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1.
Syndiotactic polystyrene (sPS) and poly(phenylene oxide) (PPO) blends, miscible in the melt state, were crystallized from the melt and the quenched state at different temperatures. The effect of the crystallization temperature on the phase behavior of the blends and the polymorphic changes in sPS was investigated by dynamic mechanical analysis (DMA), wide‐angle X‐ray diffraction (WAXD), and density measurements. In most blends, the crystallization of sPS induced segregation into two homogeneous amorphous phases of different compositions. The temperatures of the DMA relaxations of the neat homopolymers and crystallized blends were fit by the Gordon–Taylor relation to calculate the compositions of these phases. In melt‐crystallized blends, with slower crystallization, the major amorphous phase became sPS‐rich, whereas the minor phase became PPO‐rich. These major and minor amorphous phases could be tentatively assigned to interfibrillar and interlamellar regions, respectively. In cold‐crystallized blends, slower crystallization decreased the sPS concentration in both phases, and the scale of segregation was much smaller. WAXD studies and density measurements indicated a complex polymorphic behavior of sPS after it was blended with PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1975–1983, 2003  相似文献   

2.
A unique rapid scanning rate differential scanning calorimeter is used to examine the differences in melt and cold crystallized poly (l-Lactide) (PLLA), a biodegradable semi-crystalline polymer. After isothermal melt and cold crystallization at various temperatures, both melt and cold crystallized PLLA are characterized by similar melting temperatures (Tm) and exhibit multiple melting behavior on heating at 500 °C/min. However, cold crystallization results in a higher degree of crystallinity (wc) compared to melt crystallization. While the overall amorphous fraction is higher for melt crystallization, the mobile amorphous fraction (wa) is found to be higher for cold crystallization. The rigid amorphous fraction (wraf) in PLLA is determined to be higher for melt crystallization than for cold crystallization at almost all temperatures. The higher values of wraf also appear to result in higher values of the glass transition temperature (Tg) for melt crystallized samples due to a reduction in mobility of amorphous phase. These dramatic differences depending on whether the material is brought to the crystallization temperature from the melt or the glassy state, could have profound implications for processing and optimizing the properties of PLLA.  相似文献   

3.
Poly(trimethylene terephthalate) (PTT)/polycarbonate (PC) blends with different compositions were prepared by melt blending. The miscibility and phase behavior of melt-quenched and cold-crystallized blends were studied using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy. The blends of all compositions display only one glass transition (T g ) in both states. The melting temperature and the crystallinity of PTT in the blend decrease with increasing PC content. The dielectric results for the melt-quenched blends, for PC content up to 60 wt.%, exhibited two merged relaxation peaks during the heating scan; the lower temperature relaxation peak represent the normal glass-transition (α) relaxation of the mixed amorphous phase and the higher temperature relaxation due to the new-constrained mixed amorphous phase after crystallization. Cold-crystallized blends displayed only one glass transition α-relaxation whose temperatures varied with composition in manner similar to that observed by DSC. The dielectric α-relaxation of cold crystallized blends has been analyzed. Parameters relating to relaxation broadening, dielectric relaxation strength, and activation energy were quantified and were found to be composition dependent. The PTT/PC blends could be considered as two-phase system, a crystalline PTT phase and a mixed amorphous phase consisting of a miscible mixture of the two polymers. However, the crystallinity was only detected for blends containing greater than 40 wt.% PTT.  相似文献   

