全文获取类型
收费全文 | 203篇 |
免费 | 33篇 |
国内免费 | 8篇 |
专业分类
化学 | 197篇 |
晶体学 | 3篇 |
力学 | 4篇 |
物理学 | 40篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 1篇 |
2020年 | 3篇 |
2019年 | 9篇 |
2018年 | 4篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 8篇 |
2014年 | 7篇 |
2013年 | 23篇 |
2012年 | 7篇 |
2011年 | 10篇 |
2010年 | 8篇 |
2009年 | 15篇 |
2008年 | 11篇 |
2007年 | 14篇 |
2006年 | 9篇 |
2005年 | 3篇 |
2004年 | 3篇 |
2003年 | 10篇 |
2002年 | 17篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 6篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有244条查询结果,搜索用时 62 毫秒
1.
A Contribution on Ternary Oxides of the AMO4-Type (A = Ti3+, Cr3+; M = Nb5+, Ta5+ ) CrNbO4, CrTaO4, TiNbO4, and TiTaO4 were prepared by CO2-laser technique. X-ray single crystal investigations show a random distribution of the metal ions in Rutil type structure, space group D–P42/mnm. Calculations of the free energy of reaction between Ti2O3 and Nb2O5 show higher stability of TiO2 beside NbO2. In TiNbO4 both metals exhibit the oxidation state +4. 相似文献
2.
Nb6.74Ta5.26S4 has been prepared by high temperature techniques. The crystal structure has been determined from single crystal X-ray diffraction data (R/Rw = 0.0588/0.0655). The compound crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 959.11 (26) pm, b = 336.37 (10) pm, and c = 3282.51 (74) pm. The orthorhombic cell contains four formula units. Its structure is similar to that of Nb-rich sulfides, rather than to that of Ta-rich sulfides. The metal coordinations are capped distorted cubic prisms and pentagonal prisms while the coordinations of sulfur are capped trigonal prisms. 相似文献
3.
M. Boča V. Danielik Z. Ivanová E. Mikšíková B. Kubíková 《Journal of Thermal Analysis and Calorimetry》2007,90(1):159-165
The phase diagrams of the systems KF-K2TaF7 and KF-Ta2O5 were determined using the thermal analysis method. The phase diagrams were described by suitable thermodynamic model. In
the system KF-K2TaF7 eutectic points at x
KF=0.716 and t=725.4°C and at x
KF=0.214 and t=712.2°C has been calculated. It was suggested that K2TaF7 melts incongruently at around 743°C forming two immiscible liquids. The system KF-Ta2O5 have been measured up to 8 mol% of Ta2O5. The eutectic point was estimated to be at x
KF∼0.9 and t∼816°C. The formation of KTaO3 and K3TaO2F4 compounds has been observed in the solidified samples. 相似文献
4.
Yuandong Wu 《Journal of solid state chemistry》2005,178(5):1569-1574
The new ternary alkali tantalum polysulfide K2Ta2S10 has been synthesized by reacting TaS2 with an in situ formed melt of K2S3 and S at 773 K. The compound crystallizes with four formula units in the monoclinic space group P21/n (No. 14) with lattice parameters of . The structure contains two different zigzag chain anions [TaS5]−, running parallel to the crystallographic b-axis separated by potassium cations. The two crystallographically independent tantalum atoms are in a distorted bi-capped trigonal prismatic environment of eight sulfur atoms which was never observed before. The TaS8 polyhedra share three S atoms on each side to form the anionic chains. The compound was characterized with FIR and Raman spectroscopy. 相似文献
5.
Studt F MacKay BA Johnson SA Patrick BO Fryzuk MD Tuczek F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):604-618
Reaction of the side-on end-on dinitrogen complex [{(NPN)Ta}(2)(mu-H)(2)(mu-eta(1):eta(2)-N(2))] (1; in which NPN=(PhNSiMe(2)CH(2))(2)PPh), with the Lewis acids XR(3) results in the adducts [{(NPN)Ta}(2)(mu-H)(2)(mu-eta(1):eta(2)-NNXR(3))], XR(3)=GaMe(3) (2), AlMe(3) (3), and B(C(6)F(5))(3) (4). The solid-state molecular structures of 2, 3, and 4 demonstrate that the N-N bond length increases relative to those found in 1 by 0.036, 0.043, and 0.073 A, respectively. In solution complexes 2-4 are fluxional as evidenced by variable-temperature (1)H NMR spectroscopy. The (15)N{(1)H} NMR spectra of 2-4 are reported; furthermore, their vibrational properties and electronic structures are evaluated. The vibrational structures are found to be closely related to that of the parent complex 1. Detailed spectroscopic analysis on 2-4 leads to the identification of the theoretically expected six normal modes of the Ta(2)N(2) core. On the basis of experimental frequencies and the QCB-NCA procedure, the force constants are determined. Importantly, the N-N force constant decreases from 2.430 mdyn A(-1) in 1 to 1.876 (2), 1.729 (3), and 1.515 mdyn A(-1) (4), in line with the sequence of N-N bond lengths determined crystallographically. DFT calculations on a generic model of the Lewis acid adducts 2-4 reveal that the major donor interaction between the terminal nitrogen atom and the Lewis acid is mediated by a sigma/pi hybrid molecular orbital of N(2), corresponding to a sigma bond. Charge analysis performed for the adducts indicates that the negative charge on the terminal nitrogen atom of the dinitrogen ligand increases with respect to 1. The lengthening of the N-N bond observed for the Lewis adducts is therefore explained by the fact that charge donation from the complex fragment into the pi* orbitals of dinitrogen is increased, while electron density from the N-N bonding orbitals p(sigma) and pi(h) is withdrawn due to the sigma interaction with the Lewis acid. 相似文献
6.
