全文获取类型
收费全文 | 1919篇 |
免费 | 340篇 |
国内免费 | 304篇 |
专业分类
化学 | 1269篇 |
晶体学 | 111篇 |
力学 | 201篇 |
综合类 | 21篇 |
数学 | 261篇 |
物理学 | 700篇 |
出版年
2024年 | 2篇 |
2023年 | 26篇 |
2022年 | 41篇 |
2021年 | 55篇 |
2020年 | 46篇 |
2019年 | 40篇 |
2018年 | 49篇 |
2017年 | 85篇 |
2016年 | 108篇 |
2015年 | 85篇 |
2014年 | 82篇 |
2013年 | 244篇 |
2012年 | 122篇 |
2011年 | 114篇 |
2010年 | 114篇 |
2009年 | 125篇 |
2008年 | 118篇 |
2007年 | 115篇 |
2006年 | 135篇 |
2005年 | 136篇 |
2004年 | 115篇 |
2003年 | 102篇 |
2002年 | 89篇 |
2001年 | 70篇 |
2000年 | 53篇 |
1999年 | 48篇 |
1998年 | 28篇 |
1997年 | 35篇 |
1996年 | 30篇 |
1995年 | 33篇 |
1994年 | 26篇 |
1993年 | 13篇 |
1992年 | 14篇 |
1991年 | 16篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1978年 | 3篇 |
1975年 | 1篇 |
1971年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有2563条查询结果,搜索用时 156 毫秒
41.
Montserrat Barquín María J. Gonzlez Garmendia Liher Larrínaga Elena Pinilla María R. Torres 《无机化学与普通化学杂志》2005,631(11):2210-2214
The complexes of copper formato with pyrazine and dimethylpyrazines: Cu(HCOO)2(pyrz) ( 1 ), Cu2(HCOO)4(pyrz) ( 2 ), Cu2(HCOO)4(2,3‐Me2pyrz) ( 3 ), Cu2(HCOO)4(2,5‐Me2pyrz) ( 4 ), and Cu2(HCOO)4(2,6‐Me2pyrz)2 ( 5 ) have been synthesized and characterized by chemical analysis and IR and electronic spectro scopies. The three‐dimensional structure of compound 1 consists of –Cu–pyrz–Cu–pyrz– chains joined by bridging formate groups coordinated, in configuration syn‐anti, to two copper atoms. The coordination around the copper atom is orthorhombic with two Cu–O distances of 2.374(1) Å, two Cu–O of 1.952 Å and two Cu–N of 2.080 Å. Compound 5 is formed by molecular dimers with the [Cu2(μ‐HCOO)4] unit, two copper atoms and four syn‐syn fomate groups, and two ligands coordinated to the copper atoms in the axial positions. In compounds 2 and 3 chains of [Cu2(μ‐HCOO)4] dimers with pyrz or 2,3‐Me2pyrz as bridging ligands are formed. The EPR signal of 1 is orthorhombic (g = 2.23, 2.20 and 2.06). In the EPR spectra of 2 – 5 compounds the triplet (S = 1) signals are observed. The g?, g∥ and D values are been calculated. 相似文献
42.