4.
The crystallization and morphology of very‐low‐density polyethylene (VLDPE) and ultra‐low‐density polyethylene (ULDPE) blends with isotactic polypropylene (PP) were studied by differential scanning calorimetry (DSC) and hot‐stage optical microscopy (HSOM) with polarized light. In particular, the isothermal crystallization of PP in molten PE was investigated. A polypropylene homopolymer was melt‐blended with six types of VLDPEs and ULDPEs, with variations in branch content and length and in molecular weight. All the blends contained 20% PP by mass. It was found that the crystallization temperatures of PP and PE changed in the blends, and the crystallization of PP was affected by branch length and content and by the molecular weight of the PE, indicating a certain degree of miscibility between PP and PE. The isothermal crystallization rate of PP decreased in the blends; in particular, the crystallization rate of PP was slower in the ULDPE with lower MFI, suggesting that crystallization of PP was hindered by PE and that its rate was regulated by the viscosity of ULDPE. HSOM images showed that a portion of the PP crystallized from molten PE, although phase separation was obvious, providing additional information on the miscible behavior between PP and VLDPEs (or ULDPEs). Furthermore, the miscible level between the PP and the ULDPEs was higher than that between the PP and the VLDPEs because the degree of change in the crystallization behavior of the PP and PE was greater in the PP–ULDPE blends. This was possibly a result of the higher branch content in the ULDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1179–1189, 2003  相似文献   

5.
The phase behavior and crystallization of poly(ether ketone ketone)/polyimide blends was investigated by differential scanning calorimetry and dynamic mechanical analysis, and chemical interactions in the blends were probed by Fourier‐transform infrared spectroscopy. Amorphous blends were miscible over the entire range of composition, although mixing was most favorable at higher thermoplastic polyimide concentrations. Blending suppressed crystallization, especially of the minor component, but crystallization of both components, however, did occur in most of the blends. While blends quenched from the melt exhibited only a single amorphous phase, melt crystallized blends appeared to possess two amorphous phases with different compositions. Shifts in the vibration frequencies of the carbonyl and imide bonds were inconsistent with the development of strong, specific intermolecular interactions, but may be explained by a disruption of the packing of the two homopolymers by nature of the mixing. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1227–1235, 2004  相似文献   

6.
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 (Tg) 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 t1/2 and the parameters Zc 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  相似文献   

7.
Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-Tm component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-Tm component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.  相似文献   

8.
The phase behavior, crystallization, and morphology of blends based on poly (ether ether ketone) [PEEK] and bisphenol-A polyarylate [PAr] are described. This system is partially miscible in the melt. Upon quenching to an amorphous glass the system displays two glass transitions corresponding to a nearly pure PEEK phase (Tg1) and a PAr-rich mixed phase (Tg2). The presence of the PAr has a strong retarding influence on the rate of crystallization of PEEK in the blends. Cold crystallization from the amorphous glass occurs in two stages with increasing temperature, corresponding to the mobilization of the PEEK-rich and PAr-rich phases, respectively. At lower cold-crystallization temperatures (below Tg2), the immobile PAr-rich phase constrains crystallization of the PEEK-rich phase, as manifested in both a decreased rate of crystallization and decreased bulk crystallinity. Dynamic relaxation studies of the crystallized blends reveal two glass-rubber relaxations originating from interlamellar amorphous populations in the PEEK-rich and PAr-rich phases. In the PAr-rich phase, there is no evidence of large-scale PAr exclusion to interfibrillar or interspherulitic regions.  相似文献   

9.
Two commercial polymer materials, metallocene linear low density polyethylene (m‐LLDPE) and ethylene/vinyl acetate copolymer (EVA) have been used to form binary blends of various compositions. The mechanical properties, morphology, rheological behavior, dynamic mechanical properties, and crystallization of m‐LLDPE/EVA blends were investigated. It was found that with the addition of EVA, the fluidity and processability of m‐LLDPE were significantly improved, and the introduction of polar groups in this system showed no significant changes in mechanical properties at lower EVA content. As verified by morphology observation and differential scanning calorimetry analysis, miscible blends were formed within certain weight ratios. Dynamic mechanical property studies showed that flexibility of the blends was enhanced in comparion with pure m‐LLDPE, where the peak value of loss modulus shifted to lower temperature and its intensity was enhanced as EVA content increased, indicating the existence of more amorphous regions in the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 905–910, 2004  相似文献   

