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1.
The miscibility of blends of phenolphthalein poly(ether ether sulfone) (PES-C) and poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. Differential scanning calorimetry (DSC) studies showed that the PES-C/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed a single, composition-dependent glass transition temperature (Tg), and thus that PES-C and PEO are miscible in the amorphous state at all compositions at lower temperature. At higher temperature, the blends underwent phase separation, and the PES-C/PEO blend system was found to display a lower critical solution temperature (LCST) behavior. The phase separation process in the blends has also been investigated by using DSC. Annealed at high temperatures, the PES-C/PEO blends exhibited significant changes of thermal properties, such as the enthalpy of crystallization and fusion, temperatures of crystallization and melting, depending on blend composition when phase separation occurred. These changes reflect different characteristics of phase structure in the blends, and were taken as probes to determine phase boundary. From both the thermal analysis and optical microscopy, the phase diagram of the blend system was established. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1383–1392, 1997  相似文献   

2.
The temperature dependence of the mean size of nanoscale free‐volume holes, 〈Vh〉, in polymer blend system consisting of polar and nonpolar polymers has been investigated. The positron lifetime spectra were measured for a series of polymer blends between polyethylene (PE) and nitrile butadiene rubber (NBR) as a function of temperature from 100 to 300 K. The glass transition temperatures (Tg) for blends were determined from the ortho‐positronium (o‐Ps) lifetime τ3 and the mean size of free‐volume holes 〈Vh〉 versus temperature as a function of wt % of NBR. The Tgs estimated from the PALS data agree very well with those estimated from DSC in view of different time scales involved in the two measurements. Both DSC and PALS results for the blends showed two clear Tgs of a two‐phase system. Furthermore, from the variation of thermal expansivity of the nanoscale free‐volume holes, the thermal expansion coefficients of glass and amorphous phases were estimated. Variations of the o‐Ps formation probability I3 versus temperature for pure PE and blends with low wt % of NBR were interpreted on the basis of the spur reaction model of Ps formation with reference to the effects of localized electrons and trapping centers produced by positron irradiation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 227–238, 2009  相似文献   

3.
A differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) study of miscibility in blends of the semicrystalline polyester poly(3-hydroxybutyrate) (PHB) and amorphous monomer epoxy DGEBA (diglycidyl ether of bisphenol A) was performed. Evidence of the miscibility of PHB/DGEBA in the molten state was found from a DSC study of the dependence of glass transition temperature (Tg) as a function of the blend composition and isothermal crystallization, analyzing the melting point (Tm) as a function of blend composition. A negative value of Flory–Huggins interaction parameter χPD was obtained. Furthermore, the lamellar crystallinity in the blend was studied by SAXS as a function of the PHB content. Evidence of the segregation of the amorphous material out of the lamellar structure was obtained. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013  相似文献   

4.
Blends of two or more ethylene–styrene (ES) copolymers that differed primarily in the comonomer composition of the copolymers were studied. Available thermodynamic models for copolymer–copolymer blends were utilized to determine the criteria for miscibility between two ES copolymers differing in styrene content and also between ES copolymers and the respective homopolymers, polystyrene and linear polyethylene. Model estimations were compared with experimental observations based primarily on melt‐blended ES/ES systems, particularly via the analysis of the glass‐transition (Tg ) behavior from differential scanning calorimetry (DSC) and solid‐state dynamic mechanical spectroscopy. The critical comonomer difference in the styrene content at which phase separation occurred was estimated to be about 10 wt % for ES copolymers with a molecular weight of about 105 and was in general agreement with the experimental observations. The range of ES copolymers that could be produced by the variation of the comonomer content allowed the study of blends with amorphous and semicrystalline components. Crystallinity differences for the blends, as determined by DSC, appeared to be related to the overlapping of the Tg of the amorphous component with the melting range of the semicrystalline component and/or the reduction in the mobility of the amorphous phase due to the presence of the higher Tg of the amorphous blend component. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2976–2987, 2000  相似文献   

