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1.
《Polymer Photochemistry》1981,1(3):177-190
The photo-oxidative degradation of nylon 6 with light above 300 nm was investigated. The increase in the dynamic modulus (E′) and the change in the ultra-violet spectrum at 280 nm were observed on irradiation with spectrally dispersed light between 300 and 600 nm. Scission was the predominant reaction accompanying crystallisation of the broken polymer segments, as shown by the decrease in intrinsic viscosity and the development of the peaks in the X-ray diffraction pattern. E′ during the photo-oxidation above 365 nm increased linearly with time reflecting crystallisation. The activation energy was obtained as 20·0 kJ/mole according to the Arrhenius relation of the rate constant k, which was determined from the equation E′t = E′0 + kt, where E′t is E′ at time t and E′0 is that at t = 0. The effect of the photo-oxidation above 300 nm on the temperature dependence of the viscoelastic property of nylon 6 was also investigated. On irradiation, the α-relaxation at 85°C broadened, the β-relaxation at −45°C decreased in its intensity, and the γ-relaxation at −95°C was unchanged in the tan δ versus temperature curves. 相似文献
2.
Due to the presence of reactive benzylic bromide, Exxpro has much better interaction with silica in comparison with polybutadiene as demonstrated by the high bound rubber level. The better silica/Exxpro interaction is further substantiated by the low degree of filler network formation in comparison to that observed for silica filled polybutadiene as demonstrated by the much smaller deviation of low strain shear modulus from the Guth-Gold relationship for the silica filled Exxpro. Silane treatement of silica reduces filler network formation in polybutadiene but has only slight effect on silica filled Exxpro indicating that even without silane treatment silica already disperse well in Exxpro due to high degree of filler/polymer interaction. This result in silica filled Exxpro compound exhibiting better processability (lower shear viscosity) as well as dynamic performances for tire applications (higher tan δ at −20 and 0°C, lower tan δ at 60°C). We speculate that nucleophilic substitution reaction takes place between benzylic bromide and surface hydroxide group of silica. 相似文献
3.
0.5–3 wt% nanosilica was added to an epoxy resin based on diglycidyl ether of bisphenol A (DGEBA) and cured at 25, 40 or 60 °C using isophoronediamine (IPDA) as hardener. Aggregates of nanosilica were properly dispersed into the DGEBA-IPDA resin and agglomerates formation was avoided. Addition of nanosilica increased the storage modulus E′ and the area and height of the tan δ curve of DGEBA-IPDA resin cured at 25 °C, but no significant differences were found by curing at higher temperature. Gel time measurements and the results obtained by applying the Kamal model to isotherm DSC curing of DGEBA-IPDA-nanosilica revealed that nanosilica catalysed the curing reaction between DGEBA and IPDA, in less extent by increasing the curing temperature. 相似文献
4.
The preparation and properties of poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported for the first time. PVDF/clay nanocomposites were prepared by melt intercalation with organophilic clay. The composites were characterized with X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical analysis. X‐ray diffraction results indicated intercalation of the polymer into the interlayer spacing. PVDF in the nanocomposites crystallized in the β form. Differential scanning calorimetry nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity, as evidenced by the melting and crystallization peaks. Isothermal crystallization studies showed an enhanced rate of crystallization with the addition of clay, as evidenced by a reduction in the crystallization time. Dynamic mechanical analysis indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. The tan δ peak signifying the glass‐transition temperature of PVDF shifted to higher temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1682–1689, 2002 相似文献
5.
