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61.
Giuseppe Spedalotto Dr. Robert Gericke Marta Lovisari Dr. Erik R. Farquhar Dr. Brendan Twamley Dr. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11983-11990
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII2 complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date. 相似文献
62.
Petr P. Sharin Sofia P. Yakovleva Susanna N. Makharova Maria I. Vasilieva Vasilii I. Popov 《Composite Interfaces》2019,26(1):53-65
The structural-phase state of the contact zone and the factors that influence on the strength of diamond retention in the diamond carbide composites were determined. Composites were obtained by the new hybrid technology that eliminates the reheating of the metalized coating. The elaborated technology combines the thermal diffusion metallization of a diamond and the sintering by the scheme of self-dosed impregnation in a one-stage technological cycle. By the methods of electron microscopy, X-ray diffraction analysis, and Raman spectroscopy the structural and phase characteristics of the interphase boundary were investigated. The improvement of chemical and mechanical adhesion between the diamond and carbide matrix was obtained. It was shown that the specific productivity of the samples with a metalized diamond component is 39% higher than those without metallization. 相似文献
63.
Khalid Mujasam Batoo Khalid Mehmood Ur Rehman 《Chinese Journal of Physics (Taipei)》2018,56(1):108-116
A series of Sm-CoMn substituted hexagonal ferrites with chemical composition of Sr0.85-xCa0.15SmxFe12-y(Co0.5Mn0.5)yO19 (0.00?≤?x?≤?0.60, (0.00?≤?y?≤?0.50) were synthesized by the solid-state reaction method. Microstructure and magnetic properties of the hexaferrites have been investigated by the X-ray diffraction, field emission scanning electron microscopy and a permanent magnetic measuring system. A single magnetoplumbite phase is exhibited in the hexaferrites with the substitutiom of Sm (0.00?≤?x?≤?0.12) and CoMn (0.00?≤?y?≤?0.10) contents. For the hexaferrites containing Sm (x?≥?0.24) and CoMn (y?≥?0.20), impurity phases are observed in the structure. The FESEM micrographs exhibit that the hexaferrites with different Sm-CoMn contents have formed hexagonal structures and the grain size of the hexaferrites remains unchanged with increasing Sm-CoMn content. The remanence (Br), Hk/Hcj ratios, and maximum energy product [(BH)max] decrease with increasing Sm-CoMn content (0.00?≤?x?≤?0.60, (0.00?≤?y?≤?0.50). Instrinsic coercivity (Hcj) and magnetic induction coercivity (Hcb) increase with increasing Sm-CoMn content (0.00?≤?x?≤?0.12, 0.00?≤?y?≤?0.10), and then decrease with increasing Sm-CoMn content (0.12?≤?x?≤?0.36, 0.10?≤?y?≤?0.30), while for the hexaferrites with Sm (x?≥?0.36) and CoMn (y?≥?0.30), with increasing Sm-CoMn content, Hcj increases and Hcb decreases. 相似文献
64.
The emission of radiation from relativistic positrons moving in the 〈110〉 axial channels of an f.c.c. (diamond) crystal has
been studied. An expression for the radiation intensity has been obtained for the general case of positron motion. This expression
has been simplified for the particular case of well-collimated incident beam. Enhancement of the radiation over (ordinary)
bremsstrahlung has been discussed. 相似文献
65.
66.
We have investigated the pressure-induced Raman spectral changes of 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4]). We found that [emim][BF4] did not crystallize up to 1.2 GPa. The Raman CH stretching spectra arising from the CH3 groups of the ethyl-chain and the CH3 group adjacent to the imidazolium-ring in [emim]+ cation largely changed against pressure. Moreover, the Raman intensity of the CH2 (N) bending band arising from the alkyl-chain drastically changes with increasing pressure, but that of the imidazolium-ring in-plane bending band arising from the imidazolium-ring is independent of pressure. Our results show that the environment around the alkyl-chain of [emim][BF4] is largely perturbed rather than that around the imidazolium-ring upon compression. 相似文献
67.
Semiconductor diamond is considered the best heater material to generate ultra-high temperatures in a Kawai cell. In two pioneering studies, a mixture of graphite and amorphous boron (or boron carbide, B4C) was converted to semiconductor diamond in the diamond stability field and was confirmed to generate 2000°C and 3500°C, respectively. Following these works, we synthesized a homemade boron-doped graphite block with fine machinability. With this technical breakthrough, we developed a semiconductor diamond heater in a smaller Kawai-type cell assembly. Here, we report the procedure for making machinable boron-doped graphite, and the performance of the material as a heater in a Kawai cell at 15?GPa using tungsten carbide anvils and at ~50?GPa using sintered diamond anvils. Furthermore, we present a finite element simulation of the temperature distribution generated by a semiconductor diamond heater, which is much more homogeneous than that generated by a metal heater. 相似文献
68.
现代热力学的完整分类系统--非平衡非耗散热力学新领域 总被引:1,自引:0,他引:1
在同一体系中同时有多个不可逆过程时,不可逆过程之间会有相互影响,原来的非自发过程有可能在其他自发过程的影响下得以进行,这种现象就称为热力学耦合或反应耦合,长期以来,经典热力学把热力学第二定律的等式作为平衡体系的充分必要条件,其中隐含了一个前提性的假定,即经典热力学的对象只限于非耦合的体系,摈弃这一隐含的前提性假定以后,热力学自身就发展成为一个现代热力学的完整学术体系,适用于任何宏观体系(包括极其复杂的生命体系),现代热力学的完整学术体系中包含了一个崭新的非平衡非耗散热力学新领域,由于该领域属于热力学第二定律的等式部分,因此可以定量计算,并得到一系列理论计算的非平衡相图,与文献上报道的激尖低压金刚石合成等的大量实验数据相符。 相似文献
69.
Synthesis of micro- or nano-crystalline diamond films on WC-Co substrates with various pretreatments by hot filament chemical vapor deposition 总被引:4,自引:0,他引:4
Diamond films deposited on tungsten carbide can lead to major improvements in the life and performance of cutting tools. However, deposition of diamond onto cemented tungsten carbide (WC-Co) is problematic due to the cobalt binder in the WC. This binder provides additional toughness to the tool but results in poor adhesion and low nucleation density of any diamond film. A two-step chemical etching pretreatment (Murakami reagent and Caro acid, (MC)-pretreatment) and a boronization pretreatment have both been used extensively to improve adhesion of CVD diamond film on WC-Co substrates. Here we discuss the applicability of MC-pretreatment for a range of Co-containing WC-Co substrates, and demonstrate a controlled synthesis process based on liquid boronizing pretreatment for obtaining smooth and dense micro- or nano-crystalline diamond films on high Co-containing WC-Co substrates. Substrate treatments and deposition parameters were found to have major influences on the smoothness, structure and quality of the diamond films. The best quality diamond films were achieved under conditions of relatively high substrate temperature (Ts) and the best adhesion was achieved at Ts = 800 °C. 相似文献
70.