全文获取类型
收费全文 | 1564篇 |
免费 | 81篇 |
国内免费 | 215篇 |
专业分类
化学 | 1703篇 |
晶体学 | 4篇 |
力学 | 5篇 |
综合类 | 11篇 |
数学 | 2篇 |
物理学 | 135篇 |
出版年
2024年 | 3篇 |
2023年 | 11篇 |
2022年 | 29篇 |
2021年 | 69篇 |
2020年 | 54篇 |
2019年 | 38篇 |
2018年 | 43篇 |
2017年 | 64篇 |
2016年 | 76篇 |
2015年 | 46篇 |
2014年 | 54篇 |
2013年 | 125篇 |
2012年 | 60篇 |
2011年 | 60篇 |
2010年 | 59篇 |
2009年 | 84篇 |
2008年 | 106篇 |
2007年 | 72篇 |
2006年 | 91篇 |
2005年 | 90篇 |
2004年 | 54篇 |
2003年 | 52篇 |
2002年 | 52篇 |
2001年 | 51篇 |
2000年 | 46篇 |
1999年 | 47篇 |
1998年 | 54篇 |
1997年 | 46篇 |
1996年 | 52篇 |
1995年 | 48篇 |
1994年 | 31篇 |
1993年 | 14篇 |
1992年 | 14篇 |
1991年 | 19篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 11篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
排序方式: 共有1860条查询结果,搜索用时 15 毫秒
31.
Chisuzu Tokoh Keiji Takabe Minoru Fujita Hiroshi Saiki 《Cellulose (London, England)》1998,5(4):249-261
Acetobacter xylinum was cultured in Hestrin-Schramm medium (control medium) and Hestrin-Schramm medium containing acetyl glucomannan (mannan medium). Loose bundles of the cellulose microfibrils are formed in the mannan medium in contrast to the normal ribbons being produced in the control medium. Rapid-freeze and substitution method followed by metal-shadowing revealed the droplet-like structures around the microfibril synthesized in the mannan medium. The cellulose synthesized in the mannan medium was stained heavily by the periodic acid-thiocarbohydrazide-silver proteinate (PATAg) method, while the cellulose synthesized in the control medium was not stained. X-ray diffractometry and FT-IR spectroscopy indicated that the addition of mannan induced a change in the crystal structure from the algal-bacterial type to the cotton-ramie type. Thus the presence of acetyl glucomannan in the medium prevents the assembly of cellulose microfibrils and changes the crystal structure of cellulose. 相似文献
32.
E. Fleury J. Dubois C. Léonard J. P. Joseleau H. Chanzy 《Cellulose (London, England)》1994,1(2):131-144
Solutions of cellulose diacetate (CDA) from two sources (cotton linters and wood pulp Floranier) were analysed in various solvents by size exclusion chromatography (SEC). Without special precautions, the SEC chromatograms presented three peaks — or prehumps — before the main polymer peak. The first prehump which could be eliminated by ultracentrifugation corresponded to microgels whose sugar composition was determined. These microgels were also investigated by electron microscopy, X-ray and electron diffraction analysis. They corresponded mainly to cellulose triacetate (CTA-II) in the case of CDA from cotton linters and a mixture of CTA-II and xylan diacetate (XDA) in the case of CDA from the wood pulp Floranier. The second and third prehumps could be attributed to ionic effects corresponding to the association of remaining sulfate groups on the CDA molecules with residual calcium. It was found that these ionic effects could be eliminated by the addition of LiBr or LiCl to the elution solvents. This led to chromatograms devoid of prehumps.Presented in part at the Cellulose '91 meeting in New Orleans. 相似文献
33.
Paavo?Mansikkam?ki Manu?Lahtinen Kari?RissanenEmail author 《Cellulose (London, England)》2005,12(3):233-242
The completeness of mercerisation can be evaluated by investigating the changes in the crystalline regions of cellulose from
cellulose I (C-I) to cellulose II (C-II) by the X-ray powder diffraction method. Mercerisation experiments in four different
solution systems: ethanol/water, acetone, DMSO and xylene, are reported. Also the effect of some additives, external pressure,
treatment time and alkalisation temperature were studied. In two-phase solvent systems, structural changes of cellulose crystallites
depended primarily on the distribution and solubility of sodium hydroxide in the solvent phases. The sodium hydroxide concentration
in the hydrophilic phase must exceed 7–8 w/w-% before complete crystal change from C-I to C-II can occur. The precipitation
of sodium hydroxide due to high concentration prevents the successful use of one-phase ethanol/water system in slurry process.
On the contrary, the 2-propanol/water/sodium hydroxide system separates into two layers; to the water-rich lower layer and
the 2-propanol-rich upper layer, where the sodium hydroxide remains mainly in the water-rich lower layer. This prevents the
precipitation of sodium hydroxide and promotes the alkalisation of cellulose. Ammonium chloride and ammonium hydroxide clearly
had a positive effect by promoting the crystal changes, however, the urea concentration used in this study was obviously too
small. In the advantageous two-phase 2-propanol/water systems, the alkalisation time was only 15 min when the treatment temperature
was kept between 0 and 10 °C. Reduced external pressure was found to have a small but still detectable positive effect on
cellulose alkalisation while over-pressure prevented crystal changes. 相似文献
34.