Mogon Patel Anthony C. Swain Robert S. Maxwell 《Polymer Degradation and Stability》2006,91(3):548-554
Poly(m-carboranyl-siloxane) elastomers containing a mixture of di-methyl- and methylphenyl-silyl units were synthesised using the ferric chloride catalysed condensation reaction between di-chloro-diorganosilane and bis(di-methylmethoxysilyl)-m-carborane. These elastomeric materials were originally developed to have greater stability to extreme thermal environments and retain tailorable physical and chemical properties relative to comparable non-carborane containing elastomers. Prepared samples were aged either by heating in air at elevated temperatures or by gamma irradiation from a 60Co source. Multinuclear (1H, 13C and 11B) solid and solution state nuclear magnetic resonance (NMR) was used to assess degradation. This included measurements of segmental chain dynamics using a solid-echo pulse sequence reflecting changes in crosslink density and assessing changes to the carborane fragment by 11B and 1H Magic Angle Spinning (MAS) methods. Thermogravimetric measurements were also performed to assess thermal stability. Gamma radiation (to a dose of 1 MGy) was found to induce only a small degree of elastomer hardening as evidenced by a reduction in segmental chain dynamics. The carborane cage however, remained intact at these dose levels. Thermal degradation was observed to lead to oxidative crosslinking, the degree of which is dependent on temperature. At temperatures below 350 °C, only small changes in segmental dynamics were observed commensurate with only minor weight loss at this temperature. At temperatures above 350 °C, the degradation of the elastomer increased dramatically with decreased segmental dynamics and presumed partial oxidation of the carborane cage. The integrity of the m-carborane cage and the segmental dynamics were found to be significantly reduced at temperatures above 580 °C, in line with the known cage rearrangement temperature for icosahedral carboranes. 相似文献
43.
In this paper, calculating the molecular internal rotating steric factor of polymers by the radiation crosslinking method is studied and a relationship between the molecular internal rotating steric factor (σ) and crosslinking parameter βis established~([1]) by taking account of the effect of polymer chain flexibility on βvalue, σvalue of polymer obtained by this method is in agreement with that given with other method. 相似文献
44.
以乙酰丙酮镍、油酸、油胺为原料,十八烯为溶剂,聚乙烯吡咯烷酮为表面活性剂,采用溶剂热法,在不同反应条件制备了纳米级氧化镍材料.通过X射线衍射(X-ray diffraction,XRD)、透射电子显微镜(Transmission electron microscope,TEM)、紫外-可见光吸收光谱(Ultraviolet-visible spectroscopy,UV-Vis)光谱分析以及塔菲尔(Tafel)测试考察了反应物比例、保温时间、表面活性剂(PVP)、油胺的量对产物微结构、粒径、形貌、光学以及电化学活性性能的影响.实验结果表明:在反应物n[Ni(acac)2]∶n(OA)=1∶2、添加剂PVP质量分数为1.66%、油胺物质的量为30 mmol、200℃下保温8 h时,可获得粒径约为30~40 nm纯相氧化镍,具有最佳电化学活性,交换电流密度为J0=1.23×10-2 mA·cm-2. 相似文献
45.
Structural and Magnetochemical Studies on KCuGaF6 The crystal structure of KCuGaF6 was determined on the base of X‐ray single crystal data (wR2 = 0.084 for 2476 independent reflections). The compound crystallizes with a = 728.56(4), b = 989.51(6), c = 676.27(3) pm, β = 93.120(5)°, Z = 4 in space group P21/c of the pyrochlore related KCuCrF6 type. The octahedral coordinations [GaF6] and [CuF6] are slightly resp. strongly distorted (mean values Ga‐F: 188.2 pm resp. Cu‐F: 188.2/200.1/227.6 pm). The longest distances Ga‐F and the shortest ones Cu‐F are found within octahedral chains of these two kinds of atoms, running along [100] and [001], resp., and being mutually bridged as well (M‐F‐M in between 114 and 145°). The magnetic mole susceptibilities measured at powders and at a single crystal follow the isotropic Heisenberg model for S = 1/2, if effects of chain disrupture are considered in the form of some paramagnetic portion. No indication of threedimensional magnetic order is observed down to T = 2 K and low magnetic fields H < 100 G. KCuGaF6 (J/k = —71 K for the powder) is distinguished this way from the chain structure compounds KCuAlF6 und Na2CuScF7 (J/k = —76 resp. —59 K) which were also magnetically studied and yield similar antiferromagnetic exchange constants J/k. 相似文献
46.