10.
The thermal and mechanical properties of blends, obtained by mixing polyamide 6 (PA6) and an amorphous aromatic copolyamide G21 (ISO nomenclature PA 6I/6T), were investigated by differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. Quenched blends show a single glass transition temperature; the Tg-composition trend was interpreted by means of the Gordon–Taylor equation. The half-time of crystal-lization decreases by increasing the G21 content and this indicates a depression of the overall crystallization rate. A small decrease in the equilibrium melting temperature of PA6 in the blends was observed; this finding suggests that the interaction parameter in PA6/G21 blends is probably very small. The dynamic mechanical analysis of crystallized blends suggests the presence of a homogeneous amorphous phase even if the crystallization of PA6 occurred. The tensile mechanical properties reveal that G21 acts as stiffener of PA6. The collected experimental data suggest that PA6 and G21 are miscible in the composition range investigated. © 1996 John Wiley & Sons, Inc.  相似文献   

11.
Optical microscopy, differential scanning calorimetry, and small angle X‐ray scattering techniques were used to study the influence of the crystallization conditions on morphology and thermal behavior of samples of binary blends constituted of isotactic polypropylene (iPP) and a novel graft copolymer of unsaturated propylene with styrene (uPP‐g‐PS) isothermally crystallized from melt, at relatively low undercooling, in a range of crystallization temperatures of the iPP phase. It was shown that, irrespective of composition, no fall in the crystallinity index of the iPP phase was observed. Notwithstanding, spherulitic texture and thermal behavior of the iPP phase in the iPP/uPP‐g‐PS materials were strongly modified by the presence of copolymer. Surprisingly, iPP spherulites crystallized from the blends showed size and regularity higher than that exhibited by plain iPP spherulites. Moreover, the amount of amorphous material located in the interspherulitic amorphous regions decreased with increasing crystallization temperature, and for a given crystallization temperature, with increasing uPP‐g‐PS content. Also, relevant thermodynamic parameters, related to the crystallization process of the iPP phase from iPP/uPP‐g‐PS melts, were found, composition dependent. The equilibrium melting temperature and the surface free energy of folding of the iPP lamellar crystals grown in the presence of uPP‐g‐PS content up to 5% (wt/wt) were, in fact, respectively slightly lower and higher than that found for the lamellar crystals of plain iPP. By further increase of the copolymer content, both the equilibrium melting temperature and surface free energy of folding values were, on the contrary, depressed dramatically. The obtained results were accounted for by assuming that the iPP crystallization process from iPP/uPP‐g‐PS melts could occur through molecular fractionation inducing a combination of morphological and thermodynamic effects. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2286–2298, 2001  相似文献   

12.
The phase behavior and the crystallization kinetics of blends composed of isotactic polypropylene (iPP) and linear low‐density polyethylene (LLDPE) were investigated by differential scanning calorimetry. The phase behavior indicates the formation of separate crystals of iPP and LLDPE at each investigated blend composition. The crystallization trace reveals that iPP crystallizes in its normal range of temperatures (i.e., at temperatures higher than that of LLDPE), when its content in the blend is higher than 25% by weight. In the blend whose iPP content is as high as 25%, at least a portion of iPP crystallizes at temperatures lower than that of LLDPE. This behavior has been proposed by Bassett to be attributed to a change in the kind of nucleation from heterogeneous to homogeneous. From the Avrami analysis of the isothermal crystallization of iPP in the presence of molten LLDPE, n values close to 2 are always obtained. According to our previously proposed interpretation of the Avrami coefficient, it can be related to the crystallite fractal dimension, through d = n + 1, which gives values close to 3, according to the spherulitic observed morphology. The kinetics parameter, i.e., the half‐time of crystallization, and the kinetic constant k show that a decrease in the overall rate of crystallization of iPP occurs on blending. Optical microscopy photographs, taken during the cooling of the samples from the melt, confirm the above results and show increasingly less resolved spherulite texture on increasing LLDPE content in the blend. The diffusion parameters evaluated for the neat polymers and for the blends in dichloromethane, which give information on the miscibility in the amorphous state, show that the diffusional behavior of the blends is governed by iPP, suggesting a two‐phase amorphous state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3338–3346, 2003  相似文献   

