成核剂对PET非等温结晶动力学的影响

利用差示扫描量热仪(DSC)研究了滑石粉、苯甲酸钠和离子聚合物Surlyn对聚对苯二甲酸乙二醇酯(PET)非等温结晶行为的影响,并用Ozawa模型计算了非等温结晶动力学参数。结果表明:三种成核剂均是PET的良成核剂,其中苯甲酸钠的成核效果最为显著。与纯PET相比,三种成核剂的加入均使PET的结晶峰温度Tmc向高温偏移,过冷度(Tm-Tmc)明显降低,结晶速率常数K明显增大。纯PET和PET/成核剂共混体系的Ozawa指数n值介于1-4之间,均不为整数,且PET/成核剂共混体系的Ozawa指数n值小于纯PET的n值。     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

成核剂对PET/PEN共混物性能影响及其机理研究

利用差示扫描量热法、X射线衍射和转矩流变测试等手段,研究了成核剂碳酸氢钠、苯甲酸钠和乙烯-甲基丙烯酸离子键聚合物(Surlyn)对聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯（PET/PEN）共混物结晶性能和力学性能的影响。结果表明,3种成核剂均能显著提高共混物的成核作用,其中,Surlyn和苯甲酸钠能明显提高共混物结晶性能,结晶峰温度提高约20 ℃,结晶速度提升近1倍;3种成核剂中,只有Surlyn在提高结晶性能的同时,还能提高共混物的力学性能;Surlyn是PET/PEN共混物理想的成核剂。     

Crystallization behavior of poly(lactide)/poly(β‐hydroxybutyrate)/talc composites

The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetics and thermal crystallinity of recycled PET. II. Topographic study on thermal crystallinity of the injection-molded recycled PET

The injected specimens of recycled poly(ethylene terephthalate) (R-PET) and its blends with engineering PET (E-PET) are studied with differential scanning calorimetry (DSC). Specimens are dissected into three segments of (1) outer skin, (2) middle, and (3) the core for the topographic study of their separate crystallinities, which are induced by different crystallization rates in the injection mode. DSC thermograms reveal the different crystallinity states among these three segments with decreasing crystallinity from core to middle to the skin segments and the times and contact of injection-molded specimens with the mold during the cooling cycle after the injection of the specimens. With the same procedures of injection molding, comparisons of crystallinity among various specimens of virgin blow molding grade PET (B-PET), E-PET, and R-PET are made. There are little differences in crystallinity among three segments of B- or E-PET specimens. In contrast, a higher degree of crystallinity in the core segment than either middle or skin segments is observed for the R-PET. This may contribute to the faster crystallization rate of the R-PET in the mold. Specimens of R-/E-PET blends follow the R-PET pattern, even in 20% of R-PET in the blend. This faster crystallization rate of R-PET is confirmed with the lowering crystallization temperatures (T_c) of the R-PET and R-/E-PET blended specimens in the DSC heating process. Dynamic DSC cooling analysis reveals a high order of crystallinity in R-PET and R-/E-PET blends. Gel permeation chromatography (GPC) measurements of molecular weights and distributions support the orderly structure for R-PET. Terminal group analysis and intrinsic viscosity measurements of the R-PET support the chain modification of R-PET during the thermal treatments in accordance with the evidences of smaller M_w and narrower molecular-weight distribution from the GPC findings for the recycled PET. © 1996 John Wiley & Sons, Inc.     

MELTING BEHAVIOR OF POLYETHYLENE TEREPHTHALATE COPOLYESTER AND POLYSTYRENE BLENDS

The melting behavior of polyethylene terephthalate (PET) copolyester/polystyrene (PS) blends was studied using differential scanning calorimetry. Multiple melting endotherms were observed for the PET copolyester as well as the PET copolyester/PS blend at T_c = 483 and 493 K, respectively. A higher crystallization temperature resulted in the reorganization of the crystalline species and an increase in area under the reorganization peak. Higher melting temperatures for PS-rich blends may be attributed to the formation of a stiffer matrix around the crystallites and the possible inhibition of crystal thickening. Melting behavior shows that the PET copolyester and PS form miscible blends up to 30 wt.% of PS, whereas with the lowering of the isothermal crystallization temperature to 483 K, miscibility was found only up to 10 wt.% of PS.     

