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1.
The melting, crystallization, and self-packed ring patterns in the spherulites of miscible blends comprising poly(trimethylene
terephthalate) (PTT) and poly(ether imide) (PEI) were revealed by optical, scanning electron microscopies (PLM and SEM) and
differential scanning calorimetry (DSC). Morphology and melting behavior of the miscible PTT/PEI blends were compared with
the neat PTT. Ringed spherulites appeared in the miscible PTT/PEI blends at all crystallization temperatures up to 220 °C,
whereas at this high temperature no rings were seen in the neat PTT. A postulation was proposed, and interrelations between
rings in spherulites and the multiple lamellae distributions were investigated. The specific interactions and the segregation
of amorphous PEI were discussed for interpreting the morphological changes of 220 °C-melt-crystallized PTT/PEI samples. Interlamellar
segregation of PEI might be associated with multiple lamellae in the spherulites of PTT/PEI blends; therefore, rings were
more easily formed in the PTT/PEI blends at all crystallization temperatures. A postulated model of uneven lamellar growth,
coupled with periodical spiraling, more properly describes the possible origin of ring bands from combined effects of both
interactions and segregation between the amorphous PEI and PTT in blends. 相似文献
2.
Miscibility and morphology of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate)/poly(ether imide) (PEN/PTT/PEI)
blends were investigated by using a differential scanning calorimeter (DSC), optical microscopy (OM), wide-angle X-ray diffraction
(WAXD), and proton nuclear magnetic resonance (1H-NMR). In the ternary blends, OM and DSC results indicated immiscible properties for polyester-rich compositions of PEN/PTT/PEI
blends, but all compositions of the ternary blends were phase homogeneous after heat treatment at 300 °C for more than 30 min.
An amorphous blend with a single T
g was obtained in the final state, when samples were annealed at 300 °C. Experimental results from 1H-NMR identified the production of PEN/PTT copolymers by so-called “transesterification”. The influence of transesterification
on the behaviors of glass transition and crystallization was discussed in detail. Study results identified that a random copolymer
promoted the miscibility of the ternary blends. The critical block lengths for both PEN and PTT hindered the formation of
crystals in the ternary blends. Finally, the transesterification product of PEN/PTT blends, ENTT, was blended with PEI. The
results for DSC and OM demonstrated the miscibility of the ENTT/PEI blends. 相似文献
3.
The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of Tg over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc. 相似文献
4.
Pitt Supaphol Nujalee Dangseeyun Pakin Thanomkiat Manit Nithitanakul 《Journal of Polymer Science.Polymer Physics》2004,42(4):676-686
Blends of poly(trimethylene terephthalate) (PTT) and poly(ethylene terephthalate) in the amorphous state were miscible in all of the blend compositions studied, as evidenced by a single, composition‐dependent glass‐transition temperature observed for each blend composition. The variation in the glass‐transition temperature with the blend composition was well predicted by the Gordon–Taylor equation, with the fitting parameter being 0.91. The cold‐crystallization (peak) temperature decreased with an increasing PTT content, whereas the melt‐crystallization (peak) temperature decreased with an increasing amount of the minor component. The subsequent melting behavior after both cold and melt crystallizations exhibited melting point depression behavior in which the observed melting temperatures decreased with an increasing amount of the minor component of the blends. During crystallization, the pure components crystallized simultaneously just to form their own crystals. The blend having 50 wt % of PTT showed the lowest apparent degree of crystallinity and the lowest tensile‐strength values. The steady shear viscosity values for the pure components and the blends decreased slightly with an increasing shear rate (within the shear rate range of 0.25–25 s?1); those of the blends were lower than those of the pure components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 676–686, 2004 相似文献
5.