In this work, carbon nanotube (CNT) was used to fabricate poly(vinylidene fluoride) (PVDF)/high density polyethylene (HDPE) blend-based nanocomposites via a Haake mixer. Scanning electron microscopy confirmed that the CNT was mainly selectively located in the HDPE dispersed domains. Thermogravimetric analysis revealed that CNT addition improved the thermal stability of the blend (up to 61 °C increase at 3-phr CNT loading at 40 wt% loss) in air environment. Differential scanning calorimetry results revealed the enhanced nucleation of individual PVDF and HDPE upon crystallization in the composites; the presence of CNT inceased the stability of PVDF crystals. CNT addition increased the heat distortion temperature of the blend by up to 27 °C at 3-phr CNT loading. The complex viscosity and storage modulus increased due to the CNT pseudo-network formation in the reduce-sized HDPE phase of the composites. The rigidity of the blend was significantly improved after the addition of CNT. The impact strength of the blend increased by up to 66% after 2-phr CNT loading, and the electrical resistivity of the blend decreased by up to nine orders at 3-phr CNT loading due to the double percolation-like morphology formation. 相似文献
6.
Temperature-programmed desorption was performed at temperatures up to 850 K on as-received fumed and precipitated silica particles. Physisorbed water molecules on both types of silica had activation energies in the range of 38–61 kJ/mol. However, the activation energies of desorption for chemisorbed water varied from 80 to >247 kJ/mol for fumed silica, Cab-O-Sil-M-7D, and 96 to 155 kJ/mol for precipitated silica, Hi-Sil-233. Our results suggest that physisorbed water can be effectively pumped away at room temperature (or preferably at 320 K) in a matter of hours. Chemisorbed water with high activation energies of desorption (>126 kJ/mol) will not escape silica surfaces in 100 years even at 320 K, while a significant amount of the chemisorbed water with medium activation energies (80–109 kJ/mol) will leave the silica surfaces in that time span. Most of the chemisorbed water with activation energies <126 kJ/mol can be pumped away in a matter of days in a good vacuum environment at 500 K. We had previously measured about 0.1–0.4 wt% of water in silica-reinforced polysiloxane formulations containing 21% Cab-O-Sil-M-7D and 4% Hi-Sil-233. Comparing present results with these formulations, we conclude that the adsorbed H2O and the Si–OH bonds on the silica surfaces are the major contributors to water outgassing from these types of silica-filled polymers. 相似文献
7.
Takayuki Murayama Bernard Silverman 《Journal of Polymer Science.Polymer Physics》1973,11(10):1873-1878
Dynamic mechanical properties of the ultrahigh molecular weight nylon 66 film and fiber produced by thermally induced solid-state polycondensation are presented. The α peak temperature of tan δ of these treated films and fibers is shifted 8–32°C higher than that of the appropriate control nylon 66 (film and fiber) while the maximum height of the tan δ peaks is decreased. The treated fibers have higher moduli at all temperatures (20–145°C) and humidities (30% RH) than do their control counterparts. The moduli of the treated fibers at 30% RH compare favorably with control yarn at 0% RH. These yarns also have a greater per cent of the 25°C modulus retention as temperature increases. 相似文献
8.
Cuicui Ye Xiaojun Cao Hengti Wang Jiayao Wang Tao Wang Zongbao Wang Yongjin Li Jichun You 《Journal of polymer science. Part A, Polymer chemistry》2020,58(12):1699-1706
In this work, the miscibility effect on the localization of poly(butylene succinate) (PBSU) during the crystallization of PVDF in their blend has been investigated. After annealed at 200 °C and 240 °C, homogeneous and phase-separated structures can be obtained respectively, which was followed by isothermal crystallization at 141 °C. In the case of 200°C, PBSU tends to enrich in inner-spherulitic regions because of the excellent miscibility of the blend and the higher growth rate of PVDF crystals. When the specimen was annealed at 240 °C, phase separation produces PVDF and PBSU domains. Upon cooling to 141 °C, one part of PBSU is miscible with , while the other part of it remains as phase-separated domains due to the high viscosity and slow relaxation of them. The former accounts for the distribution of PBSU in inner-spherulitic regions. In the latter, however, phase-separated structures depress the diffusion of PVDF during its crystallization, leading to the lower magnitude of growth rate of spherulites. Both of them contribute to the localization of PBSU in inter-spherulitic regions. The distribution of PBSU among PVDF spherulites has been validated by long periods, pore size, and mechanical performance of the porous PVDF membranes. 相似文献
9.
