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41.
42.
The strain energies and through-space distances between the two bridgehead E atoms of a selection of 1,3-dimethyl-1,3-ditetrelbicyclo[1.1.1]pentanes
(tetrel E = Si, Ge or Sn) were examined by quantum chemical calculations at MP2 and B3LYP levels. The aim is to identify which
bridges lead to short through-space E,E distances, and simultaneously, to as low strain as possible. A short E,E distance
should improve through-space interaction, and a low strain should promote the thermal stability and possibly also facilitate
their synthesis. The bridges examined included CH2, CMe2, CtBu2, C(CH2)n (n = 2–4), O, NMe, S, PMe, SiMe2, GeMe2, and SnMe2. The calculations indicate that the phospha bridge is a good compromise providing reasonably low strain as well as E,E through-space
distances which are only longer than normal E–E single bonds by factors of 1.06–1.10.
This paper is dedicated to Professor Mitsuo Kira in recognition of his stimulating Si chemistry and his 2005 Wacker Award. 相似文献
43.
Takayasu Yamauchi Hiroyuki Sazanami Yuuichi Sasaki Kimio Higashiyama 《Tetrahedron》2005,61(7):1731-1736
1,3-Oxazolidines were easily obtained by condensation of N-substituted (R)-phenylglycinol with aldehydes. Addition of organolithium reagents to 1,3-oxazolidines by complexation with the bulky Lewis acid aluminum tris(2,6-diphenylphenoxide) (ATPH) readily produced the corresponding chiral amines with good yield and high diastereoselectivity. The configuration of the new stereogenic center was shown to be opposite to that of adducts obtained for the same 1,3-oxazolidines using Grignard reagents. The best diastereoselectivity was achieved using N-isopropyl-1,3-oxazolidines. The mechanism of addition was deduced by determining the stereochemistry of the iminium-aluminum complex by NOE experiments. 相似文献
44.
Nobuyuki Tanaka 《Journal of Thermal Analysis and Calorimetry》1996,46(3-4):1021-1031
The instantaneous elastic moduli for a nylon-6 monofilament were derived on strain recoveries right after creep, stress relaxation, and rapid elongation,E
c
,E
s
andE
e
, respectively. It was found that during strain recoveryE
s
(>E
e
) andE
e increase monotonically with increasing load,m
1, on the sample. The extrapolated value of Es atm
1=0 g is almost equal to Young's modulus, 4.06 GPa. The value ofE
c also increased with increasingm
1, and atm
1=600 g (1.93 t cm–2) reached about 14 GPa. The endothermic heat change right after creep, stress relaxation or rapid elongation,Q, was negligibly small. For comparison,E
s
,E
c
andQ were also investigated for silicone rubber. It was found thatE
s (53.8 M Pa at the draw ratioD=1.2) decreased abruptly atD=1.3. In the range ofD=1.4–1.9,E
s was only 22.6 MPa. In the case of stress relaxation,Q increased with increasingD from 4 J mol–1 (atD=1.2) to 56 J mol–1 (atD=1.9). FurthermoreE
c (5.58 MPa atm
1=133.8 g (429.4 kg cm–2)) increased gradually with increasing m1 and attained 16.6 MPa atm
1=548.4 g (1.76 t cm–2). In the case of creep,Q was in the range of 0–11.5 J mol–1 and larger when larger loads,m
2 were removed during the later stages of creep.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe author wishes to thank Mr. Keizi Igarashi and Mr. Tetsuya Yasui for helping in the experiments. 相似文献
45.
By using a micro-bomb calorimeter, the standard enthalpies of combustion of C60 and C70 have been determined to be - (25 947.1±8.5) and - (29 956.1 ± 8.9) kJ/mol respectively. A g. 1. c. analysis indicated that
the amounts of residual organic solvents in the samples were very small, and their effects on the final results were negligible.
The energy of combustion ofC60 determined in this work is in agreement in the uncertainty interval with that determined by means of traditional calorimeter
using macro amount of sample. The enthalpies of formation of these two substances have been derived. The strain energies in
the molecules of C60 and C70 were estimated by a bond energy scheme and by using corannulene as the model compound, the results estimated from different
methods are very close.
Project supported by the National Natural Science Foundation of China (Grant No. 29473143) 相似文献
46.