13.
The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000  相似文献   

14.
Tensile properties of polyethertherketone (PEEK) have been studied at 125, 25, and ?100°C for thin films prepared with different thermal histories. Initial morphology was controlled by rate of cooling from the melt. Amorphous films resulted from quenching the melt, while semicrystalline films were obtained by cooling the melt at different rates, or by crystallization of the rubbery amorphous state. The films were characterized using density, X-ray scattering, differential scanning calorimetry, and infrared spectroscopy. Scanning electron microscopy was used to examine fracture surfaces. Degree of crystallinity and rate of cooling from the melt affected the tensile properties at all test temperatures. For films with nearly the same degree of crystallinity, those which were more slowly cooled from the melt fractured at the lowest strain. The amorphous films were most tough, drawing to 233% at ?100°C and to over 500% at 125°C. Films crystallized from the rubbery amorphous state had stress–strain behavior intermediate between that of the amorphous and melt-crystallized films at all test temperatures. Density measurements on the drawn material indicate that void formation occurs simultaneously with the formation of fibrillar crystals. Necking resulted in density increases for amorphous films, and density decreases for the semicrystalline films.  相似文献   

15.
Polycarbonate blends with poly(ε-caprolactone) were prepared by both melt-blending and solution-blending techniques, and the properties of these blends were studied by thermal analytical and dynamic mechanical testing methods. Each blend composition was found to have a single glass transition temperature, and the temperature location of this transition was found to be a function only of blend composition and to be independent of the blending technique employed. This behavior led to the conclusions that these two polymers form blends containing a single amorphous phase comprised of the two materials and that this miscible phase results primarily from physical rather than chemical interactions between the two polymers. A reversible liquid-liquid-type phase separation was found to occur when the blend system was heated to high melt temperatures. The temperature required for phase separation, the lower critical solution temperature, was found to vary with blend composition and component molecular weight in the manner expected from thermodynamic considerations. The level of crystallinity of poly(ε-caprolactone) was affected by the presence of the polycarbonate. The polycarbonate also crystallized to an appreciable extent in many of the blends.  相似文献   

16.
Binary blends of poly(vinyl chloride) (PVC) with α‐methylstyrene‐acrylonitrile‐butadiene‐styrene copolymer (AMS‐ABS) were prepared via melt blending. A single glass transition temperature (Tg) was observed by differential scanning calorimetry, thus indicating that PVC is miscible with the α‐methylstyrene‐acrylonitrile‐styrene in AMS‐ABS. The results from attenuated total reflection Fourier transform infrared spectra indicated that specific strong interactions were not available in the blends. With increasing amounts of AMS‐ABS, both heat distortion temperature and thermal stability were increased considerably. With regard to mechanical properties, flexural and tensile properties decreased with increasing AMS‐ABS content. A synergism was observed in impact strength. The morphology of both impact‐fractured and tensile‐fractured surfaces, observed by scanning electron microscopy, correlated well with the mechanical properties. It is suggested that there was a transition of fracture mechanisms with the changing composition of the binary blends—from shear yielding for blends rich in PVC to cavitation for blends rich in AMS‐ABS. J. VINYL ADDIT. TECHNOL., 19:1–10, 2013. © 2013 Society of Plastics Engineers  相似文献   

17.
The miscibility and crystallization behavior of poly(ether ether ketone ketone) (PEEKK)/poly(ether imide) (PEI) blends prepared by melt‐mixing were investigated by differential scanning calorimetry. The blends showed a single glass transition temperature, which increased with increasing PEI content, indicating that PEEKK and PEI are completely miscible in the amorphous phase over the studied composition range (weight ratio: 90/10–60/40). The cold crystallization of PEEKK blended with PEI was retarded by the presence of PEI, as is apparent from the increase of the cold crystallization temperature and decrease of the normalized crystallinity for the samples anealed at 300°C with increasing PEI content. Although the depression of the apparent melting temperature of PEEKK blended with PEI was observed, there was no evidence of depression in the equilibrium melting temperature. The analysis of the isothermal crystallization at 313–321°C from the melt of PEEKK/PEI (100/0, 90/10, and 80/20) blends suggested that the retardation of crystallization of PEEKK is caused by the increase of the crystal surface free energy in addition to the decrease of the mobility by blending PEI with a high glass transition temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 769–775, 2001  相似文献   