Preparation of cellulose and cellulose derivative azo compounds 总被引:1,自引:0,他引:1
Maha Ibrahim 《Cellulose (London, England)》2002,9(3-4):337-349
Wood pulp and cotton linter are the most common sources of cellulose forindustrial use. Methyl cellulose (MC) and cellulose sulfate (CS) were preparedusing bleached wood pulp and cotton linter. Coloured azo compounds were alsoprepared from coupling cellulose, wood pulp, MC and CS with aromatic diazoniumsalt. The presence of electron-releasing or withdrawing substituents affectedthe electrophilic substitution reaction. The produced azo compounds werecharacterized by FT-IR methodology, as well as mass spectrometry, in which thefunctional groups and the ion fragments of the products were analyzed. 相似文献
35.
Regenerated cellulose films with water-resistance were obtained by an improved method ofpreparing cellulose cuoxam solution from pulps of agricultural wastes (linters, wheat straw, reedand Bamao). Experimental results showed that the mechanical properties of both the dry. and wetfilms were excellent. Data from IR, SEM and tensile strength measurements implied that thesignificant improvement of water-resistance of the films was due to the cohesion between the thinTung oil covers with hydrophobicity and the regenerated cellulose films. The films werecompletely biodegraded after being buried in soil for 100 days. The transmittance of the filmsderived from linter and reed in visible band range were 80-90%. 相似文献
36.
在自制的硅基纤维素-三(3,5-二甲基苯基氨基甲酸酯)高效液相色谱手性固定相上(HPLC-CSP),优化了1-(6'-甲氧基萘)乙醇氢酯基化反应产物-萘普生甲酯手性分离的条件,测定了相应的一系列不对称氢酯基化反应产物的对映体过剩值(e.e.值)。结果表明,在CDMPC-CSP手性柱上用HPLC测定此类不对称催化反应的光学产率,评价催化剂体系的手性选择是一种非常理想的方法。 相似文献
37.
Composite materials were processed by casting a mixture of aqueous suspensions of latex and microfibrils. These microfibrils, or whiskers, are extracted from a sea animal and are monocrystals of cellulose, with an aspect ratio around 100 and an average diameter of 20 nm. It has been found that the mechanical properties (shear modulus) are increased by more than two orders of magnitude in the rubbery state of the polymeric matrix, when the whisker content was 6% (w/w). This very large effect is discussed on the basis of different types of mechanical models and it is concluded that these whiskers form a rigid network, probably linked by hydrogen bonds. The formation of this network is assumed to be governed by a percolation mechanism. 相似文献
38.
羧甲基纤维素系列高分子表面活性剂超声合成的研究 总被引:27,自引:2,他引:27
研究了在超声波作用下羧甲基纤维素的降解反应及CMC与具有不同亲水亲油比值的活性大单体「烷基醇(酚)聚氧乙烯醚丙烯酸酯及第三单体」的超声共聚反应。经萃取提纯的共聚产物用IR,^13C NMR和UV等方法进行表证,证实通过超声反应制得了二元和三元共聚物。 相似文献
39.
Jun-ichi Azuma Nam-Hun Kim Laurent Heux Roger Vuong Henri Chanzy 《Cellulose (London, England)》2000,7(1):3-19
The cellulose system of the viscous fibrous cellulosic polysaccharide (viscan) in the viscin tissue of the European mistletoe, Viscum album L., was analyzed by chemical and physicochemical techniques including sugar analysis, optical and transmission electron microscopy, X-ray and electron diffraction together with solid state CP/MAS 13C-NMR spectroscopy. The results confirmed that in the elongated thin viscin cells, the cellulose microfibrils (having a diameter of around 3 nm) were tightly coiled with their axes perpendicular to the long axis of the cell. Upon stretching these cells became deformed by more than a hundred fold. In such a deformation, the cellulose microfibrils became unwound to be perfectly aligned along the stretching direction. Based on solid-state CP/MAS 13C-NMR spectroscopic analysis of the viscin tissue, it was found that its cellulose consisted of I and I polymorphs in the ratio 1:1. 相似文献
40.
Elizabeth Dinand Michel Vignon Henri Chanzy Laurent Heux 《Cellulose (London, England)》2002,9(1):7-18
The mercerization of homogenized primary wall cellulose extracted fromsugar beet pulp was investigated by transmission electron microscopy (TEM),X-ray diffraction together with 13C CP-MAS NMR, and FT-IR spectroscopy.For samples resulting from acid extraction, mercerization began at 9% NaOH, whereasfor samples purified by alkaline treatment, the mercerization started at 10%NaOH. The change in morphology when going from cellulose I to cellulose II wasspectacular, as all the microfibrillar cellulose morphology disappeared duringthe treatment. This change in morphology was very drastic as soon as the NaOHconcentrations were increased beyond 8 and 9% for the acid and alkalinepreparedsamples, respectively. On the other hand, the conversion was found to be moreprogressive in terms of increasing NaOH concentration when the transformationwas analyzed by X-ray diffraction or spectroscopy. Our observations of themercerization of isolated cellulose microfibrils are consistent with theconceptof cellulose microfibrils made of parallel chains in cellulose I and crystalsofcellulose II consisting of antiparallel chains. 相似文献