5.
A vinyl‐terminated benzoxazine (VB‐a), which could be polymerized through ring‐opening polymerization, was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine. This VB‐a monomer was then subjected to blending with poly(ethylene oxide) (PEO), followed by thermal curing, to form poly(VB‐a)/PEO blends. The specific interactions, miscibility, morphology, and thermal properties of these blends were investigated with Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). Before curing, we found that PEO was miscible with VB‐a, as evidenced by the existence of a single composition‐dependent glass transition temperature (Tg) for each composition. The FTIR spectra revealed the presence of hydrogen‐bonding interactions between the hydroxyl groups of poly(VB‐a) and the ether groups of PEO. Indeed, the ring‐opening reaction and subsequent polymerization of the benzoxazine were facilitated significantly by the presence of PEO. After curing, DMA results indicated that the 50/50 poly(VB‐a)/PEO blend exhibited two values of Tg: one broad peak appeared in the lower temperature region, whereas the other (at ca. 327 °C, in the higher temperature region) was higher than that of pristine poly(VB‐a) (301 °C). The presence of two glass transitions in the blend suggested that this blend system was only partially miscible. Moreover, SEM micrographs indicated that the poly(VB‐a)/PEO blends were heterogeneous. The volume fraction of PEO in the blends had a strong effect on the morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 644–653, 2007  相似文献   

6.
Positron annihilation lifetime spectroscopy and differential scanning calorimetry (DSC) measurements were performed for blends of polyacrylamide (PAM) and poly(ethylene glycol) (PEG) and blends of poly(dimethylacrylamide) (PDMAM) and PEG. The samples were prepared by codissolution in a concentration range of 0–100 wt % PEG. The thermal behavior, characterized by DSC measurements, showed similar variations of the glass‐transition temperatures (Tg's) with the PEG concentration for the two systems. Pure PAM and PDMAM presented Tg's of 188 and 111 °C, respectively. A relatively small and nearly linearly decreasing Tg was observed for the two systems in the range of 20–80 wt % PEG. PEG crystals were present in all blend compositions, and no melting point depression was observed. The thermal results pointed to the partial miscibility of the blends. The degree of crystallinity of PEG increased with increasing PEG concentration for the PDMAM/PEG systems. The ortho‐positronium lifetime (τ3) increased with increasing PEG concentration for both blends. However, the parameter of the ortho‐positronium formation probability (I3) decreased with the PEG concentration. The product τI3, which was proportional to the total free volume fraction, was approximately constant with the PEG concentration for PDMAM blends and increased with the PEG concentration for PAM systems. This result may be interpreted as a consequence of a more heterogeneous structure in PAM blends. Scanning electron microscopy micrographs of blends with 40 and 80 wt % PEG provided evidence of the regions associated with PEG crystallites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1493–1500, 2003  相似文献   

7.
The thermal properties of blends of polycarbonate (PC) and poly(ε‐caprolactone) (PCL) were investigated by differential scanning calorimetry (DSC). From the thermal analysis of PC‐PCL blends, a single glass‐transition temperature (Tg) was observed for all the blend compositions. These results indicate that there is miscibility between the two components. From the modified Lu and Weiss equation, the polymer–polymer interaction parameter (χ12) of the PC‐PCL blends was calculated and found to range from −0.012 to −0.040 with the compositions. The χ12 values calculated from the Tg method decreased with the increase of PC weight fraction. By taking PC‐PCL blend as a model system, the values of χ12 were compared with two different methods, the Tg method and melting point depression method. The two methods are in reasonably good agreement for the χ12 values of the PC‐PCL blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2072–2076, 2000  相似文献   

8.
The glass transition behavior in athermal blends of poly(α‐methyl styrene) (PaMS) and its hexamer is investigated using differential scanning calorimetry (DSC). The results, along with previous data on similar blends of PaMS/pentamer, are analyzed in the context of the Lodge–McLeish self‐concentration model. A methodology is described to partition the calorimetric transition to obtain effective Tgs for each component of the blend. The dependences of these effective Tgs on overall blend composition are described by the Lodge–McLeish model, although the self‐concentration effect is less than expected based on the Kuhn length. The length scales of the cooperatively rearranging regions for the two components in the blends are also calculated adapting Donth's fluctuation model to the partitioned DSC transitions and are found to be similar for the two components and show a slight decrease at intermediate concentrations. The kinetics associated with the glass temperature, Tg, is examined by studying the cooling rate dependence of Tg for the pure components and the blends, as well as by examining the enthalpy overshoots in the heating DSC scans. It is observed that the cooling rate dependence of Tg in PaMS/hexamer blends at intermediate concentrations is similar to that of the hexamer, indicating that the kinetics of the glass transition for blends is dominated by the high mobility oligomeric component. Moreover, compared to the pure materials, the PaMS/hexamer blends exhibit a considerably depressed enthalpy overshoot, presumably resulting from their broader relaxation time distribution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 418–430, 2008  相似文献   