Multiple melting peaks in some semicrystalline polymers such as poly(trimethylene terephthalate) (PTT) have caused some difficulty in estimating accurately the equilibrium melting points. PTT forms a miscible blend with amorphous poly(ether imide) (PEI); for comparison purposes, a miscible system of a fixed composition (PTT/PEI of weight ratio = 9/1) was determined. PTT and its miscible blend both exhibited dual melting peaks (labeled as low and high peaks: Tm,L, Tm,H), and the first peaks (Tm,L), not the second peak (Tm,H), should be used for extrapolation. The equilibrium melting temperatures (T) of neat PTT and its blend PTT/PEI (9/1) were 245.2 and 242.4 °C, respectively, by the linear Hoffman–Weeks treatment using the corrected values of Tm,L (i.e., values obtained using a heating rate close to zero). Linear and nonlinear treatments led to a significant difference in estimated T, and the relative validity of these two methods is discussed. The nonlinear estimate yielded a higher value by about 27.3 °C for neat PTT and 23.1 °C for the PTT/PEI (9/1) blend, respectively (also the correction in Tm,L at the same condition mentioned previously). Results showed melting depression in miscible PTT/PEI (9/1). In addition, the T value of neat PTT was higher than that of PTT/PEI (9/1) owing to much thicker and more‐perfect crystals in neat PTT. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1571–1581, 2002 相似文献
6.
Poly(vinylamine), PVA, complexes with cobalt chloride hexahydrate exhibit a 45 °C enhancement in the glass‐transition temperature per mol % of the d‐block metal cation. Poly(ethylene imine), PEI, complexes with CoCl2(H2O)6 exhibit a 20 °C enhancement in Tg per mol % Co2+. Since the basicities of primary and secondary amines are comparable (i.e., pKb,PVA ≈ 3.34 vs. pKb,PEI ≈ 3.27) and the rates at which each polymeric ligand displaces waters of hydration in the coordination sphere of Co2+ are similar, transition metal compatibilization is operative in blends of both polymers with CoCl2(H2O)6. These two polymers are immiscible in the absence of the inorganic component. Infrared spectroscopy suggests that nitrogen lone pairs in PVA and PEI coordinate to Co2+. The stress–strain response of a 75/25 blend of PVA and PEI with 2 mol % Co2+ reveals a decrease in elastic modulus from 4.4 × 109 N/m2 to 5.7 × 107 N/m2, a decrease in fracture stress from 3.7 × 107 N/m2 to 2.0 × 106 N/m2, and an increase in ultimate strain from 1.3 to 12% relative to the 75/25 immiscible polymer–polymer blend. A plausible explanation for this effect is based on the fact that cobalt chloride hexahydrate compatibilizes both polymers by forming a coordination bridge between nitrogen lone pairs in dissimilar chains. Hence, poly(ethylene imine), which is very weak with a Tg near −40 °C, is integrated into a homogeneous structure with poly(vinylamine) and the mechanical properties of the individual polymers are averaged in the compatibilized ternary complex. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 552–561, 2000 相似文献
7.
Mechanical,thermal and rheological properties and morphology of poly (lactic acid)/poly (propylene carbonate) blends prepared by vane extruder
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In this study, the poly (lactic acid) (PLA) and poly (propylene carbonate) (PPC) blends with different compositions were prepared by a novel vane extruder based on elongation rheology. The mechanical properties, morphologies, crystallization behavior, thermal stability, and rheological properties of the blends were investigated. Mechanical test showed that PLA could be toughened by PPC to some extent, and the impact strength of the PLA was maximized when PPC content was about 30%. Differential scanning calorimetry analysis revealed that PPC had little effect on the melting process, the crystallization behavior of PLA component in the blend was improved, and the cold crystallizability of PLA decreased with the increase of PPC content when the PPC content was less than 50%. Thermogravimetry analysis showed that the thermal stability of the blends was improved by compounding with PLA. Scanning electron microscope showed that the dispersion of PLA droplets in PPC matrix was better than that of PPC droplets in PLA matrix. Rheological test showed that the melt viscosity of the pure PLA and the blend with 10% PPC was insensitive to shear rate, and the blends melt appeared shear thinning phenomenon with the increase of PPC content. It also showed that the blends microstructure changed with the addition of PPC and the blends with PPC content in a certain range had similar stress relaxation mechanism. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
8.
Biphasic poly(ether imide)/poly(trimethyl hexamethylene terephthalamide) blends were obtained by injection moulding through the full composition range both with and without previous extrusion mixing. The extruded blends showed an improved performance, as the Tgs of the two amorphous phases changed and the changes were larger than those of directly injected blends. The Tg changes indicate the presence of the two components in the two phases of the extruded blends. The consequent low interfacial tension is proposed as the reason for the observed generally fine particle size (typically 0.3 μm). Both characteristics led to mostly ductile materials. The modulus of elasticity and the yield stress were slightly below those predicted by the rule of mixtures. As this was due to a lower orientation in the blends, both properties could improve through a change of the processing parameters. The increase in impact strength over that of pure PEI, and particularly, the sudden processability increase (35% torque decrease) upon a-PA addition, led to compatible blends that, as in the case of the 90/10 composition, could be a polymeric material alternative to unmodified PEI. 相似文献
9.
