全文获取类型
收费全文 | 4976篇 |
免费 | 896篇 |
国内免费 | 887篇 |
专业分类
化学 | 2115篇 |
晶体学 | 33篇 |
力学 | 970篇 |
综合类 | 74篇 |
数学 | 416篇 |
物理学 | 3151篇 |
出版年
2024年 | 6篇 |
2023年 | 52篇 |
2022年 | 105篇 |
2021年 | 144篇 |
2020年 | 134篇 |
2019年 | 131篇 |
2018年 | 163篇 |
2017年 | 178篇 |
2016年 | 226篇 |
2015年 | 208篇 |
2014年 | 291篇 |
2013年 | 438篇 |
2012年 | 296篇 |
2011年 | 336篇 |
2010年 | 289篇 |
2009年 | 335篇 |
2008年 | 329篇 |
2007年 | 342篇 |
2006年 | 341篇 |
2005年 | 301篇 |
2004年 | 281篇 |
2003年 | 223篇 |
2002年 | 228篇 |
2001年 | 182篇 |
2000年 | 163篇 |
1999年 | 159篇 |
1998年 | 147篇 |
1997年 | 116篇 |
1996年 | 88篇 |
1995年 | 92篇 |
1994年 | 99篇 |
1993年 | 49篇 |
1992年 | 46篇 |
1991年 | 38篇 |
1990年 | 21篇 |
1989年 | 34篇 |
1988年 | 21篇 |
1987年 | 21篇 |
1986年 | 10篇 |
1985年 | 16篇 |
1984年 | 12篇 |
1982年 | 16篇 |
1981年 | 9篇 |
1980年 | 4篇 |
1979年 | 10篇 |
1978年 | 10篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1973年 | 3篇 |
1969年 | 2篇 |
排序方式: 共有6759条查询结果,搜索用时 187 毫秒
111.
Human serum is routinely measured for total calcium content in clinical studies. A definitive high-accuracy and low-uncertainty method is required for reference measurements to underpin medical diagnoses. This study presents a novel octopole collision cell ICP-MS, high-accuracy, methodology and comparison of that technique with double-focusing sector field ICP-MS and an ICP-OES method. Double-matched isotope dilution mass spectrometry (IDMS) was employed for ICP-MS techniques and an exact matching bracketing technique using scandium as an internal standard was used for ICP-OES analysis. Medium resolution mode was utilised for double-focusing sector field ICP-MS analysis to resolve the dominant interferences on the 44Ca/42Ca isotope pair. Hydrogen reaction gas was employed to chemically resolve a number of polyatomic interferences predominantly through charge transfer reactions in the octopole collision cell. Comparison data presented for NIST CRM 909b human serum analysis from all three techniques demonstrates highest accuracy (99.6%) and lowest uncertainty (1.1%) for octopole collision cell ICP-MS. Data from ICP-OES using a non-IDMS technique produces comparably accurate data and low-uncertainties. The much higher total expanded uncertainties for double-focusing sector field ICP-MS compared with octopole collision cell data are explained by lower precision on the measurement of the 44Ca/42Ca isotope ratio. Data for octopole collision cell ICP-MS submitted for an international blind trial comparison (CCQM K-14) demonstrated excellent agreement with the mean of all participants with a low expanded uncertainty. 相似文献
112.
TIMING OF COLLISION BETWEEN THE NORTH AND SOUTH CHINA BLOCKS——THE Sm-Nd ISOTOPIC AGE EVIDENCE 总被引:8,自引:0,他引:8
Sm-Nd isotopic ages for C-type eclogite (243.9±5.6 Ma) and mafic and ultramafic rocks(230.6±30.7 Ma and 402.6±17.4 Ma) from the Qinling-Dabieshan orogenic belt are reported.These ages suggest that at the early Triassic, the North and South China Blocks have beenunited along the Qinling-Dabieshan collision zone, and before the final collision, a se-ries of ophiolite obductions took place successively away from the continental marginduring the Paleozoic. 相似文献
113.