18.
Blends of two elastomeric ethylene–octene copolymers with similar octene contents having a random (ORC) and a blocky architecture (OBC) are prepared by melt mixing. The thermal and mechanical properties of ORC, OBC and their blends are investigated by DSC, dynamic mechanical analysis and tensile tests. The morphology of the semi-crystalline samples is studied by AFM and WAXS. Two types of crystals have been observed: (i) Orthorhombic crystals forming lamellae with an estimated thickness of about 13 nm composed mainly of long polyethylene-like sequences of OBC that melt a temperature of about 120 °C and (ii) fringed micellar crystals with a thickness of 2–4 nm formed basically by short polyethylene-like sequences of ORC that have melting temperatures between 30 and 80 °C. The amorphous phase contains a relatively homogeneous mixture of segments of both components indicated by the relatively uniform shape of the loss modulus peaks from dymamic-mechanical measurements for all investigated copolymers and blends. ORC crystallization is hindered in blends as indicated by lower melting enthalpies. This might be related to the high octene content of the amorphous phase at the relevant crystallization temperature as well as geometrical constraints since ORC crystallization occurs in an already semi-crystalline polymer. The results of tensile tests show that the mechanical behavior can be tailored via blend composition and morphology of the semi-crystalline material. The findings clearly indicate that blending is a powerful strategy to optimize the properties of polyolefin-based copolymers.  相似文献   

19.
Rosario E.S. Bretas  Donald G. Baird   《Polymer》1992,33(24):5233-5244
This paper is concerned with a novel ternary blend composed of poly(ether imide) (PEI), poly(ether ether ketone) (PEEK) and a liquid crystalline polymer (LCP; HX4000, Du Pont). Different compositions were prepared by extrusion and injection moulding. Dynamic mechanical thermal analysis and the observation of the fracture surfaces, before and after annealing, allowed determination of the cold crystallization temperatures and miscibility behaviour of these systems. PEEK/PEI blends are known from previous studies to be miscible at all compositions. In this case it was observed that the PEEK/HX4000 blend was miscible up to 50 wt% HX4000 but partially miscible above this value. The PEI/HX4000 blends were found to be partially miscible in the whole concentration range. As a result, some ternary blend compositions exhibited only one phase, while others exhibited two phases. The measurement of the tensile properties showed that ternary blends with high modulus can be obtained at high LCP loadings, while compositions with high ultimate tensile strength can be obtained with high loadings of PEI or PEEK.  相似文献   

20.
Binary blends of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) were found to display a peculiar crystallization kinetics. The two biodegradable polymers were blended by melt mixing, to obtain binary blends at various compositions. Temperature‐modulated calorimetry and dynamic‐mechanical analysis indicated that the blend components are partially miscible, and display two separate glass transitions, at temperatures intermediate to those of the plain polymers. Electron microscopy analysis disclosed the morphology of PLA/PPC blends, made of PPC‐rich particles finely dispersed within the PLA‐rich matrix. The possible establishment of interactions between the functional groups of the two polymers upon melt mixing has been hypothesized as the reason for partial miscibility and compatibility of the two biodegradable polymers. The PLA/PPC blends display good mechanical properties, with enhanced performance at rupture compared with plain PLA. Most importantly, the addition of PPC affects also the crystallization kinetics of PLA, since the more mobile PPC chains favor diffusion of the stiffer PLA chain segments towards the growing crystals, which fastens the spherulite growth rate of PLA. Such positive influence of an amorphous polymer on crystal growth rate has been demonstrated here for the first time in blends that display phase‐separation in the melt. POLYM. ENG. SCI., 55:2698–2705, 2015. © 2015 Society of Plastics Engineers  相似文献   

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