9.
A miscible homopolymer–copolymer pair viz., poly(ethyl methacrylate) (PEMA)–poly(styrene‐co‐butyl acrylate) (SBA) is reported. The miscibility has been studied using differential scanning calorimetry. While 1 : 1 (w/w) blends with SBA containing 23 and 34 wt % styrene (ST) become miscible only above 225 and 185 °C respectively indicating existence of UCST, those with SBA containing 63 wt % ST is miscible at the lowest mixing temperature (i.e., Tg's) but become immiscible when heated at ca 250 °C indicating the existence of LCST. Miscibility for blends with SBA of still higher ST content could not be determined by this method because of the closeness of the Tg's of the components. The miscibility window at 230 °C refers to the two copolymer compositions of which one with the lower ST content is near the UCST, while the other with the higher ST content is near the LCST. Using these compositions and the mean field theory binary interaction parameters between the monomer residues have been calculated. The values are χST‐BA = 0.087 and χEMA‐BA = 0.013 at 230 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 369–375, 2000  相似文献   

10.
The blend system containing a poly(vinylidene fluoride/trifluoroethylene) [P(VDF/TrFE)] copolymer (68/32 mol %) and poly(vinyl acetate) (PVAc) was miscible from the results of differential scanning calorimetry (DSC) studies that exhibit the presence of a single, composition‐dependent glass transition temperature (Tg) and a strong melting point depression for the semicrystalline P(VDF/TrFE) component. However, differences between the DSC and dielectric measurements, which showed a separate P(VDF/TrFE) Tg peak, suggests that the P(VDF/TrFE)/PVAc blends are actually partially miscible. Because of the lower dielectric constant of PVAc and the reduced sample crystallinity caused by the addition of PVAc, both the dielectric constant and the remanent polarization of the copolymer blends decrease with increasing PVAc content. The presence of a small amount of PVAc stabilized the anomalous ferroelectric behavior of ice–water‐quenched P(VDF/TrFE), and the blend portrayed normal polarization reversal behavior after adding only 1 wt % PVAc. The piezoelectric response suggests small changes with an increasing number of poling cycles. It is believed that PVAc affects the DE hysteresis behavior at the interface between crystalline and amorphous phases, although much work remains to be done to confirm this hypothesis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 927–935, 2003  相似文献   

11.
Blends of amorphous poly(DL‐lactide) (DL‐PLA) and crystalline poly(L‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were prepared by both solution/precipitation and solution‐casting film methods. The miscibility, crystallization behavior, and component interaction of these blends were examined by differential scanning calorimetry. Only one glass‐transition temperature (Tg) was found in the DL‐PLA/PMMA solution/precipitation blends, indicating miscibility in this system. Two isolated Tg's appeared in the DL‐PLA/PMMA solution‐casting film blends, suggesting two segregated phases in the blend system, but evidence showed that two components were partially miscible. In the PLLA/PMMA blend, the crystallization of PLLA was greatly restricted by amorphous PMMA. Once the thermal history of the blend was destroyed, PLLA and PMMA were miscible. The Tg composition relationship for both DL‐PLA/PMMA and PLLA/PMMA miscible systems obeyed the Gordon–Taylor equation. Experiment results indicated that there is no more favorable trend of DL‐PLA to form miscible blends with PMMA than PLLA when PLLA is in the amorphous state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 23–30, 2003  相似文献   

12.
The thermal properties of physical blends containing benzoxazine monomer and polycaprolactone (PCL) were monitored by DSC and Fourier transform infrared spectroscopy (FTIR). The ring‐opening reaction and subsequent polymerization reaction of the benzoxazine were facilitated significantly by the presence of a PCL modifier. Hydrogen‐bond formation between the hydroxyl groups of polybenzoxazine and the carbonyl groups of PCL was evident from the FTIR spectra. Only one glass‐transition temperture (Tg) value was found in the composition range investigated, and the Tg value of the resulting blend appeared to be higher in the blend with a greater amount of PCL. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 736–749, 2001  相似文献   