The effectivity of solvents as electron pair donors 总被引:1,自引:0,他引:1
Y. Marcus 《Journal of solution chemistry》1984,13(9):599-624
The effectivity of solvents as electron pair donors, their donicity as expressed by their donor numbers DN, is reexamined. The linear dependence of the enthalpy and the Gibbs free energy for the reaction of donor solvents with antimony pentachloride is affirmed. Extension of the DN scale by other measured quantities, via their linear correlations for sets of solvents where both kinds of data are known is applied to Drago's E-C scale, Kamlet's scale, and Koppel's B scale. This extension, added to previous extensions employing Selbin's DI, II and Popov's 23Na, produces a DN scale for 170 solvents. The relation of DN measured for isolated solvent molecules in 1,2-dichloroethane to DN values measured for bulk solvents is examined by means of the scaled particle theory and solute-solvent interaction terms. A scale of normalized donor numbers DN
N
is presented. These values are practically the same as the scale, and for those solvents for which DN values are presented here and values are lacking, they can serve in their place for those preferring to use the scale for donor solvents. 相似文献
114.
采用改进颗粒床模型的CFD方法模拟了实验室规模冷模装置内鼓泡床的流体流动时空特性。模拟结果表明表观气速是影响气固动态特征和压力波动的主要因素之一:随表观气速的增大,气泡数目增加,气泡体积增大,压力波动增强;气速越高时均压降越大;在内循环鼓泡流化床内固体颗粒呈“单室”流型。上述与实验观察相吻合的模拟结果将有助于放大和设计商业化的内循环流化床生物质气化炉。 相似文献
115.
A theory is developed for the potential distribution around a charged spherical colloidal particle carrying ionized groups on the particle surface in a medium containing its counterions (i.e., counterions produced from dissociation of the particle surface groups) and a small amount of added salts on the basis of the theory of Imai and Oosawa. Numerical solutions to the Poisson–Boltzmann equation for the potential distribution are obtained for the case of dilute (but not infinitely dilute) particle suspensions of volume fraction 1 for
a1 (where is the Debye–Hückel parameter and a is the particle radius). Here we have taken into account the effects of (i) counterions from the particle surface groups, and (ii) the finite particle volume fraction. These effects, which are usually neglected in the conventional Poisson–Boltzmann equation, are found to be important. It is found that, as in the case of completely salt-free media, there is a certain critical value of the particle charge (which is the same as that for the completely salt-free case). When the particle charge is lower than the critical value, the potential is given by a Coulomb potential. If the particle charge is higher than the critical value, then counterions are accumulated in the vicinity of the particle surface (counterion condensation) and the potential becomes less dependent on the particle charge. The above behaviors can be observed even for the case where the electrolyte concentration is higher than the concentration of counterions from the particle surface groups, if the conditions
1 and a1are both satisfied. 相似文献
116.
Nd-Fe-B磁体烧结过程晶粒长大行为的研究 总被引:4,自引:0,他引:4
定量描述了Nd-Fe-B磁体烧结过程晶粒长大行为,分析了烧结温度、烧结时间、合金粉末粒度及其分布对烧结过程晶粒长大的影响,讨论了烧结过程晶粒长大机制。在Nd-Fe-B磁体烧结过程开始之后的0—1h时间区段,晶粒长大迅速;随着烧结时间的延长,晶粒长大速度减小。合金粉末平均粒度增大,或者合金粉末粒度分布范围增宽,显著促进Nd-Fe-B磁体烧结过程中晶粒的长大。在Nd-Fe-B磁体的烧结过程中,存在两类晶粒长大机制,即Nd2Fe14B颗粒的溶解与析出、Nd2Fe14B颗粒的并合与长大。Nd2Fe14B颗粒的并合与长大不仅使磁体的平均晶粒尺寸增大,也使晶粒尺寸分布范围增宽,是烧结Nd-Fe-B磁体显微组织中出现异常大晶粒的根本原因。 相似文献
117.