Blends of poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios, using N,N-dimethylacetamide (DMAc) as solvent. Reduced viscosity and rheological parameters of these blends were investigated. Cannon–Fenske viscometer was used to study the viscoelastic parameters of the salt-free polyelectrolyte blends and the data obtained was fitted in Fuoss–Strauss equation. Effects of temperature and concentration have been investigated. It was observed that the storage modulus (G′) and dynamic viscosity (η′) of the blends varies significantly as compare to pure SPEEK and PEI. Surface morphology and thermal behavior of the membranes were studied using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Form SEM results it was observed that the phase separation occurs at 25% PEI contents in blends. 相似文献
10.
Jieh‐Ming Huang 《Journal of Polymer Science.Polymer Physics》2004,42(9):1694-1704
We prepared blends of poly(butylene‐2,6‐naphthalate) (PBN) and poly(ether imide) (PEI) by solution‐casting from dichloroacetic acid solutions. The miscibility, crystallization, and melting behavior of the blends were investigated with differential scanning calorimetry (DSC) and dynamic mechanical analysis. PBN was miscible with PEI over the entire range of compositions, as shown by the existence of single composition‐dependent glass‐transition temperatures. In addition, a negative polymer–polymer interaction parameter was calculated, with the Nishi–Wang equation, based on the melting depression of PBN. In nonisothermal crystallization investigations, the depression of the crystallization temperature of PBN depended on the composition of the blend and the cooling rate; the presence of PEI reduced the number of PBN segments migrating to the crystallite/melt interface. Melting, recrystallization, and remelting processes occurring during the DSC heating scan caused the occurrence of multiple melting endotherms for PBN. We explored the effects of various experimental conditions on the melting behavior of PBN/PEI blends. The extent of recrystallization of the PBN component during DSC heating scans decreased as the PEI content, the heating rate, the crystallization temperature, and the crystallization time increased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1694–1704, 2004 相似文献
11.
New super‐tough poly(butylene terephthalate) (PBT)/poly(ethylene‐octene) copolymer (PEO) blends containing 2 wt% poly(ethylene‐co‐glycidyl methacrylate) (EGMA) as a compatibilizer were obtained by extrusion and injection molding. The blends comprised of an amorphous PBT‐rich phase with some miscibilized EGMA, a pure PEO amorphous phase, and a crystalline PBT phase that was not influenced by the presence of either PEO or EGMA. The blends showed a fine particle size up to 20 wt% PEO content. Super‐tough blends were obtained with PEO contents equal to or higher than 10%. The maximum toughness was very high (above 710 J/m) and was attained with 20% PEO without chemical modification of the commercial components used. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
12.
We have established time–temperature transformation and continuous-heating transformation diagrams for poly(ether–ether–ketone) (PEEK) and PEEK/poly(ether–imide) (PEI) blends, in order to analyze the effects of relaxation control on crystallization. Similar diagrams are widely used in the field of thermosetting resins. Upon crystallization, the glass transition temperature (Tg) of PEEK and PEEK/PEI blends is found to increase significantly. In the case of PEEK, the shift of the α-relaxation is due to the progressive constraining of amorphous regions by nearby crystals. This phenomenon results in the isothermal vitrification of PEEK during its latest crystallization stages for crystallization temperatures near the initial Tg of PEEK. However, vitrification/devitrification effects are found to be of minor importance for anisothermal crystallization, above 0.1°C/min heating rate. In the case of PEEK/PEI blends, amorphous regions are progressively enriched in PEI upon PEEK crystallization. This promotes a shift of the α-relaxation of these regions to higher temperatures, with a consequent vitrification of the material when crystallized below the Tg of PEI. The data obtained for the blends in anisothermal regimes allow one to detect a region in the (temperature/heating rate) plane where crystallization proceeds in the continuously close proximity of the glass transition (dynamic vitrification). These experimental findings are in agreement with simple simulations based on a modified Avrami model coupled with the Fox equation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 919–930, 1998 相似文献
13.
