全文获取类型
收费全文 | 493237篇 |
免费 | 4856篇 |
国内免费 | 1667篇 |
专业分类
化学 | 263977篇 |
晶体学 | 8341篇 |
力学 | 21565篇 |
综合类 | 18篇 |
数学 | 53458篇 |
物理学 | 152401篇 |
出版年
2019年 | 4182篇 |
2018年 | 5061篇 |
2017年 | 5012篇 |
2016年 | 7817篇 |
2015年 | 5051篇 |
2014年 | 7928篇 |
2013年 | 21379篇 |
2012年 | 15463篇 |
2011年 | 19227篇 |
2010年 | 13335篇 |
2009年 | 13140篇 |
2008年 | 17442篇 |
2007年 | 17334篇 |
2006年 | 16502篇 |
2005年 | 15143篇 |
2004年 | 13770篇 |
2003年 | 12475篇 |
2002年 | 12169篇 |
2001年 | 14237篇 |
2000年 | 10948篇 |
1999年 | 8680篇 |
1998年 | 7175篇 |
1997年 | 7021篇 |
1996年 | 6790篇 |
1995年 | 6343篇 |
1994年 | 5997篇 |
1993年 | 5929篇 |
1992年 | 6766篇 |
1991年 | 6756篇 |
1990年 | 6466篇 |
1989年 | 6480篇 |
1988年 | 6509篇 |
1987年 | 6458篇 |
1986年 | 6083篇 |
1985年 | 8163篇 |
1984年 | 8418篇 |
1983年 | 6761篇 |
1982年 | 7257篇 |
1981年 | 7083篇 |
1980年 | 6850篇 |
1979年 | 7278篇 |
1978年 | 7440篇 |
1977年 | 7417篇 |
1976年 | 7330篇 |
1975年 | 6820篇 |
1974年 | 6705篇 |
1973年 | 6901篇 |
1972年 | 4683篇 |
1971年 | 3817篇 |
1968年 | 3960篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
71.
P. Santhana Gopala Krishnan Chaobin He Christine Tay Shang Shang 《Journal of polymer science. Part A, Polymer chemistry》2004,42(16):4036-4046
Two ladder‐like polysilsesquioxanes (LPS) containing side‐chain maleimide groups have been synthesized successfully by reacting N‐(4‐hydroxyphenyl)maleimide (HPM) with LPS containing 100 mol % of chloropropyl groups (Ladder A ) and 50 mol % of each methyl and chloropropyl group (Ladder B ). HPM was synthesized by reacting maleic anhydride with 4‐aminophenol, and the resulting amic acid was imidized using p‐toluenesulfonic acid as a catalyst (Scheme 1 ). The LPSs were characterized by Fourier transform infrared (FTIR), 1H nuclear magnetic resonance (NMR), proton‐decoupled 13C NMR, 29Si NMR, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Characterization indicated that these polymers had ordered ladder‐like structures with possible defects. These polymers were soluble in common solvents at ambient temperature, which suggested that they were not crosslinked. Both the polymers and the HPM were cured, and their kinetics were followed by dynamic DSC. The Ozawa and Kissinger methods were used to calculate activation energies for curing. Curing increased the temperature at which both 5% weight loss and maximum rate of weight loss were observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4036–4046, 2004 相似文献
72.
Irada S. Isayeva Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4337-4352
This article concerns the synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments cocrosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane‐POSS) cages. Rapid and efficient network synthesis was effected by cocrosslinking diallyl‐telechelic PEG (A‐PEG‐A) and divinyl‐telechelic PDMS (V‐PDMS‐V) with pentamethylpentacyclosiloxane (D5H), using Karstedt's catalyst in conjunction with Et3N cocatalyst and water. Films were prepared by pouring charges in molds and crosslinking by heating at 60 °C for several hours. The films were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The crosslinking of octasilane‐POSS achieved by the same catalyst system was studied in separate experiments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4337–4352, 2004 相似文献
73.
K. Y. Sandhya C. K. S. Pillai K. Sree Kumar 《Journal of Polymer Science.Polymer Physics》2004,42(7):1289-1298
New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004 相似文献
74.
C. Z. Chuai S. Li K. Almdal J. Alstrup J. Lyngaae‐Jrgensen 《Journal of Polymer Science.Polymer Physics》2004,42(5):898-913
The compatibilization effect of polystyrene (PS)‐poly(dimethylsiloxane) (PDMS) diblock copolymer (PS‐b‐PDMS) and the effect of rheological properties of PS and PDMS on phase structure of PS/PDMS blends were investigated using a selective extraction technique and scanning electron microscopy (SEM). The dual‐phase continuity of PS/PDMS blends takes place in a wide composition range. The formation and the onset of a cocontinuous phase structure largely depend on blend composition, viscosity ratio of the constituent components, and addition of diblock copolymers. The width of the concentration region of the cocontinuous structure is narrowed with increasing the viscosity ratio of the blends and in the presence of the small amount diblock copolymers. Quiescent annealing shifts the onset values of continuity. The experimental results are compared with the volume fraction of phase inversion calculated with various theoretical models, but none of the models can account quantitatively for the observed data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 898–913, 2004 相似文献
75.
G. G. Bandyopadhyay S. S. Bhagawan K. N. Ninan Sabu Thomas 《Journal of Polymer Science.Polymer Physics》2004,42(8):1417-1432
The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004 相似文献
76.
