首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1704篇
  免费   65篇
  国内免费   163篇
化学   1233篇
晶体学   5篇
力学   77篇
综合类   3篇
数学   333篇
物理学   281篇
  2024年   1篇
  2023年   8篇
  2022年   24篇
  2021年   25篇
  2020年   41篇
  2019年   37篇
  2018年   24篇
  2017年   38篇
  2016年   42篇
  2015年   58篇
  2014年   94篇
  2013年   109篇
  2012年   115篇
  2011年   123篇
  2010年   107篇
  2009年   119篇
  2008年   138篇
  2007年   140篇
  2006年   95篇
  2005年   86篇
  2004年   99篇
  2003年   55篇
  2002年   45篇
  2001年   33篇
  2000年   39篇
  1999年   30篇
  1998年   25篇
  1997年   31篇
  1996年   21篇
  1995年   14篇
  1994年   25篇
  1993年   12篇
  1992年   14篇
  1991年   16篇
  1990年   9篇
  1989年   11篇
  1988年   5篇
  1987年   2篇
  1986年   1篇
  1985年   5篇
  1984年   2篇
  1983年   3篇
  1982年   2篇
  1981年   2篇
  1980年   3篇
  1979年   1篇
  1978年   1篇
  1977年   1篇
  1976年   1篇
排序方式: 共有1932条查询结果,搜索用时 15 毫秒
101.
The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q 0 parameter, which is related to the sorption capacity, corresponding to 6.3 mg g− 1 for K-10/Cd(II), 4.8 mg g− 1 for K-10/Mn(II), 11.2 mg g− 1 for NT-25/Cd(II) and 6.0 mg g− 1 for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L− 1 solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.  相似文献   
102.
Abstract

The flexural strengths of N-vinylpyrrolidone modified glass-ionomer cements were investigated. The optimal molar ratio of the monomers in copolymers, composed of the three components acrylic acid, itaconic acid and N-vinylpyrrolidone, was determined using a SAS statistical program. The copolymers were prepared using a free-radical polymerization process. The viscosities of aqueous solutions of these polymers were determined. Cements were formed by the reaction of these solutions with glass particles. Flexural strength (FS) was used as the basic screening property to find the optimum molar ratio. Statistical models were applied to predict the optimum molar ratios. All strength values were recorded on the specimens conditioned in distilled water at 37°C for 7 days. The optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on flexural strength and viscosity. The effect of molecular weight (MW) on FS was also evaluated. Copolymer with a MW of 10, 800 (Mn) showed 85% higher FS than the Ketac-Molar (KM) system, along with a reasonable working viscosity.  相似文献   
103.
This paper describes the electrocatalytic oxidation of amines on TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl)‐modified electrodes prepared by electrochemical copolymerization of TEMPO precursor containing pyrrole side chain and 2,2′‐bithiophene. The modified electrode exhibits electrocatalytic activity for the oxidation of primary and secondary amines. Cyclic voltammetric studies showed that the peak current of the cyclic voltammogram increased linearly with increasing concentration of amine in the sample solution.  相似文献   
104.
105.
Any decision-making process that relies on a probabilistic forecast of future events necessarily requires a calibrated forecast. This article proposes new methods for empirically assessing forecast calibration in a multivariate setting where the probabilistic forecast is given by an ensemble of equally probable forecast scenarios. Multivariate properties are mapped to a single dimension through a prerank function and the calibration is subsequently assessed visually through a histogram of the ranks of the observation’s preranks. Average ranking assigns a prerank based on the average univariate rank while band depth ranking employs the concept of functional band depth where the centrality of the observation within the forecast ensemble is assessed. Several simulation examples and a case study of temperature forecast trajectories at Berlin Tegel Airport in Germany demonstrate that both multivariate ranking methods can successfully detect various sources of miscalibration and scale efficiently to high-dimensional settings. Supplemental material in form of computer code is available online.  相似文献   
106.
Uniformly distributed point sets on the unit sphere with and without symmetry constraints have been found useful in many scientific and engineering applications. Here, a novel variant of the Thomson problem is proposed and formulated as an unconstrained optimization problem. While the goal of the Thomson problem is to find the minimum energy configuration of N electrons constrained on the surface of the unit sphere, this novel variant imposes a new symmetry constraint – mirror reflection symmetry with the xy plane as the plane of symmetry. Qualitative features of the two-dimensional projection of the optimal configurations are briefly mentioned and compared to the ground-state configurations of the two dimensional system of charged particles laterally confined by a parabolic potential well.  相似文献   
107.
本文研究了亚硝酸盐(NO_2~-)在纳米金和β-环糊精复合修饰碳糊电极(AuNPs-β-CD/CPE)上的电化学行为。实验结果表明,与裸CPE相比,AuNPs-β-CD/CPE对NO_2~-的电化学氧化有显著的促进作用,其氧化峰电流显著增加。同时用循环伏安法(CV)、计时电流法(CA)测定了NO_2~-在AuNPs-β-CD/CPE上的电极反应动力学参数,用线性扫描伏安法(LSV)法测得NO_2~-氧化峰电流与其浓度在6.0×10-6~8.0×10-3 mol·L-1范围内呈良好的线性关系,检出限(S/N=3)为5.7×10-7 mol·L-1。将该传感器应用于水样的检测,相对标准偏差在0.15%~1.40%之间,回收率达99.3%~104.0%,检测结果符合定量测定要求。  相似文献   
108.
PTFE nanospheres have been obtained with the assistant of different multi-walled carbon nanotubes (MWNTs) by means of a simple preparation method. The results show that the PTFE nanospheres possess the best dispersion stability using the fluorocarbon-modified MWNTs as the assistant. The products are characterized by field-emission scanning electron microscopy and X-ray photoelectron spectroscopy, respectively.  相似文献   
109.
The detection of Allura red (AR) by electrochemical reduction using a different electrode from the conventional mercury electrode is presented. A carbon paste with cobalt (II, III) oxide composite electrode (CoOx/CPE) is reported for the first time for the detection of AR. Moreover, others dyes such as tartrazine (TZ), sunset yellow (SY), amaranth (AM), Ponceaut 4‐R (P‐4R), and Sudan (SD) as well as pharmaceutical agents such as paracetamol (PMC) that are present in samples that contained AR did not show a reduced signal between 0.0 and ?0.3 V, which is the potential range where AR reduction was observed. The surface electroactivity was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The presence of CoOX increased the cathodic peak current for AR by more than 50 % and 65 % via CV and square wave voltammetry (SWV), respectively, compared with an unmodified carbon paste electrode. Under the optimal parameters, (pH=3.0, accumulation time (tACC)=60 s and accumulation potential (EACC)=0.50 V), the detection limit for AR was 0.05 μmol L?1. The new sensor was sensitive and stable for the detection of AR. Moreover, it was easily manufactured and very convenient for food samples such as soft and isotonic drinks as well as chili sauce.  相似文献   
110.
We consider the nonlinear problem of inhomogeneous Allen–Cahn equation
?2Δu+V(y)u(1?u2)=0inΩ,?u?ν=0on?Ω,
where Ω is a bounded domain in R2 with smooth boundary, ? is a small positive parameter, ν denotes the unit outward normal of ?Ω, V is a positive smooth function on Ω¯. Let Γ be a curve intersecting orthogonally with ?Ω at exactly two points and dividing Ω into two parts. Moreover, Γ satisfies stationary and non-degenerate conditions with respect to the functional ΓV1/2. We can prove that there exists a solution u? such that: as ?0, u? approaches +1 in one part of Ω, while tends to ?1 in the other part, except a small neighborhood of Γ.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号