Liming Zhu Omar Gunnarsson Bengt Wessln 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1257-1265
An amphiphilic graft copolymer was prepared by transesterification of poly(2-ethylhexyl acrylate-co-methyl methacrylate) with poly(ethylene glycol) monomethyl ether (MPEG2000). The grafting reaction was performed in melt at 155°C. The purified graft copolymer was blended into poly(methyl methacrylate) in concentrations of 1.5-30 wt %, either by mixing in chloroform solution or by melt mixing by means of a twin-screw extruder or a Brabender blender. Films of the blends were prepared by solution casting onto glass plates or by hot pressing between polished Al plates. At concentrations up to 20% of the graft copolymer homogeneous blends were obtained. At higher concentrations the blends were heterogeneous, and side-chain crystallinity was detectable by DSC analysis. The surface properties of the films were studied by measurements of water contact angles. The surface accumulation of the graft copolymer was demonstrated as a large increase in the wetting angle hysteresis, and found to depend on the procedure for film preparation as well as the casting substrate. © 1995 John Wiley & Sons, Inc. 相似文献
14.
The effects of the addition of polyarylate (PAr) on the drawing ability of poly(ether imide) (PEI)/Rodrun liquid‐crystalline 5000 (Ro LC5000) (Ro) blends and on the mechanical properties of their ribbons were studied. The compatibilizing effect of the PAr led to an increase in the drawing ability of the blends, as seen by the fact that the maximum Ro content compatible with the drawing process increased from 15 to 30%. This may lead to new applications in the field of gas barrier materials. The presence of PAr also led to an increase in the adhesion between the two phases of the blends and consequent improved ductility. However, the very high modulus of elasticity and tensile strength in the direction of orientation (up to three‐fold those of the matrix) due to the less developed fibrillation were smaller than the corresponding values before compatibilization. These very large modulus of elasticity and tensile strength values and those perpendicular to the direction of orientation, which were similar to those of the matrix, led to a high anisotropy in the extruded ribbons that increased with the draw ratio (DR) and the Ro contents. The high mechanical properties of the ribbons may be used and the anisotropy diminished by layering the ribbons in, and perpendicular to, the direction of orientation, according to the expected external load. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
15.
A series of intercalated poly(trimethylene terephthalate) (PTT)/clay nanocomposites were prepared in a twin‐screw extruder by the melt mixing of PTT with either quaternary or ternary ammonium salt‐modified clays. The morphology and structure, along with the crystallization and melting behavior, and the dynamic mechanical behavior of the composites were characterized by X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The results showed that the PTT chains could undergo center‐mass transport from the polymer melt into the silicate galleries successfully during the blending and extrusion process. More coherent stacking of the silicate layers was reserved at higher clay concentrations and shorter blend times. Compared with conventionally compounded composites, the nanoscale‐dispersed organophilic clays were more effective as crystal nucleation agents. The influence of the nanosilicates on the crystallization and melting behavior of PTT became distinct when the concentration of clay was around 3 wt %. The changes in the crystallization behavior of the polymer/clay nanocomposites depended not only on the size of the silicates but also on the intrinsic crystallization characteristics of the polymers. The resulting nanocomposites showed an increase in the dynamic modulus of PTT and a decrease in the relaxation intensity (both in loss modulus and loss tangent magnitude). © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2275–2289, 2003 相似文献
16.
Peiguang Zhou H. L. Frisch L. Rogovina L. Makarova A. Zhdanov N. Sergeienko 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2481-2491
Simultaneous IPNs of poly(dimethyl siloxane-urethane) (PDMSU)/poly(methyl methacrylate) (PMMA) and related isomers have been prepared by using new oligomers of bis(β-hydroxyethoxymethyl)poly(dimethyl siloxane)s (PDMS diols) and new crosslinkers biuret triisocyanate (BTI) and tris(β-hydroxylethoxymethyl dimethylsiloxy) phenylsilane (Si-triol). Their phase morphology have been characterized by DSC and SEM. The SEM phase domain size is decreased by increasing crosslink density of the PDMSU network. A single phase IPN of PDMSU/PMMA can be made at an Mc = 1000 and 80 wt % of PDMSU. All of the pseudo- or semi-IPNs and blends of PDMSU and PMMA were phase separated with phase domain sizes ranging from 0.2 to several micrometers. The full IPNs of PDMSU/PMMA have better thermal resistance compared to the blends of linear PDMSU and linear PMMA. © 1993 John Wiley & Sons, Inc. 相似文献
17.
