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41.
Surface modification of soft-glass capillaries for gas chromatography by treatment with water vapour
“Leaching” or “etching” by strong mineral acids seems to be a necessary pretreatment step for the most commonly used deactivation procedures of glass capillaries by reaction with either polyethylene glycol or silylation reagents. The acidic sites which are formed on the surface during this acid treatment cannot be completely removed by the subsequent deactivation process. This drawback can be overcome by performing the leaching with water vapour, resulting in an accumulation of cations at the surface and a decrease in the number of silanol groups. Capillaries of this type show excellent properties for the chromatography of strongly basic compounds. After the wash-out of the alkaline surface layer, the acidity of the support is suited for the chromatography of strongly basic as well as strongly acidic compounds. Due to a lack of reactive acidic sites, special deactivation procedures have to be applied to capillaries produced in this way. 相似文献
42.
The reduction of triphenyltin piperidyl dithiocarbamate in acetone has been investigated using d.c. polarography and cyclic
voltammetry. Polarographic reduction yielded four well-defined waves, two of which were diffusion-controlled and two of which
appear to represent adsorption processes. The cyclic voltammetric study yielded results in close agreement with the polarographic
data. Results appear to indicate the release of the dithiocarbamate moiety, followed by reduction to form the triphenyltin
radical, which undergoes dimerization, as well as reduction to the triphenyltin anion. For comparison, the polarographic reduction
of triphenyltinchloride was investigated. A mechanism similar to that proposed by earlier authors for the polarographic behaviour
of tributyltin oxide was found.
For convenience, the more commonly used terminology of piperidyl dithiocarbamate is used throughout the paper, in place of
(piperidine-1-carbodithioato) triphenyltin (IV). 相似文献
43.
J. Borrs R. Carballo A. Castieiras M. C. Gmez‐Conde M. C. Fernndez‐Vidal J. Nicls 《无机化学与普通化学杂志》2005,631(11):2221-2226
Four new dinuclear copper(II) complexes have been synthesized and have the general formula [Cu2(L)(H2O)2], where L = GLYDTO [N,N′‐bis(carboxymethyl)dithiooxamide], ALADTO [N,N′‐bis(carboxyethyl)dithiooxamide], VALDTO [N,N′‐bis(1‐carboxy‐2‐methylpropyl)dithiooxamide] and LEUDTO [N,N′‐bis(1‐carboxy‐3‐methylbutyl)dithiooxamide]. The complexes were characterized by elemental analysis as well as by IR, electronic and EPR spectroscopy. These techniques provided evidence for the presence of the CuNO2S chromophore. Magnetic susceptibility measurements on all the complexes in the range 4–300 K show the existence of a dominant antiferromagnetic interaction with ?J values greater than 300 cm?1. Thermal decomposition behaviour of the complexes was studied by thermogravimetry. 相似文献
44.
C. DurioA. Daidouh N. ChouaibiC. Pico M.L. Veiga 《Journal of solid state chemistry》2002,168(1):208-216
New sodium orthophosphates of general formula Na2M3(PO4)3 belonging to the alluaudite-type structure have been synthesized and characterized by neutron and X-ray powder diffraction. The nature of the M3 elements (M3=GaMn2, GaCd2, InMn2 and FeMnCd) was chosen in order to analyze their influence on electrical and magnetic properties. The conductivity of these materials was measured by the complex impedance method and the transport mechanism was studied from complex permittivities and modulus formalism. Electrical results including charge/discharge experiments showed two main behaviors: GaCd2 and FeMnCd behave as purely ionic conductors whereas GaMn2 and InMn2 are mixed ionic-electronic conductors. The magnetic susceptibility data reveal the antiferromagnetic behavior of FeMnCd, InMn2 and GaMn2, with a weak ferromagnetic transition at low temperatures. 相似文献
45.
层状锑磷酸嵌接式卟啉锰制备与模拟细胞色素氧化催化研究 总被引:1,自引:0,他引:1
层状锑磷酸嵌接式卟啉锰制备与模拟细胞色素氧化催化研究胡希明,皮宗新,梅治乾,古国榜,黄仲涛(华南理工大学应用化学系,华南理工大学化学工程系,广州,510641)关键词卟啉锰,层状锑磷酸,嵌接,催化性能细胞色素P450是一种含血红素的单充氧化酶,在室温... 相似文献
46.
