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1.
Polyvinyl fluoride (PVF) shows a strong crystal interference caused by the lateral distances of the chains, and is highly crystalline. Over the temperature range 0—100°C the degree of crystallinity is about 86%. Gelation of PVF in γ-butyrolactone was studied over practically the whole range of concentrations (from pure PVF to 1% solution). Gel temperatures were found practically independent of concentration (174°C). Gelation is coupled with crystallization. The swollen samples showed no differences in degree of crystallinity and quality of the crystals compared with the pure polymer at the same temperature. Therefore the degree of crystallinity of the gels is solely a function of temperature. The crosslinks of the network are formed by crystalline regions. Only the amorphous regions in the gels can take up solvent. Caused by the high crystallinity the gels have a crumb-like nature. 相似文献
2.
In this study, the relationship between the polymer–solvent interaction and the network structure of poly(vinyl alcohol) (PVA) gels prepared with organic solvents such as N-methylpyrrolidone (NMP) and ethylene glycol (EG) are investigated. The values of the intrinsic viscosity [η] and Huggins constant k′ of dilute PVA solutions indicate that the attractive interaction between PVA and NMP is higher than that between PVA and EG. The X-ray result shows that PVA–EG gels have a (101) diffraction peak of PVA crystal that appeared at about 2θ = 19°, while PVA–NMP gels only show a broad amorphous scattering peak. On the other hand, Fourier transform infrared results of PVA/EG gels also clearly show an intense peak at 1141 cm−1 due to the crystalline absorption. The results of H1 pulsed nuclear magnetic resonance show that the spin–spin relaxation time, and respectively, related to the polymer-rich and polymer-poor components decrease, and the fractional amount of the polymer-rich component, fs, increases, while that of the polymer-poor component, fl, decreases with an increase in the concentration of polymer. At a given concentration, the value of fs in the PVA–EG gel is larger than that in the PVA–NMP one. These facts indicate that the crystallinity in the PVA–EG gel is higher than that in the PVA–NMP gel, implying that the aggregation of PVA chains is much easier in the poor solvent, EG, than in the good solvent, NMP. The structural change with aging time in the PVA–EG gel is very remarkable because of the significant syneresis, indicating that the opaque PVA–EG gel with higher crystallinity has a comparatively heterogeneous and unstable network structure than the PVA–NMP gel does. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2477–2486, 1998 相似文献
3.
The relationship between the polymer–solvent interaction and gelation behavior of poly(vinyl alcohol) (PVA) solutions prepared from ethylene glycol/water (EG/water) mixed solvents was investigated using a viscometer, light scattering, FTIR, X‐ray, and pulsed NMR analyses. The viscometric result showed that the affinity to PVA for water is higher than that for EG. The light scattering result showed that the spinodal decomposition rate of the PVA solution decreases rapidly as the water content in the EG/water mixed solvent is increased. On the other hand, the FTIR and X‐ray results both indicated that the crystallinity of the PVA gel decreases with water content. These results imply that the water molecules must improve the affinity of the solvent to PVA to inhibit the aggregation or crystallization of PVA chains. The pulsed NMR measurement results showed that the spin–spin relaxation times related to the polymer‐rich and polymer‐poor phases of the PVA gel increase, and the fractional amount of the polymer‐poor phase increases while that of the polymer‐rich phase decreases with increasing water content. These facts indicated that the increase in the mobility of PVA chains must give rise to the difficulty in chain aggregation of PVA solutions with increasing water content. Two transition temperatures were found in the phase transition of the polymer‐rich phase. The lower transition temperature was attributed to the destruction of the denser chain entanglements in the polymer‐rich phase and the higher transition temperature was mainly concerned with the melting of the crystallites. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1113–1120, 2001 相似文献
4.
In this work, the Flory–Huggins parameters corresponding to the amorphous phase of a polyethylene (PE) and two ethylene–vinyl acetate (EVA) copolymers (with 18 and 33 % vinyl acetate content, respectively) samples, with different solvents have been determined below the melting temperature of the polymers, in order to quantify the bulk interactions of these polymer/solvent systems. The employed solvents were a dispersion solvent (cyclohexane), a polar solvent (vinyl acetate) and an association solvent (methanol). Initially, the inverse gas chromatography measurements allowed obtaining the retention volumes, activity coefficients and overall Flory–Huggins parameters of every polymer/solvent system. According to these parameters, in all cases, the more compatible solvent was cyclohexane, so it was selected as the probe to calculate the percentages of crystallinity at room temperature, whose results were in agreement the literature data (35 % for PE, 29 % for EVA18, and 12 % for EVA33). The percentage of crystallinity allowed determining the amorphous Flory–Huggins parameters which are the ones which take into account just the bulk interactions in a polymer/solvent mixture. The Flory–Huggins parameter results show that, to accurately study the vapor–liquid equilibrium between a polymer and a solvent (bulk interactions), when the range of studied temperatures is below the melting point of the polymer, it is crucial to calculate the amorphous contribution (χ amorphous) on the overall Flory–Huggins parameter. In the case of this study, the lower the vinyl acetate content (higher crystallinity), the higher the difference between the overall and amorphous Flory–Huggins parameters is. Analyzing the interactions between the three polymeric materials and the solvents it can be noticed that, for the most compatible solvent (cyclohexane), χ amorphous represents the less contribution, or the highest correction, to the overall Flory–Huggins parameter (around 50 % for PE and EVA18, and 79 % for EVA33, the less crystalline polymer). 相似文献
5.