Michael A. Carpenter Susana Rios Wilson Crichton 《Journal of solid state chemistry》2007,180(1):360-369
Lattice parameters of a synthetic powder sample of Ca0.35Sr0.65TiO3 perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO3 perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure. 相似文献
47.
由于分段三次参数Hermite插值的切矢往往被作为变量,故可对其进行优化以使得构造的插值曲线满足特定的要求.为了构造兼具保形性与光顺性的平面分段三次参数Hermite插值曲线,给出了一种通过同时极小化导数振荡和应变能来确定切矢的方法.首先以导数振荡函数和应变能函数为双目标建立了切矢满足的方程系统;然后证明了方程系统存在唯一解,并给出了解的具体表达式;最后给出了误差分析,并通过数值算例表明方法的有效性.结果表明,相对于导数振荡极小化方法和应变能极小化方法,所提出的导数振荡和应变能极小化方法同时兼顾了平面分段三次参数Hermite插值曲线的保形性和光顺性. 相似文献
48.
Min Seong Kim Yung Lee Junseong Ahn Seonggi Kim Kyungnam Kang Hyuneui Lim Byeong-Soo Bae Inkyu Park 《Advanced functional materials》2023,33(3):2208792
Conventional elastomeric polymers used as substrates for wearable platforms have large positive Poisson's ratios (≈0.5) that cause a deformation mismatch with human skin that is multidirectionally elongated under bending of joints. This causes practical problems in elastomer-based wearable devices, such as delamination and detachment, leading to poorly reliable functionality. To overcome this issue, auxetic-structured mechanical reinforcement with glass fibers is applied to the elastomeric film, resulting in a negative Poisson's ratio (NPR), which is a skin-like stretchable substrate (SLSS). Several parameters for determining the materials and geometrical dimensions of the auxetic-structured reinforcing fillers are considered to maximize the NPR. Based on numerical simulation and digital image correlation analysis, the deformation tendencies and strain distribution of the SLSS are investigated and compared with those of the pristine elastomeric substrate. Owing to the strain-localization characteristics, an independent strain-pressure sensing system is fabricated using SLSS with a Ag-based elastomeric ink and a carbon nanotube-based force-sensitive resistor. Finally, it is demonstrated that the SLSS-based sensor platform can be applied as a wearable device to monitor the physical burden on the wrist in real time. 相似文献
49.
Diamond,as an ultra-wide bandgap semiconductor,has become a promising candidate for next-generation microelec-tronics and optoelectronics due to its numerous advantages over conventional semiconductors,including ultrahigh carrier mo-bility and thermal conductivity,low thermal expansion coefficient,and ultra-high breakdown voltage,etc.Despite these ex-traordinary properties,diamond also faces various challenges before being practically used in the semiconductor industry.This review begins with a brief summary of previous efforts to model and construct diamond-based high-voltage switching diodes,high-power/high-frequency field-effect transistors,MEMS/NEMS,and devices operating at high temperatures.Following that,we will discuss recent developments to address scalable diamond device applications,emphasizing the synthesis of large-area,high-quality CVD diamond films and difficulties in diamond doping.Lastly,we show potential solutions to modulate diamond’s electronic properties by the“elastic strain engineering”strategy,which sheds light on the future development of diamond-based electronics,photonics and quantum systems. 相似文献
50.
采用紫外光刻工艺(ultraviolet lithography technique,UVL),在互补金属氧化物半导体(complementary metal oxide semiconductor,CMOS)兼容的硅基平台上制作了基于悬空微桥结构在Ge/SiGe多量子阱材料中引入双轴张应变的低偏振相关电吸收调制器。利用拉曼光谱测试了器件引入双轴张应变的大小,并对器件在横电(transverse electric,TE)偏振和横磁(transverse magnetic,TM)偏振下的光电流响应、调制消光比和高频响应等性能进行了测试。器件的低偏振相关消光比在0 V/4 V工作电压下可达5.8 dB,3 dB调制带宽在4 V反向偏置电压时为8.3 GHz。与电子束光刻工艺(electron beam lithography technique,EBL)相比,采用UVL制作的器件在调制消光比、高频响应带宽等性能上略差一点,但具有曝光时间短、成本低和可大批量生产等优势,应用前景广阔。 相似文献