/MAH-g-SEBS/epoxy blends

Abstract

A new method concerning the simultaneous reinforcing and toughening of polypropylene (PP) is reported. Dynamic cure of the epoxy resin with 2-ethylene-4-methane-imidazole was successfully applied in the PP/maleic anhydride grafted styrene–ethylene–butylene–styrene (MAH-g-SEBS) triblock co-polymer, and the obtained blends were named as dynamically cured PP/MAH-g-SEBS/epoxy blends. The stiffness and toughness of the blends are in a good balance, and the smaller size of the epoxy particle in the PP/MAH-g-SEBS/epoxy blends shows that MAH-g-SEBS was also used as a compatibiliser. The structure of the dynamically cured PP/MAH-g-SEBS/epoxy blends is the embedding of the epoxy particles by MAH-g-SEBS. The cured epoxy particles as organic filler increase the stiffness of the PP/MAH-g-SEBS blends, and the improvement in the toughness is attributed to the embedded structure. The tensile strength and flexural modulus of the blends increase with increasing epoxy resin content, and the impact strength reaches a maximum of 342 J m^?1 at the epoxy resin content of 10wt-%. Differential scanning calorimetry analysis shows that the epoxy particles in the dynamically cured PP/MAH-g-SEBS/epoxy blends could have contained embedded MAH-g-SEBS, decreasing the nucleating effect of the epoxy resin. Wide angle X-ray diffraction analysis shows that the dynamical cure and compatibilisation do not disturb the crystalline structure of PP in the blends.     

Cure kinetics, morphological and dynamic mechanical analysis of diglycidyl ether of bisphenol-A epoxy resin modified with hydroxyl terminated poly(ether ether ketone) containing pendent tertiary butyl groups

Hydroxyl terminated poly(ether ether ketone) based on tert-butyl hydroquinone (PEEKTOH) was used to modify a diglycidyl ether of bisphenol-A epoxy resin. A diamine, 4,4′-diaminodiphenylsulfone was used as the curing agent. Isothermal differential scanning calorimetric measurements of the blends were carried out at 180, 165 and 150 °C. The extent of reaction was found to decrease with the addition of PEEKTOH. The phenomenological model developed by Kamal was used for kinetic analysis of curing reaction. The curing reaction followed autocatalytic mechanism regardless of the presence and amount of oligomer present in the epoxy resin. The experimental and theoretical reaction rates were in good agreement during the initial stages of the reaction. The experimental values were lower than theoretical rate during the final stages of reaction due to increase in the viscosity of the system. A semiemperical model was used to explain diffusion control during final stages of reaction. The cured blends exhibited two phase morphology at all the curing temperatures. A uniform particle size distribution was observed at all compositions. The domain size decreased slightly with increase in oligomer content and with decrease in curing temperature. Finally, the viscoelastic properties were analysed using dynamic mechanical thermal analysis. Two T_gs corresponding to epoxy rich and thermoplastic rich phases were evident from the dynamic mechanical spectrum.     

端异氰酸酯聚醚增韧环氧树脂固化动力学研究

采用差示扫描量热（DSC）技术测定了在芳胺类为固化剂的条件下,增韧环氧体系固化反应过程中的热行为,得出固化反应过程的动力学参数,实验数据表明,以芳胺为固化剂的体系中,固化反应表观活化能及动力学频率因子,反应级数均有明显降低。     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

聚对苯二甲酸丙二醇酯的结晶性能研究

采用热台偏光显微镜和DSC差示扫描量热仪对PET、PTT和PBT的结晶性能进行了研究。实验得到的结果是:PBT具有极强的结晶能力。在相同的△T下,PTT的结晶诱导期和球晶出现的时间比PET短,球晶的生长速率也比PET快;同时,在相同的△T下,PTT的总结晶速率大于PET。PET和PTT在较高的温度下等温结晶时倾向于异相成核,而随着等温结晶温度的降低,开始倾向于均相成核。     

Correlation between crystallization kinetics and melt phase behavior of crystalline-amorphous block copolymer/homopolymer blends