A. Zubeldia M. Larraaga P. Remiro I. Mondragon 《Journal of Polymer Science.Polymer Physics》2004,42(21):3920-3933
The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004 相似文献
77.
Shu‐Ling Huang Wei‐Kuo Chin W. P. Yang 《Journal of Polymer Science.Polymer Physics》2004,42(18):3476-3486
The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004 相似文献
78.
K. P. O. Mahesh M. Sivakumar Y. Yamamoto Y. Tsujita H. Yoshimizu S. Okamoto 《Journal of Polymer Science.Polymer Physics》2004,42(18):3439-3446
A crystalline δ form of a syndiotactic polystyrene (sPS) membrane was prepared from a solution of sPS (1 wt %) and p‐chlorotoluene (p‐CT) by a solution‐casting method. The mesophase (δ empty form) of sPS was obtained by the extraction of the guest solvent from the δ form of sPS by a stepwise solvent‐extraction method. The sPS/p‐CT mesophase membrane [p‐CT (A‐M)] was used for the sorption of 1 mol % p‐CT for different times and for the sorption of different concentrations of p‐CT, chlorobenzene (CB), p‐xylene (p‐X), toluene, and chloroform for 48 h. The presence of solvents in the sPS membrane was confirmed by IR analysis. A thermal study revealed that the sorption amount of 1 mol % p‐CT increased with increasing immersion time, and the sorption amounts of different solvents increased with increasing solvent concentration. Differential scanning calorimetry results showed that the desorption peak temperature increased as the amount of the solvent increased in the clathrated sPS membrane. Wide‐angle X‐ray diffraction results showed that 2θ at 8.25° was slightly shifted toward 8°, and there was no change in the peak position at 10° for p‐CT (A‐M), which was immersed in different solvents (1 mol %); however, the intensity of 2θ at 10° was not similar for all the samples. Among the solvents used for the sorption studies at 1 mol %, p‐CT (A‐M) could sorb more p‐CT and CB than p‐X, toluene, and chloroform. The solvent sorption isotherm was the Langmuir sorption mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3439–3446, 2004 相似文献
79.
Suresh K Kumar Prabhakara S Rao L Krishnaiah B Jayaraj P Chiranjeevi 《Analytical sciences》2004,20(6):951-953
A simple and highly sensitive reagent of salicylaldehyde 3-oxobutanoylhydrazone (salicylaldehyde acetoacetic acid hydrazone, SAAH) was synthesized and studied for the spectrophotometric determination of nickel in detail. In the pH range 6, which greatly increased the selectivity, nickel reacted with SAAH to form a 1:1 yellow complex, having a sensitive absorption peak at 405 nm. Under the optimal conditions, Beer's law was obeyed over the range from 0.0117 to 0.1174 microg cm(-3). The apparent molar absorptivity was 3.025 x 10(5) dm3 mol(-1) cm(-1). The detection limit and the variation coefficient were found to be 1.752 ng cm(-3) and 1.0%, respectively. The method has been applied to the quantitative determination of nickel in different alloys and leaves. 相似文献
80.
W.H. Lim M.J. Lawrence 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):449-457
Photon correlation spectroscopy and freeze-fracture electron microscopy have been used to determine the ability of a range of micelle-forming, polyoxyethylene (20) sorbitan monoesters (Tweens) to solubilise vesicles prepared from phosphatidylcholines of different acyl chain lengths and degrees of saturation with a view to rationalising (in terms of their membrane toxicity) which of the micelle-forming surfactants to use as drug delivery vehicles. The phosphatidylcholines used were dimyristoyl-, dipalmitoyl-, distearoyl- and dioleoylphosphatidylcholine (DMPC, DPPC, DSPC and DOPC, respectively) while the nonionic polyoxyethylene sorbitan monoesters studied were polyoxyethylene (20) sorbitan monolaurate (Tween 20), a 9:1 weight ratio mixture of polyoxyethylene (20) sorbitan monopalmitate and monostearate (Tween 40), a 1:1 weight ratio mixture of polyoxyethylene (20) sorbitan monopalmitate and monostearate (Tween 60), and polyoxyethylene (20) sorbitan monooleate (Tween 80). The ability of the Tween micelles to solubilise phospholipid vesicles was found to depend both upon the length of the surfactant acyl chain and the length of the acyl chains of the phospholipid comprising the vesicle. Vesicles composed of long saturated diacyl chain phospholipids, namely DSPC and DPPC, were the most resistant to solubilisation, while those prepared from the shorter acyl chained DMPC were more readily solubilised. In terms of their solubilisation behaviour, vesicles made from phospholipids containing long, unsaturated acyl chains, namely DOPC behaved more akin to those vesicles prepared from DMPC. None of the Tween surfactants were effective at solubilising vesicles prepared from DPPC or DSPC. In contrast, there were clear differences in the ability of the various surfactants to solubilise vesicles prepared from DMPC and DOPC, in that micelles formed from Tween 20 were the most effective solubilising agent while those formed by Tween 60 were the least effective. As a consequence of these observations it was considered that Tween 60 was the surfactant least likely to cause membrane damage in vivo and, therefore, is the most suitable surfactant for use as a micellar drug delivery vehicle. 相似文献