全文获取类型
收费全文 | 176篇 |
免费 | 8篇 |
国内免费 | 11篇 |
专业分类
化学 | 161篇 |
力学 | 3篇 |
综合类 | 2篇 |
数学 | 13篇 |
物理学 | 16篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 4篇 |
2019年 | 4篇 |
2018年 | 2篇 |
2017年 | 6篇 |
2016年 | 3篇 |
2015年 | 4篇 |
2014年 | 6篇 |
2013年 | 14篇 |
2012年 | 3篇 |
2011年 | 5篇 |
2010年 | 3篇 |
2009年 | 12篇 |
2008年 | 8篇 |
2007年 | 7篇 |
2006年 | 8篇 |
2005年 | 6篇 |
2004年 | 11篇 |
2003年 | 7篇 |
2002年 | 8篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 11篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
排序方式: 共有195条查询结果,搜索用时 0 毫秒
1.
Govindarajan Sankar A. Sultan Nasar 《Journal of polymer science. Part A, Polymer chemistry》2007,45(8):1557-1570
A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, 1H NMR, and 13C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature 1H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007 相似文献
2.
We consider a composite material composed of fibres included in a resin which becomes solid when it is heated up (reaction of reticulation). The mathematical modelling of the cure process is given by a kinetic equation describing the evolution of the reaction of reticulation coupled with the heat equation. In this paper, we are interested in the computation of approximate solutions. We propose a family of discretized problems depending on two parameters (β1, β2) ε [0, 1]2 which split the linear and non‐ linear terms in implicit and explicit parts. We prove the stability and convergence of the discretization for any (β1, β2) ε [½, 1 ] × [0, 1]. We present also some numerical results. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
3.
F. Román S. Montserrat J. M. Hutchinson 《Journal of Thermal Analysis and Calorimetry》2007,87(1):113-118
The procedure for
the fabrication of epoxy-based polymer layered silicate nanocomposites is
important in respect of the nanostructure that is developed. To further our
understanding of this, the influence of an organically modified clay (montmorillonite,
MMT) on the curing kinetics of an epoxy resin has been studied by differential
scanning calorimetry. Clay loadings of 10 and 20 mass% are used, and isothermal
as well as dynamic cures have been investigated. For both cure schedules the
effect of the MMT is to advance the reaction. Kinetic analysis yields values
for the activation energy, but shows that the reaction cannot be described
simply by the usual autocatalytic equation. The glass transition of the cured
nanocomposites is lower than that for the cured neat resin, a result that
is attributed to homopolymerisation taking place in addition to the epoxy–amine
reaction. 相似文献
4.
C.?Korah Bina K.?G.?Kannan K.?N.?NinanEmail author 《Journal of Thermal Analysis and Calorimetry》2004,78(3):753-760
The urethane forming cure reactions of hydroxyl terminated polybutadiene (HTPB) binder with three different isocyanate curatives, viz., toluene diisocyanate (TDI), isophorone diisocyanate (IPDI) and 4,4-methylene bis(cyclohexyl isocyanate) (MCHI), were investigated by differential scanning calorimetry (DSC). The effect of two cure catalysts, viz., dibutyl tin dilaurate (DBTDL) and ferrric tris-acetylacetonate (FeAA) on the cure reactions was also studied. Cure kinetics was evaluated using the multiple heating rate Ozawa method. The reactivities of the three isocyanates and catalytic efficiencies were compared based on the DSC reaction temperatures, activation energies and rate constants. Viscosity build-up in these systems at isothermal temperature was also studied and compared with the results from DSC. 相似文献
5.
Mu-Shih Lin Kuen-Tay Jeng 《Journal of polymer science. Part A, Polymer chemistry》1992,30(9):1941-1951
Poly(ethylene glycol) diacrylate was synthesized from poly(ethylene glycol) of molecular weight 600 with acryloyl chloride in a molar ratio of 1:2. Poly(ethylene glycol) diacrylate (PEGDA) was then blended with diglycidyl ether of bisphenol A (DGEBA) in various ratios, followed by curing with 2,2′-azobisisobutyronitrile (AIBN) and isophronediamine (IPDA) simultaneously. Viscosity changes before and during IPN formation were examined with a Brookfield viscometer. Formation of H-bonding and functional group changes were investigated with FTIR. Exothermic curing thermograms were recorded with dynamic DSC. Optically clear IPNs thus obtained were characterized with rheometric dynamic spectroscopy (RDS) and scanning electron microscopy (SEM) to check possible compatibility of the two networks. Experimental results revealed that during IPN formation hydrogen bonds between PEGDA and DGEBA and interlock of networks had profound effect on viscosity change and pot-life. Complete compatibility of the IPNs was found as DGEBA content was higher than 50% by weight. The compatibility between PEGDA and DGEBA networks was evidenced from inner shift of a single damping peak in RDS. In the meantime, SEM micrographs confirmed the coincidence with the result of RDS © 1992 John Wiley &Sons, Inc. 相似文献
6.