Hyun Ju Lim Sung Jun Lee Han Gon Choi Jung Ae Kim Chul Soon Yong Sung Soo Han Seok Kyun Noh Jinho Jang Won Seok Lyoo 《应用聚合物科学杂志》2007,106(5):3268-3272
High‐molecular‐weight atactic poly(vinyl alcohol) (a‐PVA) gels loaded with (R,S)‐2‐(3‐benzoylphenyl)propionic acid (ketoprofen) were prepared from 5, 6, 7, and 8 g/dL solutions of a‐PVA with a number‐average degree of polymerization of 4000 in an ethylene glycol/water mixture with an aging method to identify the effect of the initial polymer concentration on the swelling behavior, morphology, and thermal properties of a‐PVA gels. Then, the release behavior of ketoprofen from a‐PVA gels was investigated. As the polymer concentration decreased, the ability for network formation decreased, and the degree of swelling of the a‐PVA gels increased. In addition, the enthalpy increased with an increase in the a‐PVA concentration, but the melting temperatures of the gels prepared at different initial polymer concentrations were the same; this indicated that tighter gel networks would be formed by a higher polymer chain density. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 相似文献
6.
Thermal analysis, solvent sorption, density measurement, and X-ray diffraction techniques were used to investigate structural changes in a variety of PVC compounds which were extruded or compression-molded at temperatures in the range 150–220°C. In all cases processing at lower temperatures in this range resulted in a disappearance of primary crystallinity and a concomitant development of secondary crystallinity, of lower order. In many cases processing above 190–200°C caused a small increase in crystallinity. It is believed that this is more ordered secondary crystallinity, which is therefore detectable by X-ray diffraction and also capable of influencing density and solvent sorption behavior. The observed structural behavior depends on shear as well as temperature. Primary crystallinity is higher in compression moldings, which have experienced lower shear levels, and the increase in crystallinity at higher temperatures is also greater. Equilibrium solvent sorption depends on the presence of primary and ordered secondary crystallinity. Diffusion is, however, unaffected as it occurs through amorphous and disordered crystalline regions only. 相似文献
7.
This study intended to establish a solvent map for formation of crystalline and amorphous paclitaxel by a solvent evaporation
process. Crystalline paclitaxel was produced by evaporation with polar solvents (acetone, acetonitrile, ethanol, isobutyl
alcohol, methanol, methyl ethyl ketone, and n-butyl alcohol) having a polarity index above 4.00. On the other hand, amorphous
paclitaxel was produced by evaporation with non-polar solvents (methylene chloride, n-butyl chloride, and toluene) having
a polarity index of about 4.00 or lower. The formation of paclitaxel was very closely associated with the polarity index of
the organic solvent used in the solvent evaporation process. In the case of crystalline paclitaxel, the higher the polarity
index and the lower the viscosity of the organic solvent (n-butyl alcohol, methyl ethyl ketone, and acetonitrile), the higher
the degree of crystallinity. In the case of amorphous paclitaxel, the shape and size of particles varied according to the
solvent (methylene chloride, n-butyl chloride, and toluene) used in the solvent evaporation process. 相似文献
8.
Polypropylene microporous tubular membranes were prepared by using camphene as solvent and through thermally induced phase
separation at various quenching temperatures. Characterization of the resulting membrane included scanning electron microscopy,
differential scanning calorimetry, and wide angle X-ray scattering. Microscopic observation showed that the membrane was composed
of spherical clusters and had a leafy structure. The crystallinity increased with the quenching temperature. The crystalline
structure was of smectic form. Permeation performance was also determined, including pure water permeability and retention
of dextran. The results showed that at lower quenching temperatures, the structure of membrane was denser. Therefore, the
permeability was lower and the retention was higher. 相似文献
9.