Binary organic-inorganic gels have been prepared by mixing a carbonaceous hydrosol and a Nb2O5 or Ta2O5 sol derived by hydrolysis of the alkoxides. The gels are pyrolyzed under an inert atmosphere into precursors in which carbon and the metal oxides are mixed very intimately. High temperature treatment converts the precursors into the cubic face centered carbides. The precursors as well as the carbides have been shown to be micro- and mesoporous materials. Measurements of nitrogen adsorption reveal a characteristic change of the shapes of the isotherms (Type I Type IV) and of the hysteresis loops (H4H2H1) during the thermal processes. Pore widening has been observed with rising temperature. The phenomena of crystallization, carbothermal reduction and sintering were found to control the pore shape and size. The results of the adsorption measurement correlate well with those of the thermoanalytical and X-ray diffraction studies.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
7.
A. I. Yanovsky N. Ya. Turova A. V. Korolev D. E. Chebukov A. P. Pisarevsky Yu. T. Struchkova 《Russian Chemical Bulletin》1996,45(1):115-121
Anodic oxidation of tantalum in isopropyl alcohol or prolonged reflux of an alcohol solution of Ta(OPri)5 afford crystalline oxoisopropoxide Ta2O(OPri)8 · PriOH (1). In its molecule, two octahedra about Ta atoms are linkedvia the shared edge [(OPri)O]. Compound1 is the first example of oxoalkoxide containing such a small number of metal atoms. Unlike the known polynuclear molecules M
n
O
m
(OR)
p
, oxoalkoxide1 is stable in solutions; on transition to the gas phase, this compound is desolvated to form a very stable molecule Ta2O(OPri)8 (apparently, consisting of two octahedra with a shared edge). According to the data of mass spectrometry, analogous molecules exist in the gas phase over Ta(OAlk)5 (Alk = Me, Et, Pri, or Bu11). When compound1 is heated invacuo (10–2–10–3 Torr), Ta(OPri)5 is sublimated. Crystals of Ta7O9(OPri)17 (2) were formed upon prolonged storage of solutions of1 in PriOH. Heptanuclear molecule2 consists of two [Ta4] tetrahedra with a shared vertex. These tetrahedra are additionally linked togethervia one 3-oxo and two 2-OPri groups. Complex2 is a representative of heptameric oxoalkoxides of a new structural type.Deceased in I995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–131, January, 1996. 相似文献
8.
Raana Kashfi‐Sadabad Laura Gonzalez‐Fajardo Derek Hargrove Bahar Ahmadi Daniel Munteanu Sina Shahbazmohamadi Michael Jay Xiuling Lu 《Particle & Particle Systems Characterization》2019,36(4)
Nonspecific high‐energy radiation for treatment of metastatic ovarian cancer is limited by damage to healthy organs, which can be mitigated by the use of radiosensitizers and image‐guided radiotherapy. Gold (Au) and tantalum oxide (TaOx) nanoparticles (NPs), by virtue of their high atomic numbers, find utility in the design of bimetallic NP systems capable of high‐contrast computed tomography (CT) imaging as well as a potential radiosensitizing effect. These two radio‐dense metals are integrated into dendritic mesoporous silica NPs (dMSNs) with radial porous channels for high surface‐area loading of therapeutic agents. This approach results in stable, monodispersed dMSNs with a uniform distribution of Au on the surface and TaOx in the core that exhibits CT attenuation up to seven times greater than iodine or monometallic dMSNs without either TaOx or Au. Tumor targeting is assessed in a metastatic ovarian cancer mouse model. Ex vivo micro‐CT imaging of collected tumors shows that these NPs not only accumulate at tumor sites but also penetrate inside tumor tissues. This study demonstrates that after intraperitoneal administration, rationally designed bimetallic NPs can simultaneously serve as targeted contrast agents for imaging tumors and to enhance radiation therapy in metastatic ovarian cancer. 相似文献
9.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(9):1045-1052
A new tantalum phosphate, tridecasodium distrontium ditantalum nonaphosphate, Na13Sr2Ta2(PO4)9, was prepared using the high‐temperature flux method. The structure can be described as a three‐dimensional open framework containing isolated [TaV2(PO4)9]17− units that are interlocked by Na and Sr ions. Band structure studies by the first‐principles method revealed that Na13Sr2Ta2(PO4)9 is an insulator with an indirect band gap of 4.78 eV, which makes it suitable as a luminescent host matrix. A series of solid solutions, i.e. Na13Sr2–xTa2(PO4)9:xDy3+ (x = 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12 and 0.14), were prepared and their photoluminescence properties studied. Under 350 nm light excitation, these emit two typical emissions of the Dy3+ ion, i.e. the 4F9/2→6H15/2 transition centred at 476 nm and the 4F9/2→6H13/2 transition centred at 570 nm. 相似文献