13.
We prepared two block copolymers 1 and 2 consisting of a third‐generation dendron with poly(ethylene oxide) (PEO) peripheries and a linear polystyrene (PS) coil. The PS molecular weights were 2000 g/mol and 8000 g/mol for 1 and 2 , respectively. The differential scanning calorimetry (DSC) data indicated that neither of the block copolymers showed glass transition, implying that there was no microphase separation between the PEO and PS blocks. However, upon doping the block copolymers with lithium triflate (lithium concentration per ethylene oxide unit = 0.2), two distinct glass transitions were seen, corresponding to the salt‐doped PEO and PS blocks, respectively. The morphological analysis using small angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM) demonstrated that a hexagonal columnar morphology was induced in salt‐doped sample 1‐Li+ , whereas the other sample ( 2‐Li+ ) with a longer PS coil revealed a lamellar structure. In particular, in the SAXS data of 2‐Li+ , an abrupt reduction in the lamellar thickness was observed near the PS glass transition temperature (Tg), in contrast to the SAXS data for 1‐Li+ . This reduction implies that there is a lateral expansion of the molecular section in the lamellar structure, which can be interpreted by the conformational energy stabilization of the long PS coil above Tg. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2372–2376, 2010  相似文献   

14.
Thermosetting blends composed of phloroglucinol‐cured bisphenol S epoxy resin and poly(ethylene oxide) (PEO) were prepared via the in situ curing reaction of epoxy in the presence of PEO, which started from initially homogeneous mixtures of diglycidyl ether of bisphenol S, phloroglucinol, and PEO. The miscibility of the blends after and before the curing reaction was established on the basis of thermal analysis (differential scanning calorimetry). Single and composition‐dependent glass‐transition temperatures (Tg's) were observed for all the blend compositions after and before curing. The experimental Tg's could be explained well by the Gordon–Taylor equation. Fourier transform infrared spectroscopy indicated that there were competitive hydrogen‐bonding interactions in the binary thermosetting blends upon the addition of PEO to the system, which was involved with the intramolecular and intermolecular hydrogen‐bonding interactions, that is, OH···O?S, OH···OH, and OH, versus ether oxygen atoms of PEO between crosslinked epoxy and PEO. On the basis of infrared spectroscopy results, it was judged that from weak to strong the strength of the hydrogen‐bonding interactions was in the following order: OH···O?S, OH···OH, and OH versus ether oxygen atoms of PEO. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 359–367, 2005  相似文献   

15.
The effects of supercritical carbon dioxide (SC CO2) fluids on the morphology and/or conformation of poly(ethylene oxide) (PEO) in PEO/poly(methyl methacrylate) (PMMA) blends were investigated by means of differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and Fourier transform infrared (FTIR). According to DSC data for a given blend, the melting enthalpy and, therefore, degree of crystallinity of PEO were increased, whereas the melting temperature of PEO was decreased, with SC CO2 treatment. The enhancement of PEO crystallization with SC CO2 treatment, as demonstrated by DSC data, was supported by WAXD data. According to FTIR quantitative analyses, before SC CO2 treatments, the conformation of PEO was transformed from helix to trans planar zigzag via blending with PMMA. This helix‐to‐trans transformation of PEO increased proportionally with increasing PMMA content, with around 0.7% helix‐to‐trans transformation per 1% PMMA incorporation into the blend. For a given blend upon SC CO2 treatments, the conformation of PEO was transformed from trans to helix. This trans‐to‐helix transformation of PEO decreased with increasing PMMA contents in the blends because of the presence of interactions between the two polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2479–2489, 2004  相似文献   