A series of physically crosslinked complex hydrogels of poly(vinyl alcohol) (PVA) and sodium carboxymethylcellulose (CMC) were prepared via physical mixing and a freeze/thaw technique. The morphology of the CMC/PVA complex gels was analyzed with differential scanning calorimetry and wide‐angle X‐ray diffraction. It was found that the crystallinity and melting temperature of the complex gels decreased, whereas the glass‐transition temperature increased, with an increase in the content of CMC. The reswelling of the complex gels was pH‐responsive and relied on the content of CMC and the freeze/thaw cycles. A network structure model of the complex gel was presented. PVA crystalline regions served as physical crosslinks; the interaction between CMC and PVA resulted in intramolecular entanglements. It was also found that the model drug hemoglobin was released completely from the complex hydrogels in 4 h, and its release rate increased with an increase in the content of CMC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
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11.
Poly(vinyl alcohol) (PVA) cast gels with high degrees of polymerization and hydrolysis were prepared at room temperature. After sufficient exchange of the outer solvent by fresh pure water, the gel was re-dissolved in pure water at a high temperature. Using this solution, the cast gel was prepared again. This re-dissolution process was repeated again, and a third cast gel was prepared. During each swelling process after each cast-drying process, the amount of elution from the gel was measured and the molecular weight distributions of PVA in the gel as well as in the outer solvent were quantitatively evaluated. The molecular weight distribution of the eluted PVA was found to depend on that of the PVA in the gel; the average molecular weight gradually increased as the re-dissolution process was repeated, while the polydispersity indices of both the PVA from the gel and the eluted PVA decreased. 相似文献
12.
Diana Gregor‐Svetec 《应用聚合物科学杂志》2006,100(2):1067-1082
The influence of drawing on the limiting draw ratio upon formation of the morphological structure of fibers spun from binary polypropylene (PP) blends was studied. Fibers were spun from a fiber‐grade CR‐polymer and from the blends of a fiber‐grade CR‐polymer with a molding‐grade polymer in the composition range of 10–50 wt % added. As‐spun fibers were immediately moderately and additionally highly drawn at the temperature of 145°C. The structure and morphology of these fibers were investigated by small‐angle X‐ray scattering, wide‐angle X‐ray scattering, differential scanning calorimetry, scanning electron microscopy, density, birefringence, and sound velocity measurements. It was shown that continuously moderately drawn fibers are suitable precursors for the production of high tenacity PP fibers of very high modulus, because of so called oriented “smectic” structure present in these fibers. With drawing at elevated temperature, the initial metastable structure of low crystallinity was disrupted and a c‐axis orientation of monoclinic crystalline modification was developed. Hot drawing increased the size of crystallites and crystallinity degree, the orientation of crystalline domains, and average orientation of the macromolecular chains and resulted in extensive fibrillation and void formation. It was found that the blend composition has some influence on the structure of discontinuously highly drawn fibers. With increasing the content of the molding‐grade polymer in the blend, the size of crystalline and amorphous domains, density and crystallinity, as well as amorphous orientation decreased. Relationship has been established between the mechanical properties, crystallinity, and orientation of PP fibers. It was confirmed that by blending the fiber‐grade CR‐polymer by a small percentage of the molding‐grade polymer, maximization of elastic modulus is achieved, mainly because of higher orientation of amorphous domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1067–1082, 2006 相似文献
13.
The crystalline morphologies of PBT (poly butylene terephthalate) and its glass fiber reinforced composite systems were investigated in a thin‐film form by polarized optical microscopy and wide‐angle X‐ray diffraction. Three different types of PBT morphology were identified in the Maltese cross pattern: 45° cross pattern (usual type) by solvent crystallization, 90° cross pattern (unusual type) by melt crystallization at low crystallization temperature, and mixed type by melt crystallization at crystallization temperatures higher than 160°C. The glass fibers increased the number density of spherulites and decreased the size of crystallites acting as crystallization nucleation sites without exhibiting trans‐crystallinity at the vicinity of the glass fiber surfaces. Finally, the storage modulus was analyzed by using a dual‐phase continuity model describing the modulus by the power‐law sum of the amorphous‐ and crystalline‐phase moduli. The crystalline‐phase modulus was extracted out from the PBT polymer and composite systems containing different amount of crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 478–488, 2002 相似文献
14.
Solutions of linear low density polyethylenes in organic solvents formed thermoreversible gels on cooling. Gel-melting temperatures of the polymers in tetralin, decalin, and o-xylene were measured. They increased slowly with increasing polymer concentration. Experimental data were analyzed by the thermodynamic theory of Takahashi, Nakamura, and Kagawa, which is derived for the gel-melting temperature of a crystalline linear copolymer gel. A plot of the gel-melting temperature by the theory depended considerably on the kind of comonomer of the polymer. 相似文献
15.