We show that the phase behavior of the strongly segregated blend consisting of a crystalline-amorphous diblock copolymer (C-b-A) and an amorphous homopolymer (h-A), which depends on the degree of wetting of A blocks by h-A, can be probed by the crystallization kinetics of the C block. A lamellae-forming poly(ethylene oxide)-block-polybutadiene (PEO-b-PB) was blended with PB homopolymers (h-PB) of different molecular weights to yield the blends exhibiting ‘wet brush’, ‘partially dry brush’, and ‘dry brush’ phase behavior in the melt state. The crystallization rate of the PEO blocks upon subsequent cooling, as manifested by the freezing (crystallization) temperature (T_f), was highly sensitive to the morphology and spatial connectivity of the microdomains governed by the degree of wetting of PB blocks. As the weight fraction of h-PB reached 0.48, for instance, T_f experienced an abrupt rise as the system entered from the wet-brush to the dry-brush regime, because the crystallization in the PEO cylindrical domains in the former required very large undercooling due to a homogeneous nucleation-controlled mechanism while the process could occur at the normal undercooling in the latter since PEO domains retained lamellar identity with extended spatial connectivity. Our results demonstrate that as long as the C block is present as the minor constituent the melt phase behavior of C-b-A/h-A blends can also be probed using a simple cooling experiment operated under differential scanning calorimetry (DSC).     

Cure kinetics and morphology of blends of epoxy resin with poly (ether ether ketone) containing pendant tertiary butyl groups

The cure kinetics and morphology of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin modified with a poly (ether ether ketone) based on tertiary butyl hydroquinone (PEEK-T) cured with diamino diphenyl sulphone (DDS) were investigated using differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (DMTA). The results obtained from DSC were applied to autocatalytic and diffusion controlled kinetic models. The reaction mechanism broadly showed autocatalytic behaviour regardless of the presence of PEEK-T. At higher PEEK-T concentration, more diffusion controlled mechanism was observed. The rate of curing reaction decreased with increase in thermoplastic content and also with the lowering of curing temperature. The activation energies of the blends are higher than that of the neat resin. The blends showed a phase separated morphology. The dispersed phase showed a homogeneous particle size distribution. The T_g of the neat resin decreased with the decrease in cure temperature. Two T_g's corresponding to the epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum. The storage modulus of 10 and 20 phr PEEK-T blends are found to be greater than the neat resin.     

PEN／MMT纳米复合材料结晶动力学的研究

采用熔融插层法制备聚2,6-萘二甲酸乙二酯(PEN)/蒙脱土(MMT) 纳米复合材料,用Avrami方程和张志英方法对所得数据进行了等温结晶和非等温结晶动力学的研究.结果表明,在PEN/MMT共混物中由于MMT的加入,降低了PEN/MMT的结晶活化能,导致共混物的结晶速率提高;MMT含量影响共混物的结晶速度,加入少量的MMT可以明显提高共混物的结晶速率;共混物的表面活化能的变化与Avrami方程得出的n值变化相似,MMT的含量影响共混物成核结晶速度.     

聚乳酸（PLA）／己二酸-对苯二甲酸-丁二酯共聚物（PBAT）／乙酰化柠檬酸三丁酯（ATBC）共混物的结晶行为

采用熔融共混法制备聚乳酸（PLA）／己二酸-对苯二甲酸-丁二酯共聚物（PBAT）／乙酰化柠檬酸三丁酯（ATBC）共混物。用差示扫描量热仪（DSC）和偏光显微镜（POM）分析了乙酰化柠檬酸三丁酯（ATBC）对共混物PLA结晶行为的影响。结果表明当PLA／PBAT含量为80／20（质量比）时,随着ATBC量的增加,PLA的Tg、Tc和Tm降低,结晶度提高,球晶生长速率增加。     

Mechanical and dielectric breakdown properties of PBT/TPE,PBT/PBT/PET,and PBT/antioxidant blends

To improve the thermal aging flexibility of poly(butylene terephthalate) (PBT), PBT was melt‐blended with three type thermoplastic elastomer [poly ether‐ester type (TPE1), polyester‐ester type (TPE2), and poly(buthylene 2,6‐naphthalate)/poly(tetramethylene glycol) block copolymer type (TPE3)], PBT/poly(ethylene terephthalate), (PET) alloy (Alloy), and phosphate type antioxidant (T1). The content of the three type TPEs and Alloy was fixed at 20 parts per 100 g of PBT. The morphology and thermal behavior of these blends have been investigated with scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetry (TG). In the case of PBT/Alloy‐20 and PBT/TPE3–20 blends show clean fractured surface, whereas for PBT/TPE1–20 and PBT/TPE2–20 blends, the elongated pieces or fiber can be seen abundantly which indicates a good compatibility. TG traces show a significant shift of the weight loss toward higher temperature for PBT/Alloy‐20, whereas PBT/TPE1–20, PBT/TPE2–20 and PBT/TPE3–20 blend decrease in thermal stability than PBT. To investigate the applicability for insulation material, the prepared blend samples were extruded an electric wire and flexibility and electric breakdown voltage (BDV) of wire after thermal aging were studied. For PBT/TPE1–20 and PBT/TPE2–20 blends did not show any cracks after flexibility test at 130°C for 6 h and 225°C for 30 min. In contrast PBT, PBT/Alloy‐20, PBT/TPE3–20, and PBT/T1–1 showed a partial crack in the insulation after flexibility test at 130°C for 6 h although its good flexibility at 225°C for 30 min. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization kinetics and morphology of poly(trimethylene terephthalate)