16.
Miscibility and hydrogen bonding interaction have been investigated for the binary blends of poly(butylene adipate‐co‐44 mol % butylene terephthalate)[P(BA‐co‐BT)] with 4,4'‐thiodiphenol (TDP) and poly(ethylene‐ oxide)(PEO) with TDP; and the ternary blends of P(BA‐co‐BT)/PEO/TDP by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The DSC results indicated that the binary blends of P(BA‐co‐BT)/TDP and PEO/TDP were miscible because each blend showed only one composition‐dependent glass‐transition over the entire range of the blend composition. The formation of intermolecular hydrogen bonds between the hydroxyl groups of TDP and the carbonyl groups of P(BA‐co‐BT), and between the hydroxyl groups of TDP and the ether groups of PEO was confirmed by the FTIR spectra. According to the glass‐transition temperature measured by DSC, P(BA‐co‐BT) and PEO, their binary blends were immiscible over the entire range of blend composition, however, the miscibility between P(BA‐co‐BT) and PEO was enhanced through the TDP‐mediated intermolecular hydrogen bonding interaction. It was concluded that TDP content of about 5–10% may possibily enhance miscibility between P(BA‐co‐BT) and PEO via a hydrogen bonding interaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2971–2982, 2004  相似文献   

17.
The miscibility and thermal properties of polyethylene oxide(PEO)/oligoester resin (OER) blends and PEO/crosslinked polyester (PER) blends were studied by differential scanning calorimetry (DSC). The effect of quenching process on the crystallization behavior of PEO for these two systems were investigated and discussed in details. It has been found that a single, composition dependent glass transition temperature (Tg) was observed for all the blends, indicating that the two systems are miscible in the amorphous state at overall compositions. From the melting point depression of PEO, the interaction parameter χ12 for PEO/OER blends and that for PEO/PER blends were found to be −1.29 and −2.01, respectively. The negative values of χ12 confirmed that both PEO/OER blends and PEO/PER blends are miscible in the molten state. Quenching process has a greater hindrance on the crystallization of PEO/OER blends than on that of PEO/PER blends. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3161–3168, 1997  相似文献   

18.
The miscibility and thermal properties of poly(N‐phenyl‐2‐hydroxytrimethylene amine)/poly(N‐vinyl pyrrolidone) (PHA/PVP) blends were examined by using differential scanning calorimetry (DSC), high‐resolution solid‐state nuclear magnetic resonance (NMR) techniques, and thermogravimetric analysis (TGA). It was found that PHA is miscible with PVP, as shown by the existence of a single composition‐dependent glass transition temperature (Tg) in the whole composition range. The DSC results, together with the 13C crosspolarization (CP)/magic angle spinning (MAS)/high‐power dipolar decoupling (DD) spectra of the blends, revealed that there exist rather strong intermolecular interactions between PHA and PVP. The increase in hydrogen bonding and in Tg of the blends was found to broaden the line width of CH—OH carbon resonance of PHA. The measurement of the relaxation time showed that the PHA/PVP blends are homogeneous at least on the scale of 1–2 nm. The proton spin‐lattice relaxation in both the laboratory frame and the rotating frame were studied as a function of the blend composition, and it was found that blending did not appreciably affect the spectral densities of motion (sub‐Tg relaxation) in the mid‐MHz and mid‐KHz frequency ranges. Thermogravimetric analysis showed that PHA has rather good thermal stability, and the thermal stability of the blend can be further improved with increasing PVP content. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 237–245, 1999  相似文献   

19.
Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to 1H and 13C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226  相似文献   

20.
Crosslinkable interpolymer complexes of novolac resin and poly(ethylene oxide) (PEO) were prepared by mutual mixing ethanol solutions of novolac and PEO. Fourier transform infrared (FTIR) studies revealed that the driving force for the formation of novolac/PEO complex is hydrogen bonding interaction between the hydroxyl groups of novolac and the ether oxygens of PEO. The morphology and thermal properties of the complexes before and after curing were investigated by optical microscopy and differential scanning calorimetry (DSC). It was found that the uncured novolac/PEO complexes had a single composition-dependent glass transition temperature (Tg). The curing with 15 wt % hexamine (HMTA) (relative to novolac content) resulted in disappearing of Tg behaviour for both the neat novolac and the novolac-rich complexes, owing to less mobility of the novolac chain segments. The melting temperature (Tm) and crystallization rate of the HMTA-cured novolac/PEO complexes decreased with increasing novolac content, and no Tm was observed for the cured complexes with PEO content less than 50%. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 401–411, 1998  相似文献   

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