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91.
92.
项益智李小年 《中国化学工程学报》2005,13(5):696-700
Co and Mo bimetallic nitrides supported on Mg(Al)O, MgO and γ-Al2O3 were prepared in temperatureprogrammed reactions with NH3. The surface morphology, chemical composition and catalytic activity for NH3 decomposition on the supported Co and Mo bimetallic nitrides were studied by X-ray diffractometer (XRD), NH3 temperature-programmed desorption and mass spectrometer (NH3-TPD-MS), temperature-programmed desorption and mass spectrometer (TPD-MS), H2 temperature-programmed surface reaction (H2-TPSR) and activity test. The phases of Co3Mo3N and MoN could be formed on Mg(Al)O, MgO and Al2O3 during the nitridation, and they might be more uniformly dispersed on Mg(Al)O and MgO than on γ-Al2O3. Transition metallic nitrides are generally considered as potential catalysts for hydrogen-involving reactions due to the entrance of hydrogen atoms into subsurface and the lattice of metallic nitrides. The diffusion of nitrogen in the bulk and the structure transformation of Co and Mo nitride compounds occur during NH3-TPD, but the supported Co and Mo bimetallic nitrides are not easily reduced at H2 atmosphere. Co3Mo3N/Mg(Al)O catalyst exhibits the highest activity, while Co3Mo3N/Al2O3 exhibits the lowest activity for NH3 decomposition. Furthermore, the catalytic activity of Co and Mo bimetallic nitrides is not only much higher than that of supported single metallic nitride, but also highly dependent upon the surface acidity and BET surface area of support. 相似文献
93.
Tert‐butyl hydroquinone–based poly(cyanoarylene ether) (PENT) was synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate in a nitrogen atmosphere at 200°C. PENT‐toughened diglycidyl ether of bisphenol A epoxy resin (DGEBA) was developed using 4,4′‐diaminodiphenyl sulfone (DDS) as the curing agent. Scanning electron micrographs revealed that all blends had a two‐phase morphology. The morphology changed from dispersed PENT to a cocontinuous structure with an increase in PENT content in the blends from 5 to 15 phr. The viscoelastic properties of the blends were investigated using dynamic mechanical thermal analysis. The storage modulus of the blends was less than that of the unmodified resin, whereas the loss modulus of the blends was higher than that of the neat epoxy. The tensile strength of the blends improved slightly, whereas flexural strength remained the same as that of the unmodified resin. Fracture toughness was found to increase with an increase in PENT content in the blends. Toughening mechanisms like local plastic deformation of the matrix, crack path deflection, crack pinning, ductile tearing of thermoplastic, and particle bridging were evident from the scanning electron micrographs of failed specimens from the fracture toughness measurements. The thermal stability of the blends were comparable to that of the neat resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3536–3544, 2006 相似文献
94.
Factors influencing the impact toughness of two impact polypropylene copolymers (IPC) with almost the same ethylene content, molecular weight and molecular weight distribution were studied by temperature gradient extraction fractionation (TGEF), scanning electron microscopy (SEM), nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). The results indicate that poor interfacial adhesion between the disperse phase and the continuous matrix, larger dimensions and non-uniform distribution of disperse phases are main reasons for the low impact toughness of IPC B that possesses of a low content of ethylene-propylene segmented copolymer with long crystallizable PE and PP sequences as a compatibilizer between the disperse phase and the matrix. 相似文献
95.
96.
Statistical prediction of fracture parameters of concrete and implications for choice of testing standard 总被引:2,自引:0,他引:2
This article shows how the fracture energy of concrete, as well as other fracture parameters such as the effective length of the fracture process zone, critical crack-tip opening displacement and the fracture toughness, can be approximately predicted from the standard compression strength, maximum aggregate size, water-cement ratio, and aggregate type (river or crushed). A database, consisting of 238 test data, is extracted from the literature and tabulated, and approximate mean prediction formulae calibrated by this very large data set are developed. A distinction is made between (a) the fracture energy, Gf, corresponding to the area under the initial tangent of the softening stress-separation curve of cohesive crack model, which governs the maximum loads of structures and is obtained by the size effect method (SEM) or related methods (Jenq-Shah two-parameter method and Karihaloo's effective crack model, ECM) and (b) the fracture energy, GF, corresponding to the area under the complete stress-separation curve, which governs large postpeak deflections of structures and is obtained by the work-of-fracture method (WFM) proposed for concrete by Hillerborg. The coefficients of variation of the errors in the prediction formulae compared to the test data are calculated; they are 17.8% for Gf and 29.9% for GF, the latter being 1.67 times higher than the former. Although the errors of the prediction formulae taking into account the differences among different concretes doubtless contribute significantly to the high values of these coefficients of variation, there is no reason for a bias of the statistics in favor of Gf or GF. Thus, the statistics indicate that the fracture energy based on the measurements in the maximum load region is much less uncertain than that based on the measurement of the tail of the postpeak load-deflection curve. While both Gf and GF are needed for accurate structural analysis, it follows that if the testing standard should measure, for the sake of simplicity, only one of these two fracture energies, then Gf is preferable. 相似文献
97.