Marta Sánchez-Cabezudo Margarita G. Prolongo Catalina Salom Rosa M. Masegosa 《Journal of Thermal Analysis and Calorimetry》2006,86(3):699-705
The cure kinetics
and morphology of diglycidyl ether of bisphenol A (DGEBA) modified with polyvinyl
acetate (PVAc) using diaminodiphenylmethane (DDM) as hardener were investigated
through differential scanning calorimetry (DSC) and environmental scanning
electron microscopy (ESEM). Isothermal curing measurements were carried out
at 150, 120 and 80°C. The kinetic parameters were obtained using the general
autocatalytic chemically controlled model. The comparison of the kinetic data
indicates that the presence of PVAc does not change the autocatalytic nature
of the cure reaction. Two T
g’s
were observed in the fully cured samples of the modified systems. ESEM micrographies
confirm the biphasic morphology. 相似文献
7.
Xu W. B. Zhou Z. F. He P. S. Pan W.-P. 《Journal of Thermal Analysis and Calorimetry》2004,78(1):113-124
The Flory's gelation theory, non-equilibrium thermodynamic fluctuation theory and Avrami equation have been used to predict
the gel time t
g and the cure behavior of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposites at various temperatures
and organo-montmorillonite loadings. The theoretical prediction is in good agreement with the experimental results obtained
by dynamic torsional vibration method, and the results show that the addition of organo-montmorillonite reduces the gelation
time t
gand increases the rate of curing reaction, the value of k, and half-time of cure after gelation point t1/2 decreases with the increasing of cure temperature, and the value of n is ~2 at the lower temperatures (<60°C) and decreases to ~1.5 as the temperature increases, and the addition of organo-montmorillonite
decreases the apparent activation energy of the cure reaction before gelation point, but has no apparent effect on the apparent
activation energy of the cure reaction after gelation point. There is no special curing process required for the formation
of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposite.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
8.
Fluorinated copolymers are well known for their large range of applications. These applications can be improved by grafting or crosslinking of several agents. The mechanism of crosslinking of hexamethylene diamine and 2,4,4-trimethyl-1,6-hexanediamine is well known and occurs in four different steps. To elaborate a film of commercially available poly(VDF-co-HFP) copolymer crosslinked by 2,4,4-trimethyl-1,6-hexanediamine, a step of press cure under air is necessary. Temperature, time and pressure were optimised by regarding the solubility of the press cured films, the mechanical properties, the swelling rate in methyl ethyl ketone, and the degradation of the films. The best temperature, time and pressure for press cure were 150 °C, from 15 to 30 min, and 20 bars, respectively. Other properties of crosslinked poly(VDF-co-HFP) copolymers containing 10 mol.% and 20 mol.% of HFP were characterized. First, all films were insoluble in concentrated HCl. Secondly, swelling rates of different amounts of diamine crosslinked copolymers were measured in ethylene carbonate/dimethyl carbonate and in methyl ethyl ketone; it was proved that the higher the molar percentage of diamine, the higher the crosslinking density, so the lower the swelling rate. Concerning thermal properties, glass transition temperature mainly increased when the amount of diamine increased. Thermal stability measurements showed a higher decomposition temperature when the percentage of diamine was very low (5 mol.%). Finally, mechanical properties were measured by dynamic mechanical analysis; the storage tensile modulus (E′) of a diamine crosslinked Kynar® copolymer versus temperature exhibited a high drop because Kynar® was a highly amorphous copolymer. Moreover, the higher the amount of diamine, the higher the rubbery modulus. 相似文献
9.
A simple optical method for quantitative comparison of the effectiveness of epoxy cure accelerators, used for speeding up the crosslinking process of epoxy resins with cyclic anhydrides, is described. Fluorescent molecular probes and a miniature fiber optic spectrometer have been applied for measurement of the cure kinetics of a model epoxy resin/anhydride composition in the presence of various cure accelerators. A quantitative index of accelerator performance has been determined for several of the most common accelerators. 相似文献
10.
A series of shape memory polyurethanes were synthesized from poly(tetramethylene glycol), 4,4‐methylene diphenyl diisocyanate, and 1,3‐butanediol. The prepolymers with different molecular weights (Mc) were capped with 2‐hydroxyl ethylacrylate or 3‐aminopropyltriethoxysilane (APTES) and crosslinked by UV curing or a sol–gel reaction. Variations of the crosslinker functionality (f), subchain density (N), and hard segment content (HSC) produced systematic variations of the glass transition temperature (6–45 °C), accompanied by changes in the mechanical, dynamic mechanical and shape memory properties. More than 95% of shape fixity and 98% of shape recovery up to the fourth cycles were obtained with APTES crosslinked 3000Mc with 30% of HSC. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1473–1479 相似文献