In this work, the isothermal crystallization kinetics of polytrimethylene terephthalate (PTT) was first investigated from two temperature limits of melt and glass states. For the isothermal melt crystallization, the values of Avrami exponent varied between 2 and 3 with changing crystallization temperature, indicating the mixed growth and nucleation mechanisms. Meanwhile, the cold crystallization with an Avrami exponent of 5 indicated a character of three-dimensional solid sheaf growth with athermal nucleation. Through the analysis of secondary nucleation theory, the classical regime I→II and regime II→III transitions occurred at the temperatures of 488 and 468 K, respectively. The average work of chain folding for nucleation was ca. 6.5 kcal mol⁻¹, and the maximum crystallization rate was found to be located at ca. 415 K. The crystallite morphologies of PTT from melt and cold crystallization exhibited typical negative spherulite and sheaf-like crystallite, respectively. Moreover, the regime I→II→III transition was accompanied by a morphological transition from axialite-like or elliptical-shaped structure to banded spherulite and then non-banded spherulite, indicating that the formation of banded spherulite is very sensitive to regime behavior of nucleation.     

Cure kinetics, morphology and miscibility of modified DGEBA-based epoxy resin - Effects of a liquid rubber inclusion

Kinetics of the curic reaction and morphology of a diglycidyl ether of bisphenol-A based epoxy resin (DGEBA), using an anhydride hardener (nadic methyl anhydride) at different weight contents of carboxyl-terminated copolymer of butadiene and acrylonitrile liquid rubber (CTBN) was investigated using a differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and scanning electron microscopy (SEM). The aim of the work is to understand the effects of inclusion of the liquid rubber phase in the transition phenomena that occur during the curing reaction. The curic reaction at three different curic temperatures and at varying rubber contents in the range of 5-20 wt% has been studied. The reaction rate and conversions that occurred at the curic temperatures were analyzed. The increase in the rate with the curic temperature showed this as a thermally catalyzed reaction. The rate of the reaction was found to decrease in liquid rubber-modified epoxies due to the effect of dilution and viscosity increase as obtained from the gelation times. The experimental data showed an autocatalytic behavior of the reaction, which is explained by the model predicted by Kamal. This model includes two reaction constants k₁ and k₂ and two reaction orders m and n. The order of the overall reaction was found to be approximately 2. The activation energies Ea₁ and Ea₂ were estimated at all curic temperatures for neat and all modified epoxies. The results obtained from the DSC data were also applied to diffusion controlled kinetic models. A schematic model to represent the curic reaction and phase separation was introduced and the molecular mechanism of this curing reaction was discussed. During the curic reaction, phase separation of the liquid rubber from the epoxy matrix took place and the modified epoxies showed phase separated morphology. The dispersed phase showed a homogenous particle size distribution. The size of the phase separated domains increased with increasing concentration of the CTBN and decreased with rise in curing temperature. The glass transition temperature (T_g) of the modified epoxies decreased with increase in curic temperature as studied from dynamic mechanical thermal analysis. Addition of the liquid rubber lowered the T_g of the network. This became prominent in the modification of the matrix with 15 and 20 wt% of the elastomer. This is attributed to flexibilization of the matrix. The dissolved rubber plasticizes the epoxy network. The T_g of the neat rubber in the low-temperature region was shifted to higher temperature upon addition of the elastomer. A higher shift was noted for 15 and 20 phr inclusion. This was due to dissolved epoxy in the rubber-rich phase that increased the modulus of the rubbery phase. The inclusion of a large wt% of carboxyl-terminated butadiene-co-acrylonitrile (CTBN) decreased the cross-linking density of the thermoset matrix.     