Marilyn L. Minus 《Polymer》2006,47(11):3705-3710
Shearing of poly(vinyl alcohol) (PVA)/single wall carbon nanotube (SWNT) dispersions result in the formation of self-assembled oriented PVA/SWNT fibers or ribbons, while PVA solution results in the formation of unoriented fibers. Diameter/width and length of these self-assembled fibers was 5-45 μm and 0.5-3 mm, respectively. High-resolution transmission electron micrographs showed well resolved PVA (200) lattice with molecules oriented parallel to the nanotube axis. Nanotube orientation in the self-assembled fibers was also determined from Raman spectroscopy. PVA fibers exhibited about 48% crystallinity, while crystallinity in PVA/SWNT fibers was 84% as determined by wide angle X-ray diffraction. PVA and carbon nanotubes were at an angle of 25-40° to the self-assembled fiber axis. In comparison to PVA, PVA/SWNT samples exhibited significantly enhanced electron beam radiation resistance. This study shows that single wall carbon nanotubes not only nucleate polymer crystallization, but also act as a template for polymer orientation. 相似文献
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17.
In this paper, different strategies to promote PLA crystallization were investigated with the objective of increasing the crystalline content under typical polymer processing conditions. The effect of heterogeneous nucleation was assessed by adding talc, sodium stearate and calcium lactate as potential nucleating agents. The PLA chain mobility was increased by adding up to 10 wt% acetyl triethyl citrate and polyethylene glycol as plasticizers. The crystallization kinetics were studied using DSC analysis under both isothermal and non-isothermal conditions. The isothermal data showed that talc is highly effective in nucleating the PLA in the 80-120 °C temperature range. In the non-isothermal DSC experiments, the crystallinity developed upon cooling was systematically studied at cooling rates of 10, 20, 40, and 80 °C/min. The non-isothermal data showed that the combination of nucleant and plasticizer is necessary to develop significant crystallinity at high cooling rates. The nucleated and/or plasticized PLA samples were injection molded and the effect of mold temperature on crystallinity was determined. It was possible to mold the PLA formulations using mold temperatures either below 40 °C or greater than 60 °C. At low temperature, the molded parts were nearly amorphous while at high mold temperatures, the PLA formulation with proper nucleation and plasticization was shown to achieve crystallinity levels up to 40%, close to the maximum crystalline content of the material. Tensile mechanical properties and temperature resistance of these amorphous and semi-crystalline materials were examined. 相似文献
18.
The morphology of fluorescent polyfluorene (PF) derivatives has strong effects on their electroluminescent (EL) performance. Herein, the influence of processing solvents on the morphology of PF-based white emissive polymer and its correlation to the EL behavior is studied. It is found that the PF copolymer films prepared from chlorobenzene:toluene (CB:TOL) solvent mixtures show stronger tendency to form crystalline α phase PF upon thermal annealing than those prepared from pure TOL or CB solvents. The evaporation rate difference in solvent mixtures can assist in the formation of crystal nucleus and enhance the crystallinity of PF backbone after thermal annealing. The results also reveal that the solvent mixture-processed fluorescent PF-based white emissive polymer not only shows more efficient blue emission, but also more balanced electron and hole transport. Accordingly, both the white emission purity and the light-emitting efficiency of the light-emitting diodes based on PF-based white emissive polymer are greatly enhanced. 相似文献
19.
The microstructural changes in isotactic polypropylene (PP), subsequent to quench from the melt to around Tg were studied using dynamic mechanical loss, volume dilatometry, small and wide angle X-ray scattering, infrared and NMR spectroscopy. The β-transition loss tangent and the specific volume decreased linearly with logarithm of aging time. Dynamic mechanical loss and NMR spectroscopy results established that amorphous chain mobility reduced during aging. X-ray and IR techniques showed that the crystallinity, the crystalline density, and the average chain conformation do not change during aging. Tensile tests indicated that diffusion of air or moisture into the polymer is not a competitive mechanism for the aging phenomenon. A simple free-volume model is quantitatively consistent with these observations. The fraction of the material which cannot age increased as the quench temperature decreased. Further, at lower temperatures a portion of the nonageable fraction is shown to reside in the amorphous fraction. 相似文献
20.
X-ray diffraction experiments with poly(p-phenylene) pellets demonstrated an increase in crystallinity with increase in molding temperature or annealing temperature. The increase in crystallinity may be attributed to annealing effects and loss of chlorine under severe conditions. Lattice constants for the crystalline polymer are presented, and the crystallographic data are compared with those of the lower oligomers. Poly(p-phenylene) was investigated also in relation to oxidative thermal stability, chemical and solvent resistance, and the effect of temperature and variation in molding conditions on fracture strength. The decrease in strength at elevated temperatures appears to be related to the increase in crystallinity. 相似文献