Jaeyoung Ko Youngsoo Park Soonja Choe 《Journal of Polymer Science.Polymer Physics》1998,36(11):1981-1986
Molecular relaxation behavior in terms of the α, β, and γ transitions of miscible PS/PPO blends has been studied by means of DMTA and preliminary work has been carried out using DSC. From DSC and DMTA (by tan δ), the observed α relaxation (Tα or Tg) of PS, PPO, and the blends, which are intermediate between the constituents, are in good agreement with earlier reports by others. In addition, the β transition (Tβ) of PS at 0.03 Hz and 1 Hz is observed at −30 and 20°C, respectively, while the γ relaxation (Tγ) is not observed at either frequency. The Tβ of PPO is 30°C at 0.03 Hz and is not observed at 1 Hz, while the Tγ is −85°C at 0.03 Hz and −70°C at 1 Hz. On the other hand, blend composition-independent β or γ relaxation observed in the blends may be a consequence of the absence of intra- or intermolecular interaction between the constituents at low temperature. Thus it is suggested that at low temperature, the β relaxation of PS be influenced solely by the local motion of the phenylene ring, and that the β or γ relaxation of PPO be predominated by the local cooperative motions of several monomer units or the rotational motion of the methyl group in PPO. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1981–1986, 1998 相似文献
10.
Pristine multi-walled carbon nanotubes (MWNTs) were incorporated into poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA), and PVDF/PMMA blends to achieve binary and ternary nanocomposites. MWNTs were more compatible with the PVDF matrix than with the PMMA-containing matrices. MWNT addition did not alter the development of α-form PVDF crystals in the binary/ternary composites. Nucleation and overall isothermal crystallization of PVDF were enhanced by the presence of MWNTs, and enhancements were optimal in the PVDF/MWNT binary composites. Avrami analysis revealed that addition of MWNTs led to more extensive athermal-type nucleation of PVDF, and that PMMA slightly decreased the crystal growth dimension of PVDF. The equilibrium melting temperature (Tm°) of PVDF increased in the binary composites but remained nearly constant in the ternary system. Thermal stability was enhanced in the binary/ternary composites, and enhancements were more evident in the air environment than in nitrogen. Rheological property measurements revealed that the intensely entangled chains of high-molecular weight PVDF dominated the rheological response of PVDF-included samples in the melt state. A (pseudo)network structure was developed in each of the PVDF-included samples as well as in the 1 phr MWNT-added PMMA/MWNT composite. The storage moduli of the PVDF, PMMA, and PVDF/PMMA:1/1 blend increased to 37%, 22% and 34%, respectively, at 40 °C after addition of 1 phr MWNT. 相似文献
11.
《Journal of Polymer Science.Polymer Physics》2018,56(7):588-597
Polymer blends based on poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO) have been prepared to analyze the crystallization kinetics of poly(ethylene oxide) confined in semicrystalline PVDF with different ratios of both polymers. Both blend components were dissolved in a common solvent, dimethyl formamide. Blend films were obtained by casting from the solution at 70 °C. Thus, PVDF crystals are formed by crystallization from the solution while PEO (which is in the liquid state during the whole process) is confined between PVDF crystallites. The kinetics of crystallization of the confined PEO phase was studied by isothermal and nonisothermal experiments. Fitting of Avrami model to the experimental DSC traces allows a quantitative comparison of the influence of the PVDF/PEO ratio in the blend on the crystallization behavior. The effect of melting and further recrystallization of the PVDF matrix on PEO confinement is also studied. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 588–597 相似文献
12.
13.