PBT /纳米SiO2非等温结晶动力学研究

熔融制备了PBT/纳米SiO₂复合材料,用DSC分别研究了SiO₂在低含量(0.3%质量分数)和高含量(3%)时的非等温结晶行为;并分析了PBT/纳米SiO₂复合材料的结晶动力学。结果表明,纳米SiO₂对PBT有异相成核作用,加入纳米SiO₂后,显著提高了PBT结晶温度,加快了其结晶速率。结晶动力学表明,莫志深法很好的吻合了PBT/纳米SiO₂复合材料体系,而Ozawa方法并不太适合。通过结晶活化能的计算,表明在低含量(0.3%)时有更好的结晶能力。     

PBT/PTT合金的非等温结晶行为

采用差示扫描量热法(DSC)研究了聚对苯二甲酸丁二酯(PBT)/聚对苯二甲酸丙二酯(PTT)合金的非等温结晶动力学.随着降温速率的增大,PBT/PTT合金的结晶峰温均降低,结晶峰均加宽.采用Jeziorny法、莫志深法和Flyn-Wall-Ozawa法分析非等温结晶过程,Jeziorny法能够描述PBT/PTT合金的初期结晶过程,对后期结晶存在一定偏差,各PBT/PTT合金的结晶维数变化不大;莫志深和Flyn-Wall-Ozawa法能很好地描述PBT/PTT合金的非等温结晶过程,随PTT含量增加,由Flyn-Wall-Ozawa法求得PBT/PTT合金的活化能呈增加趋势.相对结晶度为0.5,m(PBT)/m(PTT)分别为90∶10,70∶30,50∶50时,PBT/PTT合金的活化能分别为-201.9,-116,0,-66.6 kJ/mol;相对结晶度为0.5时,m(PBT)/m(PTT)为50∶50的合金活化能比PTT(-77.4 kJ/mol)还高.     

The effect of brominated epoxy on epoxy/phenolic reactive blends

Innovative reactive blends containing epoxy and brominated epoxy (BE) incorporated with resole-type phenolic were studied with the aim to elucidate the curing kinetics and the final thermomechanical characteristics of this unique system. Curing kinetics was investigated by means of the activation energy determined using differential scanning calorimetry (DSC ) at various heating rates analyzed by the Arrhenius equation. Both DSC and Fourier transform infrared revealed that bromine elimination at elevated temperatures (above 220 °C) had lowered the activation energy in the case of BE containing phenolic blends. The thermomechanical properties showed that the addition of conventional epoxy to resole decreased its thermal properties and modulus compared to neat resole. Distinctively, BE/resole blends exhibited increased glass-transition temperature, compared to diglycidyl ether of bisphenol A/resole blends in combination with higher elongation and toughness compared to neat resole. It was concluded that BE/epoxy resin/phenolic reactive systems offer high T _g, mechanical properties and toughness and hence are applicable for structural adhesives and for matrices of polymer-fiber composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47172.     

Crystallization behavior of PHA/PEDEA oligoester blends

The crystallization behavior of oligoester blends prepared from crystalline poly(hexanediol adipate) (PHA) and amorphous poly(ethylene diethylene glycol adipate) (PEDEA) was studied using POM, WAXD, and DSC. The crystal form of both PHA and the blends are spherulites. The crystallinity, melting enthalpies, and crystallization rate increased with increased PHA content in the blends. Two sharp diffraction peaks of each blend were detected at the same position, where, respectively, 2θ = 21.3° and 24.1°. The research on the crystallization kinetics showed that the Avrami exponent of all the oligoester blends is approximately 4. It was demonstrated that the crystallization mechanism of PHA is not disturbed by amorphous PEDEA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1363–1368, 2002; DOI 10.1002/app.10268     

Crystallization kinetics of some new olefinic block copolymers

Blocky ethylene-octene copolymers synthesized by chain-shuttling polymerization differ from statistical copolymers in their rapid rate of crystallization and in the formation of space-filling spherulites even when the crystallinity is as low as 7%. The bulk crystallization rate, measured with DSC, was rapid even in copolymers with a relatively large fraction of non-crystallizable soft block and only slowed somewhat as the amount of crystallizable hard block decreased from 100 to 18 wt%. As measured with the polarized optical microscope, the linear spherulite growth rate exhibited the same dependence on soft block content as the bulk crystallization rate. The fold surface energy was extracted from an analysis of the growth rate according to the Lauritzen-Hoffman theory. A gradual increase in the fold surface energy with soft block content reflected some increasing disorder of the fold surface. In contrast, even a small amount of statistically distributed comonomer was very effective in disrupting the fold surface regularity as demonstrated by the high fold surface energy.