Morphology,rheological, crystallization behavior,and mechanical properties of poly(L‐lactide)/ethylene‐co‐vinyl acetate blends with different VA contents

Poly(L‐lactide)/ethylene‐co‐vinyl acetate (PLLA/EVA) blends with different contents of Vinyl Acetate (VA) in EVA phase were prepared through melt blending process. Although the composition of the blends was invariant (70/30), different phase morphologies were observed, namely, sea‐island morphologies for the blends with VA contents of 7.5, 18, and 28 wt %, whereas approximate co‐continuous morphology for the blend with VA content of 40 wt % was observed. The interfacial interaction between PLLA and EVA was visualized by Fourier transform infrared and rheological measurements. The nonisothermal and isothermal crystallization behaviors of the blends were investigated by wide angle X‐ray diffraction, Differential scanning calorimetry, and polarization optical microscope. Post‐thermal treatment was applied to improve the crystalline structure of PLLA. The results show that all the samples are mainly in amorphous state during the injection molding process. However, annealing promotes the second crystallization of PLLA matrix, leading to the improvement of the crystalline structure. Especially, the effect of annealing on crystalline structure of PLLA matrix is greatly dependent on the VA content of EVA. As expected, addition of EVA results in the improvement of the ductility and fracture toughness of the blends. The decreased tensile modulus and tensile strength can be enhanced through annealing process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The morphology and property of HDPE in the presence of oscillation pressure and poly(ethylene terephthalate)

The injection‐molded specimens of neat HDPE and the PET/HDPE blends were prepared by conventional injection molding (CIM) and by pressure vibration injection molding (PVIM), respectively. The effect of oscillation pressure and PET phase with different shapes on superstructure and its crystal orientation distribution of injection molded samples were characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and two‐dimension wide‐angle X‐ray diffraction techniques (2D‐WAXD). Hermans' orientation functions were determined from the wide‐angle X‐ray diffraction patterns. With the PET particles added, the shear viscosity of blend increase and crystallization rate of HDPE phase is enhanced. For the neat HDPE samples, with the promotion from oscillation shear, the orientation parameter experienced a large increase, moreover, the PVIM can induce transverse lamellae (kebabs) twisting in growth direction. Because of the redefined flow field and nucleation effect of PET particles, the crystal orientation of blend is also increased. So the tensile strength of vibration samples enhanced and elongation at break declined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of filler treatment on the properties of TPU/PP blends: I. Thermal properties and stability

Commercially available organosilane (3‐glycidoxypropyltrimethoxysilane (GPTMS)) coupling agent was used to treat talc in order to improve the affinity relative between the filler and the polymer in composites as well as filler and polymer in the thermoplastic polyurethane/polypropylene (TPU/PP) blends (talc content was 5 wt%). The talc particles were first modified with GPTMS and then introduced into TPU, PP as well as TPU/PP blends with different weight ratios of polymers using blending method and subsequently injection molded in a hydraulic press. The aim was to report the effect of silane coupling agent on the thermal and morphological properties of talc filled composites and blends. The results showed that the thermal properties of the TPU, PP composites and TPU/PP blends were improved with the addition of silane treated talc (higher melting (T_m), crystallization (T_c) temperatures and degree of crystallinity (χ_c)). The glass transition temperature (T_g) obtained by dynamic mechanical analysis (DMA) of the TPU soft segments in TPU/PP blends increased with the addition of untreated and silane treated talc due to lower mobility of the soft segments in TPU and better miscibility of TPU and PP. TPU/PP blends with the silane treated talc show better thermal stability than the TPU/PP blends with untreated talc. POLYM. ENG. SCI., 55:1920–1930, 2015. © 2014 Society of Plastics Engineers     

Crystallization of poly(ethylene terephthalate)/polycarbonate blends. I. Unreinforced systems

The crystallization and transition temperatures of poly(ethylene terephthalate) (PET) in blends with polycarbonate (PC) is considered using thermal analysis. Additives typically used in commercial polyester blends, transesterification inhibitor and antioxidant, are found to enhance the crystallization rate of PET. Differential scanning calorimetry (DSC) reveals two glass transition temperatures in PET/PC blends, consistent with an immiscible blend. Optical microscopy observations are also consistent with an immiscible blend. Small shifts observed in the T_g of each component may be due to interactions between the phases. The degree of crystallinity of PET in PET/PC blends is significantly depressed for high PC contents. Also, in blends with PC content greater than 60 wt %, two distinct crystallization exotherms are observed in dynamic crystallization from the melt. The isothermal crystallization kinetics of PET, PET modified with blend additives, and PET in PET/PC blends have been evaluated using DSC and the data analyzed using the Avrami model. The crystallization of PET in these systems is found to deviate from the Avrami prediction in the later stages of crystallization. Isothermal crystallization data are found to superimpose when plotted as a function of time divided by crystallization half-time. A weighted series Avrami model is found to describe the crystallization of PET and PET/PC blends during all stages of crystallization. © 1996 John Wiley & Sons, Inc.     

