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21.
Mitsutoshi Jikei Daisuke Uchida Yuuki Haruta Yuuki Takahashi Kazuya Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2012,50(18):3830-3839
Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB2 monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling 13C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
22.
《Journal of computational chemistry》2017,38(2):101-109
The branching ratio of unimolecular decomposition can be evaluated by solving the rate equations. Recent advances in automated reaction path search methods have enabled efficient construction of the rate equations based on quantum chemical calculations. However, it is still difficult to solve the rate equations composed of hundreds or more elementary steps. This problem is especially serious when elementary steps that occur in highly different timescales coexist. In this article, we introduce an efficient approach to obtain the branching ratio from a given set of rate equations. It has been derived from a recently proposed rate constant matrix contraction (RCMC) method, and termed full‐RCMC (f‐RCMC). The f‐RCMC gives the branching ratio without solving the rate equations. Its performance was tested numerically for unimolecular decomposition of C3H5 and C4H5. Branching ratios obtained by the f‐RCMC precisely reproduced the values obtained by numerically solving the rate equations. It took about 95 h to solve the rate equations of C4H5 consisting of 234 elementary steps. In contrast, the f‐RCMC gave the branching ratio in less than 1 s. The f‐RCMC would thus be an efficient alternative of the conventional kinetic simulation approach. © 2016 Wiley Periodicals, Inc. 相似文献
23.
LI YuQiang 《中国科学 数学(英文版)》2014,(10)
We consider a kind of site-dependent branching Brownian motions whose branching laws depend on the site-branching factorσ(·).We focus on the functional ergodic limits for the occupation time processes of the models in R.It is proved that the limiting process has the form ofλξ(·),where A is the Lebesgue measure on IE andξ(·)is a real-valued process which is non-degenerate if and only ifσis integrable.Whenξ(·)is non-degenerate,it is strictly positive for t0.Moreover,ξconverges to O in finite-dimensional distributions if the integral ofσtends to infinity. 相似文献
24.
Dr. Heng Liao Dr. Liu Zhong Dr. Zefan Xiao Dr. Ting Zheng Prof. Haiyang Gao Prof. Qing Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):14048-14055
A series of novel α‐diamine nickel complexes, (ArNH‐C(Me)‐(Me)C‐NHAr)NiBr2, 1 : Ar=2,6‐diisopropylphenyl, 2 : Ar=2,6‐dimethylphenyl, 3 : Ar=phenyl), have been synthesized and characterized. X‐ray crystallographic analysis showed that the coordination geometry of the α‐diamine nickel complexes is markedly different from conventional α‐diimine nickel complexes, and that the chelate ring (N‐C‐C‐N‐Ni) of the α‐diamine nickel complex is significantly distorted. The α‐diamine nickel catalysts also display different steric effects on ethylene polymerization in comparison to the α‐diimine nickel catalyst. Increasing the steric hindrance of the α‐diamine ligand by substitution of the o‐methyl groups with o‐isopropyl groups leads to decreased polymerization activity and molecular weight; however, catalyst thermal stability is significantly enhanced. Living polymerizations of ethylene can be successfully achieved using 1 /Et2AlCl at 35 °C or 2 /Et2AlCl at 0 °C. The bulky α‐diamine nickel catalyst 1 with isopropyl substituents can additionally be used to control the branching topology of the obtained polyethylene at the same level of branching density by tuning the reaction temperature and ethylene pressure. 相似文献
25.
The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB2 polycondensation with substitution effect were derived by the kinetic mechanism.The reactivity difference between the B group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained.The concentration of terminal units has a maximum with the increase of the conversion of A groups(x).The higher the reactivity ratio(r) of linear B group to branched one is,the later the maximum appears and the larger it is.The degree of branching of the hyperbranched polymers obtained is controllable by adjusting the parameters of r and x,which increases with increasing both x and r. 相似文献
26.
The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB_2 polycondensation with substitution effect were derived by the kinetic mechanism.The reactivity difference between the B group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained.The concentration of terminal units has a maximum with the increase of the conversion of A groups(x).The higher the reactivity... 相似文献
27.
A variety of linear and 3-arm star polyethylene (PE) model polymers covering a wide range of molecular weight are synthesized by the living polymerization of butadiene and the subsequent hydrogenation. Several rheological parameters of these model linear and 3-arm star PE samples are analyzed for detecting the long chain branching (LCB) structure. It is found that the analyses based on zero shear viscosity, vGP plot and flow activation energy are very sensitive to the 3-arm star PEs. The information on the presence of LCB can be obtained with these methods even for low molecular weight samples, which can not be determined by GPC-MALLS. However the information about the LCB structure can not be obtained by the rheological methods alone. 相似文献
28.
29.
LI JunPing & LIU ZaiMing School of Mathematical Science Computing Technology Central South University Changsha China 《中国科学 数学(英文版)》2011,(5)
We consider a modified Markov branching process incorporating with both state-independent immigration-migration and resurrection. The effect of state-independent immigration-migration is firstly in- vestigated in detail. The explicit expressions for the extinction probabilities and mean extinction times are presented. The ergodicity and stability properties of the process incorporating with resurrection structure are then investigated. The conditions for recurrence, ergodicity and exponential ergodicity are... 相似文献
30.