S. Makhija E. M. Pearce T. K. Kwei 《Journal of polymer science. Part A, Polymer chemistry》1992,30(13):2693-2698
Thermal oxidation of poly(ethylene oxide) (PEO) and its blends with poly(methyl methacrylate) (PMMA) were studied using oxygen uptake measurements. The rates of oxidation and maximum oxygen uptake contents were reduced as the content of PMMA was increased in the blends. The results were indicative of a stabilizing effect by PMMA on the oxidation of PEO. The oxidation reaction at 140°C was stopped at various stages and PMMA was separated from PEO and its molecular weights were measured by gel permeation chromatography (GPC). The decrease in the number-average molecular weight of PMMA was larger as the content of PEO increased in the blends. The visual appearance of the films suggested that phase separation did not occur after thermal oxidation. The activation energy for the rates of oxidation in the blends was slightly increased compared to pure PEO. © 1992 John Wiley & Sons, Inc. 相似文献
18.
Dae Woo Ihm Soo Young Park Cheol Gyu Chang Yoon Sung Kim Hwan Kwang Lee 《Journal of polymer science. Part A, Polymer chemistry》1996,34(14):2841-2850
The effects of transesterification on the miscibility of poly(ethylene terephthalate)/poly(ethylene 2,6-naphthalate) were studied. Blends were obtained by solution precipitation at room temperature to avoid transesterification during blend preparation. The physical blends and transesterified products were analyzed by wide-angle x-ray scattering, differential scanning calorimetry, and nuclear magnetic resonance spectroscopy. It was found that the physical blends are immiscible and when the extent of transesterification reaches 50% of the completely randomized state, independent of blend composition, the blends are not crystallizable and show a single glass transition temperature between those of starting polymers. The interchange reactions were significantly influenced by annealing temperature and time but negligibly by blend composition. © 1996 John Wiley & Sons, Inc. 相似文献
19.
采用自设计的双螺杆结构挤出制备聚乳酸(PLA)/醋酸淀粉(AS)的全生物降解材料,考察材料的AS的含量和取代度对复合材料动态流变性能、机械性能的影响。研究结果表明,AS含量明显影响复合材料的力学性能、复合黏度和储能模量:当AS含量从45%增加到70%,材料的拉伸强度下降,复数黏度和储能模量则提高。随着AS取代度由1.0上升为3.0,复合材料的复数黏度和储能模量下降,拉伸强度由12.0MPa上升为15.5MPa。对复合材料进行电镜扫描分析发现,AS以海岛结构形式分散在PLA的连续相中,取代度2.0的AS与PLA相容性最好,当其质量含量达到70%,材料的拉伸强度仍然不低于10.0MPa,具有较好的机械强度。 相似文献
20.
Fang‐Chyou Chiu Kai‐Hung Huang Jen‐Chang Yang 《Journal of Polymer Science.Polymer Physics》2003,41(19):2264-2274
This work examined the miscibility, crystallization kinetics, and melting behavior of melt‐mixed poly(trimethylene terephthalate) (PTT)/poly(ethylene‐co‐cyclohexane 1,4‐dimethanol terephthalate) (PETG) blends. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction techniques were used to approach the goals. The single composition‐dependent glass‐transition temperatures of the blends and the equilibrium melting temperature (T) depression of PTT in the blends indicated the miscible characteristic of the blend system at all compositions. T of pure PTT, determined with a conventional extrapolative method, was 525.8 K. Furthermore, the Flory–Huggins interaction parameter was estimated to be ?0.38. The dynamic and isothermal crystallization abilities of PTT were hindered by the incorporation of PETG. A complex melting behavior was observed for pure PTT and its blends. The observed complex melting behavior resulted mainly from the recrystallization and/or reorganization of the originally formed crystals during the heating scans. For the samples crystallized under the same conditions, the degree of recrystallization and/or reorganization declined with increasing PETG contents in the blends. The preliminary results obtained from the DSC experiments suggested that untraceable interchange reactions occurred in the studied blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2264–2274, 2003 相似文献