Effects of filler size and content on shrinkage and gloss of injection molded PBT/PET/talc composites

Effects of filler size and content on the shrinkage of injection molded poly(butylene terephthalate)/poly(ethylene terephthalate)/talc (PBT/PET/talc) composites were investigated. Circular plate specimens were examined by a field emission scanning electron microscope and a numerical analysis code was used for modeling of the injection molding. Orientation effects of polymer molecules and fillers on the shrinkage behavior of PBT/PET/talc composites were illustrated by using schematic diagrams. It was found that the planes of talc particles were aligned parallel to the mold wall due to applied shear stresses and the largest axes of the disk‐like talc particles were oriented along the flow direction. Shrinkage of the PBT/PET/talc composites was decreased more rapidly along the flow direction than along the transverse direction as the talc content was increased. Small‐sized talc was more effective for reduction of the surface shrinkage of PBT/PET composites than titanium dioxide (TiO₂) or large‐sized talc. Although the PBT/PET polymer matrix almost covered the surface of talc particles, surface gloss of the particle filled composites was decreased as the size of mineral filler was increased. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Crystallization behavior of polypropylene filled with surface-modified talc

Talc-filled polypropylene (PP) composites were prepared by extrusion in a wide composition range (0–40 wt %). To improve the affinity relation between talc and the PP matrix, we modified the talc surface with silane coupling agents. Differential scanning calorimetry investigations on test samples, prepared by injection moulding, revealed that the talc content and its surface modification had a pronounced effect on the crystallization behavior of the filled PP composites. The experimental results indicate that a talc concentration of 2 wt % strongly affects the nonisothermal crystallization process of the PP, especially when talc is silane treated Isothermal crystallization experiments on samples with minimum amounts of talc (2 wt %) revealed an improved nucleation activity with silane-treated talc. © 1996 John Wiley & Sons, Inc.     

Orientation in composite of polypropylene and talc

X-ray diffraction and microscopical investigation of test samples prepared by injection molding from composites of isotactic polypropylene with talc revealed a preferred orientation of the talc and polypropylene matrix. Contrary to the situation in polypropylene alone, the preferred orientation in polypropylene–talc composites survived melting and a new crystallization. Crystallization rate measurements confirmed the nucleation activity of talc for polypropylene crystallization.     

Morphology development and non isothermal crystallization behaviour of drawn blends and microfibrillar composites from PP and PET

Microfibrillar composites (MFC) were prepared from the blends of polypropylene (PP) and poly (ethylene terephthalate) (PET) at a fixed weight ratio of 85/15. The blending of the mixture was carried out in a single screw extruder, followed by continuous drawing at a stretch (draw) ratio 5. The stretched blends were converted into MFC by injection moulding. Scanning electron microscopy (SEM) studies showed that the extruded blends were isotropic, but both phases possessed highly oriented fibrils in the stretched blends, which were generated insitu during drawing. The PET fibrils were found to be randomly distributed in the PP matrix after injection moulding. The non isothermal crystallization behaviour of the as extruded blend, stretched blend and MFC was compared. The analysis of the crystallization temperature and time characteristics revealed that the PET fibrils in the stretched blend had a greater nucleating effect for the crystallization of PP than the spherical PET particles in the as extruded blend and short PET fibrils in the MFC.     

Primary structure and physical properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) resin blends

The morphology and properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) that were injection molded under various conditions were studied. Under injection molding conditions that make it possible to secure transparency, blends did not show clear crystallinity at blending ratios of more than 20 mol% in spite of the fact that crystallinity can be observed in the range of PEN content up to 30 mol%. Because both transparency and crystallinity could be secured with a PEN 12 mol% blend, this material was used in injection molding experiments with various injection molding cycles. Whitening occurred with a cycle of 20 sec, and transparency was obtained at 30 sec or more. This was attributed to the fact that transesterification between PET and PEN exceeded 5 mol% and phase solubility (compatibility) between the PET and PEN increased when the injection molding time was 30 sec or longer. However, when the transesterification content exceeded 8 mol%, molecularly oriented crystallization did not occur, even under stretching, and consequently, it was not possible to increase the strength of the material by stretching. PET/PEN blend resins are more easily crystallized by stretch heat‐setting than are PET/PEN copolymer resins. It was understood that this is because residual PET, which has not undergone transesterification, contributes to crystallization. However, because transesterification reduces crystallinity, the heat‐set density of blends did not increase as significantly as that of pure PET, even in high temperature heat‐setting. Gas permeability showed the same tendency as density. Namely, pure PET showed a substantial decrease in oxygen transmission after high temperature heat‐setting, but the decrease in gas permeability in the blend material was small at heat‐set temperatures of 140°C and higher.     