Thin and surface adhesive ferroelectric poly(vinylidene fluoride) films with β phase‐inducing amino modified porous silica nanofillers
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Vimal K. Tiwari Ravindra V. Ghorpade Kang Lib Kim Giyoung Song Taehee Kim Haksoo Han Cheolmin Park 《Journal of Polymer Science.Polymer Physics》2016,54(23):2401-2411
We report an efficient route for ferroelectric polar β phase generation in poly(vinylidene fluoride) (PVDF) through incorporation of amine functionalized, porous silica (MCM‐41 and fumed silica) based nanofillers. These porous highly functionalized surfaces exhibit the efficient secondary interaction with polymer chain via hydrogen bonding. Structural analysis through FTIR, XRD, and TEM confirm high degree of ferroelectric polar β phase generation of PVDF through incorporation of amino modified porous silica nanofillers. Optimized loading (5 wt %) of amine functionalized, porous silica in PVDF matrix enhances relative intensity of β phase up to 75%. Disappearance of spherulite structure of PVDF with amino modified porous silica nanofillers, as confirmed through POM, TEM, SEM and AFM studies also supports the above conclusion. The P‐E hysteresis loop at sweep voltage of ±50 V of a thin PVDF‐amino modified porous nanofiller film shows excellent ferroelectric property with nearly saturated high remnant polarization 2.8 µC.cm?2 owing to its large proportion of β PVDF, whereas, a nonpolar pure PVDF thin film shows unsaturated hysteresis loop with 0.6 µC.cm?2 remnant polarization. PVDF films with the nanofillers exhibit strong adhesive strength over different metallic substrates making them have edge over PVDF in various thin film applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2401–2411 相似文献
14.
Several kinds of organic–inorganic hybrids were synthesized from an epoxy resin and a silane alkoxide with a primary amine‐type curing agent or tertiary amine curing catalyst. In the hybrid systems cured with the primary amine‐type curing agent, the storage modulus in the high‐temperature region increased, and the peak area of the tan δ curve decreased. Moreover, the mechanical properties were improved by the hybridization of small amounts of the silica network. However, these phenomena were not observed in the hybrid systems cured with the tertiary amine catalyst. The differences in the network structures of the hybrid materials with the different curing processes were characterized with Fourier transform infrared (FTIR). In the hybrid systems cured with the primary amine‐type curing agent, FTIR results showed the formation of a covalent bond between silanol and hydroxyl groups that were generated by the reaction of an epoxy group with an active hydrogen of the primary amine. However, this phenomenon was not observed in the hybrids cured with the tertiary amine. The hybrids with the primary amine showed a homogeneous microstructure in transmission electron microscopy observations, although the hybrids cured with the tertiary amine showed a heterogeneous structure. These results mean that the differences in the interactions between the organic and inorganic phases significantly affect the properties and microstructures of the resultant composites. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1071–1084, 2001 相似文献
15.
Dominique Gomes Irmgard Buder Suzana P. Nunes 《Journal of Polymer Science.Polymer Physics》2006,44(16):2278-2298
New functionalized particles were prepared by attaching sulfonated aromatic bishydroxy compounds onto fumed silica surface. First, a bromophenyl group was introduced onto the silica surface by reaction of bromophenyltrimethoxysilane with fumed silica. Then, sulfonated bishydroxy aromatic compounds were chemically attached to the silica surface by nucleophilic substitution reactions. The structure of the modified silica was characterized by elemental analysis: 13C‐NMR, 29Si‐NMR, and FTIR. Afterward, novel inorganic–organic electrolyte composite membranes based on sulfonated poly(ether ether ketone) have been developed using the sulfonated aromatic bishydroxy compounds chemically attached onto the fumed silica surface. The composite membrane prepared using silica with sulfonated hydroxytelechelic, containing 1,3,4‐oxadiazole units, has higher proton conductivity values in all range of temperatures (40–140 °C) than the membrane containing only the plain electrolyte polymer, while the methanol permeability determined by pervaporation experiment was unchanged. A proton conductivity up to 59 mS cm?1 at 140 °C was obtained. The combination of these effects may lead to significant improvement in fuel cells (fed with hydrogen or methanol) at temperatures above 100 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2278–2298, 2006 相似文献
16.
