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981.
The stoichiometric solubility constant of eitelite (NaMg
0.5
CO
3
+2H+ ⇄ Na++0.5Mg
2+
+CO
2
(g)+H
2
O, log*K
pso
I
=14.67±0.03 was determined at I=3 m (mol kg−1) (NaClO
4
) and 25°C. The stability of magnesium (hydrogen-)carbonato complexes in this ionic medium was explicitely taken into account.
Consequently, trace activity coefficients of free ionic species, calculated from the Pitzer model with ion-interaction parameters
from the literature, were sufficient for an evaluation of the thermodynamic solubility constants and Gibbs energies of formation
for eitelite (−1039.88±0.60), magnesite (−1033.60±0.40), hydromagnesite (−1174.30±0.50), nesquehonite (−1724.67±0.40), and
brucite (−835.90±0.80 kJ-mol
−1
). The increasing solubilities of nesquehonite and eitelite at higher sodium carbonate molalities were explained by invoking
a magnesium dicarbonato complex (Mg2++2CO
3
2−
⇄ Mg(CO3)
2
2−
, log βz = 3.90 ± 0.08). A set of ion-interaction parameters was obtained from solubility and dissociation constants for carbonic
acid in 1 to 3.5 m NaClO
4
media
which reproduce these constants to 0.02 units in log K. The following Pitzer parameters are consistent with the previously
studied formation of magnesium (hydrogen-)carbonato complexes in 3m NaClO
4
. The model and Gibbs functions of solid phases derived here reproduce original solubility data (−log [H+], [Mg
2+
]
tot
) measured in perchlorate medium within experimental uncertainty.
Presented at the XXII International Conference on Solution Chemistry, July 14–19, 1991, Linz, Austria. 相似文献
982.
采用低湿溶液缩聚的方法合成了对苯二甲酰氯,二甲基联苯胺和己二醇为单体的芳酯族液晶聚酯酰胺。用DSC,X光衍射分析和偏光显微镜等手段研究了该系列聚酯酰胺的热致液晶行为,确认了二甲基联苯胺单体用量在20%(mol)的情况下,所得聚酯酰胺仍为向列型液晶聚合物。由于聚酯酰胺分子间聚酰胺链段之间的氢键作用,随着二甲基联苯胺用量增加至60mol%时,所得的聚酯酰胺己无液晶转变温度,其液晶区间即从熔融温度直至分 相似文献
983.
With frontal analysis(FA),the dependence of adsorption isotherms of insulin on the composition of mobile phase in reversed phase liquid chromatography (RPLC) has been investigated,This is also a good example to employ the stoichiometric displacement theory (SDT) for ivestigating solute adsorption in physical chemistry.Six kinds of mobile phase in RPLC were employed to study the effects on the elution curves and adsorption isotherms of insulin.the key points of this paper are:(1) the stability of insulin due to delay time after preparing,the organic solvent concentration,the kind and the concentration of ion-pairing agent in mobile phase were found to affect both elution curve and adsorption isotherm very seriously.(2)To obtain a valid and comparable result,the composition of the mobile phase employed in FA must be as same as possible to that in usual RPLC of either analytical scale or preparative purpose.(3)Langmuir Equation and the SDT were employed to imitate these obtained adsorption isotherms.The expression for solute adsorption from solution of the SDT was found to have a better elucidation to the insulin adsorption from mobile phase in RPLC. 相似文献
984.
尼龙1010/尼龙6共聚物的表观相图研究 总被引:2,自引:0,他引:2
采用显微熔点法和DSC测定了尼龙1010/尼龙6共聚物的表观相图;分析了投料比与链节结构单元含量的关系。最低熔点时尼龙1010/尼龙6的理论重量投料比为60/40,摩尔比为33.3/66.7,实验结果与此相近。 相似文献
985.
986.
Summary The chromatographic behaviour of C6F5(CH2)3SiCl3, C6H5(CH2)3SiCl3, CF3(CF2)7CH2CH2SiCl3 and n-C10H21SiCl3 as well as the bonding of these ligands to silica is described. Phases with partially fluorinated ligands show entirely different chromatographic characteristics to analogous phases, where hydrogen replaces fluorine. The silica with the pentafluorophenyl-3-n-propyl-C6F5(CH2)3-ligand has higher k-values and a better selectivity for aromatic hydrocarbons than that with phenyl-3-n-propyl C6H5(CH2)3-groups, whereas the phase with the fluorinated carbon chain is less useful than the silica modified with n-decyltrichlorosilane n-C10H21SiCl3. The first effect can be explained by complex formation, and the second may be due to a different contact area between the ligand and the solute. The normal hydrocarbon chains hinder each other sterically and expose many adsorption sites, in contrast the perfluorinated chains are sterically fixed and are the first example of real brushes in HPLC. 相似文献
987.
M. Nagy 《Colloid and polymer science》1985,263(3):245-265
988.
J. R. Conder 《Journal of separation science》1984,7(11):615-619
The original plate model of chromatography is extended to the sorption process occurring at the column inlet and the desorption process at the column exit. At the column inlet it is shown that sufficiently wide feed bands undergo no change in concentration but a fall in band width, i.e., the volume of mobile phase occupied by the solute band is reduced. The reduction factor is (1 + k) where k is the mass distribution ratio (capacity factor). Narrower bands suffer partial reduction in both band width and concentration. On desorption at the outlet, however, the change is always in band width and not concentration. A perfect detector registers the true concentration-time profile of the band in the column if the solute mass fraction in the stationary phase is below 10?3 at the column outlet. The risks of stripping the stationary phase at high solute concentrations in analytical and preparative or production gas chromatography are compared. 相似文献
989.
Summary The chiral discrimination of phenoxypropionic acid herbicides by reversed-phase chromatography on a teicoplanin phase has been re-examined using the perturbation method to calculate the solute distribution isotherms. The effects of both temperature and the methanol (organic modifier) content of the mobile phase on the chiral discrimination mechanism were well described by the bi-Langmuir model. The method confirmed a change in the mechanism of enantiomer retention at a critical temperature, T*, and showed that the mechanism was independent of (i) herbicide molecular structure, i.e. the position of the chloro group on the phenol ring, and (ii) the absolute configuration of the carbon atom. Enantioselectivity was enhanced by increasing the mobile phase methanol content. Use of this approach also revealed that secondary sites on the teicoplanin surface were involved in the processes determining both retention and selectivity. It was clearly demonstrated that these secondary sites of low affinity were not affected by the temperature change and were not involved in the chiral recognition mechanism. 相似文献
990.
An anomaly is found in the vicinity of Tmax 560$ K on electric resistance versus temperature curves for yttrium hightemperature superconductors of the 123 phase. Xray phase analysis suggests a structural phase transition in the vicinity of Tmax due to oxygen redistribution in the mobile sublattice of this compound. Investigation of samples with Y partially replaced by Ca has shown that the structural phase transition does not depend on carrier concentration in the conduction band. 相似文献