Effects of nucleating agent on nonisothermal crystallization of syndiotactic polystyrene

The effects of nucleating agent on nonisothermal crystallization were examined for syndiotactic polystyrene (SPS) using Differential Scanning Calorimetry (DSC). The crystallization peak temperature T_c, the crystallization rate parameter (CRP), the enthalpy of crystallization and melting, and the recrystallization behavior were compared between organic (DMBS, 1,3,2,4-dis-5-(3,4-dimethyl benzylidene) sorbitol) and inorganic (talc) nucleating agents. Both of the nucleation agents promoted the crystallization rate of SPS until some critical concentration of about 3,000 ppm. DMBS worked more effectively as a nucleating agent than talc, although the T_c showed lower level in SPS/DMBS than SPS/talc.     

Mechanical properties,morphology, and crystallization behavior of new thermoplastic polyimide (N‐TPI)/poly(ether sulfone) blends

Blends of wholly aromatic new thermoplastic polyimide (N‐TPI) and poly(ether sulfone) (PES) were prepared by melt‐mixing and subsequent injection molding. Their mechanical properties, morphology, and crystallization behavior were investigated. A synergistic effect on the flexural properties was observed for the N‐TPI/PES blends over the whole compositions. Differential scanning calorimetric analysis confirmed that the blend is an immiscible system and that the crystallinity of the N‐TPI component is very low (0.4–1.4%) irrespective of the composition. Scanning electron microscopic analysis suggested that the improvement in flexural properties is likely due to the reinforcement of the PES matrix by the fibrous N‐TPI phase for the N‐TPI/PES (40/60, 20/80) blends. For N‐TPI/PES (80/20, 60/40), the orientation of the matrix N‐TPI rather than the fibrillation of the PES phase along the melt‐flow direction may contribute to the synergism observed. Also, study of the isothermal crystallization behavior of the blends revealed that the addition of 10 wt % PES accelerates the crystallization of N‐TPI and further addition causes the retardation of it. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1366–1374, 2002     

Crystallization of oriented isotactic polypropylene (iPP) in the presence of in situ poly(ethylene terephthalate) (PET) microfibrils

The present article reports the nonisothermal crystallization process and morphological evolution of oriented iPP melt with and without in situ poly(ethylene terephthalate) (PET) microfibrils. The bars of neat iPP and PET/iPP microfibrillar blend were fabricated by shear controlled orientation injection molding (SCORIM), which exhibit the oriented crystalline structure (shish-kebab), especially in the skin layer. The skin layer was annealed at just above its melting temperature (175 °C) for a relatively short duration (5 min) to preserve a certain level of oriented iPP molecules. It was found that the existence of ordered clusters (i.e. oriented iPP molecular aggregates) leads to the primary nucleation at higher onset crystallization temperature, and formation of the fibril-like crystalline morphology. However, the overall crystallization rate decreases as a result that the relatively high crystallization temperature restrains the secondary nucleation. With the existence of PET microfibrils, the heterogeneous nucleation distinctly occurs in the unoriented iPP melt and results in the increase of crystallization peak temperature and overall crystallization rate, for the first time, we observed that the onset crystallization temperature has been enhanced further with addition of PET microfibrils in the oriented iPP melt, indicating the synergistic effect of row nucleation and heterogeneous nucleation under quiescent condition.     

Effect of compatibilization on the oxygen‐barrier properties of poly(ethylene terephthalate)/poly(m‐xylylene adipamide) blends

The improvement of the oxygen‐barrier properties of poly(ethylene terephthalate) (PET) via blending with an aromatic polyamide [poly(m‐xylylene adipamide) (MXD6)] was studied. The compatibilization of the blends was attempted through the incorporation of small amounts of sodium 5‐sulfoisophthalate (SIPE) into the PET matrix. The possibility of a transamidation reaction between PET and MXD6 was eliminated by ¹³C‐NMR analysis of melt blends with 20 wt % MXD6. An examination of the blend morphology by atomic force microscopy revealed that SIPE effectively compatibilized the blends by reducing the MXD6 particle size. Thermal analysis showed that MXD6 had a nucleating effect on the crystallization of PET, whereas the crystallization of MXD6 was inhibited, especially in compatibilized blends. Blending 10 wt % MXD6 with PET had only a small effect on the oxygen permeability of the unoriented blend when it was measured at 43% relative humidity, as predicted by the Maxwell model. However, biaxially oriented films with 10 wt % MXD6 had significantly reduced oxygen permeability in comparison with PET. The permeability at 43% relative humidity was reduced by a factor of 3 in compatibilized blends. Biaxial orientation transformed spherical MXD6 domains into platelets oriented in the plane of the film. An enhanced barrier arose from the increased tortuosity of the diffusion pathway due to the high aspect ratio of MXD6 platelets. The aspect ratio was calculated from the macroscopic draw ratio and confirmed by atomic force microscopy. The reduction in permeability was satisfactorily described by the Nielsen model. The decrease in the oxygen permeability of biaxially oriented films was also achieved in bottle walls blown from blends of PET with MXD6. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1361–1370, 2005     

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