In this paper are described the main characteristics of the plasma spraying process of alumina deposits, i.e., the temperature and flow field of the plasma jets obtained with the classical spraying torches, the injection of the particles into the plasma jet, the particle surface temperature and velocities in the plasma (measured for calibrated alumina particles), and the coating generation. The measurements on the alumina particles are compared with the predictions of a mathematical model. The experimental and computed particle velocities are in rather good agreement. However, this is not the case for the particle surface temperature. Possible reasons for the discrepancy are proposed (influence of the carrier gas, thermophoretic forces, and poor penetration of the particles into the plasma core even for an injection velocity twice that of the optimal calculated one, as shown by recent measurements). Finally the correlations between the particle velocities and surface temperature, and the properties of the alumina coating (porosity, crystal structure, mechanical properties) are studied. 相似文献
118.
Xianmei Xie Xiurong Ren Jinping Li Xiaojun Hu Zhizhong Wang 《天然气化学杂志》2006,15(2):100-104
Ultrasonic technology has been intensively studied recently due to its special features. In this paper, an ultrasonic crystallization method was introduced for the preparation of ZnAl-Hydrotalcite-Like compounds (ZnAl-HTLcs). Samples with high crystallinity, small particle size and narrow particle size distribution were obtained and fully characterized using conventional techniques of XRD, FT-IR and TGDTA. The results prove that both ultrasonic frequency and ultrasonic power have effects on the sizes of the product particles. By varying the ultrasonic power from 250 W to 88 W, with the ultrasonic frequency fixed at 59 kHz, the median particle size of the samples increased from 0.37 μm to 0.82 μm. By altering the hydrothermal treatment time from 1 h to 5 h at 110℃, the median particle size of ZnAl-HTLcs synthesized via ultrasonic crystallization increased from 0.88 μm to 1.11 μm. 相似文献
119.
The kinetic method is one of the most widely used experimental techniques for the measurement of thermochemical parameters by mass spectrometry. Recently it has been realized that it can also be used to determine reaction entropies, but the validity of this approach has not been established. This Perspective evaluates kinetic method plots in cases where there is a significant entropy difference between the competing fragmentation channels (i.e. between sample and reference compounds in the dissociating cluster ion). The concept underlying this study is to calculate mass spectra theoretically, based on known thermochemical parameters and as a function of experimental conditions. This can be done accurately using the RRKM-based MassKinetics software. The resulting mass spectra are then interpreted by the kinetic method, yielding DeltaH and DeltaS values. These values are, in turn, compared with the true values used to generate the calculated mass spectra. The results show that the reaction entropy difference between sample and reference has a very large influence on kinetic method plots. This should always be considered when studying energy-dependent mass spectra (using metastable ions or low- or high-energy collision-induced dissociation (CID)), even if only DeltaH is to be determined. Kinetic method plots are not strictly linear and this becomes a serious issue in the case of small molecules showing a large entropy effect. In such cases, results obtained at a low degree of excitation are more accurate. Energy and entropy effects can be evaluated in a relatively straightforward manner: first, the apparent Gibbs energy (DeltaG(app)) and effective temperature (T(eff)) are determined from kinetic method plots (intercept and slope, respectively), obtained from experiments using various degrees of excitation. Second, the resulting DeltaG(app) is plotted against T(eff), the slope yielding DeltaS while the intercept (extrapolation to zero temperature) yields DeltaH. This data evaluation yields more accurate results than alternative methods used in the literature. The resulting DeltaH values are fairly accurate, with errors, in most cases, <4 kJ mol(-1). On the other hand, DeltaS is systematically underestimated by 20-40%. Empirically scaling DeltaS values determined by the kinetic method by 1.35 results in a DeltaS value within 20% (or 10 J mol(-1) K(-1)) of the theoretical value. 相似文献
120.
We present a unified approach for linear and nonlinear sensitivity analysis for models of reaction kinetics that are stated in terms of systems of ordinary differential equations (ODEs). The approach is based on the reformulation of the ODE problem as a density transport problem described by a Fokker-Planck equation. The resulting multidimensional partial differential equation is herein solved by extending the TRAIL algorithm originally introduced by Horenko and Weiser in the context of molecular dynamics (J. Comp. Chem. 2003, 24, 1921) and discussed it in comparison with Monte Carlo techniques. The extended TRAIL approach is fully adaptive and easily allows to study the influence of nonlinear dynamical effects. We illustrate the scheme in application to an enzyme-substrate model problem for sensitivity analysis w.r.t. to initial concentrations and parameter values. 相似文献