Semi1 and semi2 interpenetrating polymer networks (IPNs) of PVC and in situ formed PMMA have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PMMA, respectively. These two types of IPNs have been compared w.r.t their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi1 IPNs displayed a decrease in their mechanical parameters and the physical properties as well, while in contrast, the semi2 IPNs exhibited a marginal increase in the corresponding values after an initial drop upto about 15% of crosslinked PMMA incorporation when compared to the crosslinked PVC in the case of semi1 IPN and linear PVC in the case of semi2 IPN. The various samples of semi1 and semi2 IPNs showed a two‐stage degradation typical of PVC, while confirming the increased stability with the samples having higher percentages of PMMA. The influence of crosslinking of the major matrix in semi1 IPN was almost counterbalanced by the influence of crosslinking in the dispersed PMMA phase in the case of semi2 IPN. The softening characteristics as detected by the extent of penetration of the probe, as has been detected by thermomechanical analysis, are in conformity with their mechanicals. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1725–1735, 2005 相似文献
98.
We prepared poly(p‐phenylene pyromellitimide) (PMDA–PDA), poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide), and their copolyimides with various compositions to explore the relationship between the water sorption and structure. The water sorption behaviors were gravimetrically investigated as a function of composition and temperature and interpreted with a Fickian diffusion model in films. Overall, the water sorption behaviors were strongly dependent on the changes in morphological structure, which originated from the variations in composition. When the content of the bulky hexafluoroisopropylidene group (6FDA) was increased, the water uptake decreased from 5.80 to 3.18 wt %, whereas the diffusion coefficient increased from 3.6 × 10?10 to 11.3 × 10?10 cm2/s. The relatively high water uptake in the PMDA–PDA polyimide film was successfully healed by the incorporation of 6FDA, which may have resulted from the increases in the intermolecular packing order and hydrophobicity. The degree of orientation and crystallinity, which are in‐plane characteristics, were directly correlated to the diffusion coefficient and activation energy in the polyimide film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3442–3446, 2003 相似文献
99.
Louise Therese Pick Eileen Harkin‐Jones Maria Jovita Oliveira Maria Clara Cramez 《应用聚合物科学杂志》2006,101(3):1963-1971
This article examines changes to the morphology of rotationally molded metallocene catalyzed linear low density polyethylene brought about by varying the cooling rate during processing. These changes in morphology lead to variations in the impact performance, which is reflected in the dynamic mechanical characteristics of the materials. Various analytical techniques are used in an attempt to explain the differences in impact behavior. Slow cooling is shown to result in high crystallinity, and in the formation of large spherulites, which in turn is detrimental to the impact performance of the material, particularly at low temperatures. The high crystallinity corresponds with a shift in the β transition of the material to a higher temperature, and is shown to result in a higher brittle–ductile transition. A case study was also carried out on samples from a finished part provided by an industrial molder, one section of which failed in a brittle manner when impact tested while the other failed in a ductile manner. Microscopy results showed that the brittle material had large spherulites at the inside surface, while the ductile material showed incipient degradation at this surface, which has previously been shown to be of benefit to impact strength in rotationally molded parts. Dynamic mechanical studies again showed a β transition at a higher temperature in the brittle samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1963–1971, 2006 相似文献
100.
The effects of the blend composition and compatibilization on the morphology of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were studied. The blends showed dispersed/matrix and cocontinuous phase morphologies that depended on the composition. The blends had a cocontinuous morphology at an EVA concentration of 40–60%. The addition of the compatibilizer first decreased the domain size of the dispersed phase, which then leveled off. Two types of compatibilizers were added to the polymer/polymer interface: linear low‐density polyethylene‐g‐maleic anhydride and LLDPE‐g phenolic resin. Noolandi's theory was in agreement with the experimental data. The conformation of the compatibilizer at the blend interface could be predicted by the calculation of the area occupied by the compatibilizer molecule at the interface. The effects of the blend ratio and compatibilization on the dynamic mechanical properties of the blends were analyzed from ?60°C to +35°C. The experiments were performed over a series of frequencies. The area under the curve of the loss modulus versus the temperature was higher than the values obtained by group contribution analysis. The loss tangent curve showed a peak corresponding to the glass transition of EVA, indicating the incompatibility of the blend system. The damping characteristics of the blends increased with increasing EVA content because of the decrease in the crystalline volume of the system. Attempts were made to correlate the observed viscoelastic properties of the blends with the morphology. Various composite models were used to model the dynamic mechanical data. Compatibilization increased the storage modulus of the system because of the fine dispersion of EVA domains in the LLDPE matrix, which provided increased interfacial interaction. Better compatibilization was effected at a 0.5–1% loading of the compatibilizer. This was in full agreement with the dynamic mechanical spectroscopy data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4526–4538, 2006 相似文献