基于Ziegler-Natta催化剂的氯硅烷功能化非共轭α,ω-双烯烃与丙烯共聚,在水的引发下脱水缩合可有效地形成长支链结构的聚丙烯树脂.而氢气常作为丙烯聚合中的链转移剂,调控聚丙烯的分子量,基于此,研究了氢气对氯硅烷功能化非共轭α,ω-双烯烃与丙烯共聚物链结构的影响.核磁共振氢谱(~1H-NMR)测试结果表明,氢气抑制了氯硅烷功能化非共轭α,ω-双烯烃的插入,随着氢气用量的增加,共聚物分子链中端基乙烯基含量由0.12 mol%降低到0.05 mol%.熔体流变行为测试结果显示,聚合物熔体的储能模量、损耗模量和零剪切黏度均随着氢气用量增加而降低,这主要是由于相对分子质量减小和长支链密度的减少. 相似文献
47.
Tubular halloysite can be used as a template to fabricate a novel metallized ceramic microstructure through electroless plating. Reduction of Pd ions by methanol is conducted to initiate Ni plating. There is a simultaneous deposition of Ni nanoparticles on the outer surface and discontinuous wires in the lumen site of the halloysite template obtained. The different deposition could be caused by the different composition distribution of ferric oxide impurity in the wall due to the isomorphic substitution during the formation of halloysite template. Its magnetic property is mainly attributed to the Ni nanoparticles, not the wires. The metallized ceramic microstructure has the potential to be utilized as a novel magnetic material. 相似文献
48.
采用实验室小型RIM机制备了一组不同芳香二胺扩链的嵌段聚氨酯-脲(PUU)弹性体,借助于IR、DSC、DMTA、SEM以及拉伸试验等测试手段对其结构与性能进行了研究.通过比较由MDA、DETDA以及CAMDA三种不同活性和结构的芳香二胺扩链剂与二异氰酸酯反应形成的硬链段对RIMPUU弹性体的结构与性能的影响,表明:MDA基RIMPUU中软、硬链段微区界面作用指数很小,微相分离程度却很大,其性能最差;DETDA基RIMPUU弹性体有理想的界面作用指数,以及适当的微相分离程度,其性能位于三者之中最佳.DMTA研究证实在一定的温度范围内DETDA基RIMPUU的模量稳定性最好. 相似文献
49.
The microstructure of a series of high conversion copolymers of methyl acrylate (MA) and N-vinylcarbazole (NVC) was characterized by NMR. 1H- and 13C-NMR spectra were assigned by comparison to the homopolymers and by using heteronuclear shift correlation spectroscopy. MA-centered triad distributions were obtained from the carbonyl carbon. Distributions of NVC sequences were determined from aromatic carbons 1 and 8a, and aromatic proton 1 These experimentally determined sequence distributions were compared to those calculated from reactivity ratios approximated from the copolymer compositions. Agreement was very good for low NVC content copolymers. Three signals were particularly useful in providing rapid assessment of the distribution of NVC units within low NVC content copolymers: proton 1 and carbon 1 of NVC and the carbonyl carbon of MA. © 1992 John Wiley & Sons, Inc. 相似文献
50.
钇对2618合金组织及性能的影响 总被引:7,自引:1,他引:7
采用X射线,光学显微镜及扫描电镜等手段研究了2618合金中的组织与相结构,并研究了元素钆在2618合金中的存在形式及其对合金力学性能的影响。结果表明,微量钆元素在铝合金中是以化合物形式存在的;钆对合金中的铸态组织及Al9FeNi仃形态没有影响。由于微量钆的加入,降低了铜与镁在2618合金中的固溶量,减少了时效析出相A2CuMg数量,从而降低2618合金的室温强度帮在250℃的高温瞬时强度;但由于微量钆减少了铜与镁在2618合金中的扩散速度,延缓了时效机的粗化,并由于第二相数量的增多,因此提高了2618合金在250℃经100h高温热暴露后的高温瞬时强度。 相似文献