Silica is used as a reinforcing filler in the rubber product such as a tire. When silica contents increased in the composite, deterioration of the processability and silica dispersion in silica-rubber composites cannot be overcome only by adding a silane coupling agent. Therefore, silica wet-masterbatch (WMB) technology is considered for manufacturing highly silica filled composites. Herein, we investigated silica dispersion, cure behavior, mechanical properties, abrasion characteristics, and viscoelastic properties of 3 types of WMB blend composites. Up to 82% improvement in silica dispersion was determined by the Payne effect and confirmed by atomic-force microscopy. The tensile strength and elongation at break increased and tan δ at 60 °C decreased by improving silica dispersion. The silica WMB is suitable for manufacturing highly silica filled composites. 相似文献
17.
Copolymerization reactions between cyclic(arylene disulfide) oligomers were studied. The cyclic disulfide oligomers derived from 4,4′-isopropylidene bisbenzenethiol gave soluble polysulfanes via copolymerization with S8. The copolymerization reactions were studied both in solution and melt by GPC and NMR. Solution copolymerization reactions can only form polysulfanes with up to three to four sulfur linkages; however, melt copolymerization reactions gave polysulfanes with up to seven sulfur linkages (average). The melt copolymerization reactions between cyclic disulfide oligomers derived from 4,4′-thiobis(benzenethiol) and S8 were studied using DSC, TGA, and DMTA. With increasing contents of sulfur in the polysulfanes, Tgs, 5% weight losses by TGA, and tan δ decreased. With seven sulfur linkages in the polymer, it is a rubber with a Tg of 12°C, a 5% weight loss by TGA of 249°C, and tan δ of 44°C, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2961–2968, 1997 相似文献
18.
Thermogravimetry, differential thermal analysis, and IR spectroscopy were used to investigate the process of thermal destruction
of adsorbed polydimethylsiloxane (PDMS) in air. The disperse adsorbents were pristine fumed silica and modified fumed silica
whose surface contained oxygen compounds of phosphorus.
It was shown that under the given experimental conditions the thermal destruction of PDMS on the fumed silica surface was
accompanied by the complete transformation of the adsorbed PDMS to SiO2. In the case of phosphorus-containing silica, the thermal destruction proceeded in a different way. It was found that at
140–300°C depolymerization of the siloxane chains of a certain part of the adsorbed polymer took place with the concurrent
removal of volatile products of the reaction. However, the remaining part of the adsorbed PDMS interacted with the modified
silica surface to form chemisorbed dimethylsilyl structures. The thermal destruction of the chemisorbed fragments of PDMS
in air was initiated at 400°C or above for both types of silica investigated.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
19.
The decay of the 1,4-polybutadiene absorbance (infra-red) was found to correlate with the decrease in tan δ at ?80°C during the photo- and thermal oxidation of ABS. Both parameters correlate with loss of impact resistance. 相似文献
20.
The toughening mechanism of polypropylene (PP)/ethylene-co-vinyl acetate (EVA) dynamically crosslinked blend was investigated. The results indicated that dynamical crosslinking technology not only improved the interfacial adhesion between PP and EVA, but also increased the mechanical properties of PP/EVA blend. The quantitative and qualitative analysis of scanning electron microscopy (SEM) micrographs demonstrated that dynamical crosslinking technology could refine EVA particles in PP/EVA blend and promote the size distribution of EVA particles. The critical matrix ligament thickness of dynamically crosslinked and uncrosslinked blend was about 0.55 μm and 0.6 μm, respectively, indicating that the brittle-ductile transition occurred. Dynamic mechanical analysis (DMA) results illustrated that the tan δ peak of PP component in the dynamically crosslinked blend moved toward lower temperature compared with that of pure PP and the PP component in uncrosslinked blend; and the tan δ value of the dynamically crosslinked blend was higher than that of the uncrosslinked blend, which interpreted the toughening mechanism of dynamical crosslinking technology from the dynamic mechanical property of the blend. 相似文献