Hydraulic conductivity of rock fractures 总被引:26,自引:0,他引:26
The flow of a single-phase fluid through a rough-walled rock fracture is discussed within the context of fluid mechanics. The derivation of the cubic law is given as the solution to the Navier-Stokes equations for flow between smooth, parallel plates - the only fracture geometry that is amenable to exact treatment. The various geometric and kinematic conditions that are necessary in order for the Navier-Stokes equations to be replaced by the more tractable lubrication or Hele-Shaw equations are studied and quantified. In general, this requires a sufficiently low flow rate, and some restrictions on the spatial rate of change of the aperture profile. Various analytical and numerical results are reviewed pertaining to the problem of relating the effective hydraulic aperture to the statistics of the aperture distribution. These studies all lead to the conclusion that the effective hydraulic aperture is less than the mean aperture, by a factor that depends on the ratio of the mean value of the aperture to its standard deviation. The tortuosity effect caused by regions where the rock walls are in contact with each other is studied using the Hele-Shaw equations, leading to a simple correction factor that depends on the area fraction occupied by the contact regions. Finally, the predicted hydraulic apertures are compared to measured values for eight data sets from the literature for which aperture and conductivity data were available on the same fracture. It is found that reasonably accurate predictions of hydraulic conductivity can be made based solely on the first two moments of the aperture distribution function, and the proportion of contact area. 相似文献
47.
A. El Sayed S. S. Abd El Rehim H. Mansour 《Monatshefte für Chemie / Chemical Monthly》1991,122(12):1019-1027
Summary The electrochemical behaviour of pure indium in KOH solutions (1–4M) was studied at different temperatures (25–70°C) by potentiostatic techniques. Two anodic peaks corresponding to the formation of In(OH)3 and In2O3 were observed. The heights of the two peaks increased with the increase of alkali concentration. An increase of temperature increased the peak currents and shifted their corresponding potentials to more negative values. The variation of the peak currents and peak potentials with scan rate suggested that the anodic dissolution of indium was a diffusion controlled process. In cyclic voltammetry, the reverse scan consistently showed one peak which was attributed to the reduction of anodic oxidation products into indium. X-ray diffraction analysis confirmed the presence of In(OH)3 at the first anodic peak, In(OH)3 and In2O3 at the second anodic peak and In2O3 in the permanent passive region.
Zum elektrochemischen Verhalten einer Indium-Elektrode in konzentrierter Kalilauge bei verschiedenen Temperaturen
Zusammenfassung Es wurde das Verhalten von reinem Indium in 1 – 4M KOH-Lösungen bei Temperaturen zwischen 25 und 70°C mittels potentiostatischer Methoden untersucht. Zwei anodische Peaks, entsprechend der Bildung von In(OH)3 und In2O3, traten auf. Die Höhe der beiden Peaks wurde mit zunehmender Alkalikonzentration gesteigert. Eine Temperaturerhöhung verstärkte die Peakströme und verschob die entsprechenden Potentiale zu negativeren Werten. Die Abhängigkeit der Peakströme und Peakpotentiale von der Scangeschwindigkeit legte den Schluß nahe, daß die anodische Lösung von Indium in einem diffusionskontrollierten Prozeß stattfindet. Bei der cyclischen Voltammetrie zeigte der reverse Scan einheitlich einen Peak, der der Reduktion der anodischen Oxidationsprodukte zu Indium zugeschrieben wurde. Röntgendiffraktionsanalyse bestätigte die Präsenz von In(OH)3 beim ersten anodischen Peak, In(OH)3 beim zweiten Peak und In2O3 im permanent passiven Bereich.相似文献
48.
Barral L. Cano J. López J. López-Bueno I. Nogueira P. Ramírez C. Abad M. J. 《Journal of Thermal Analysis and Calorimetry》1999,55(1):37-45
A study of an epoxy-cycloaliphatic amine system has been realized using a thermogravimetric technique (TG). Isothermal and
non-isothermal (dynamic) methods were employed to determine the kinetic data of this system.
Five methods were used for determining the activation energies of this system in the dynamic heating experiments. In two of
them (Flynn-Wall-Ozawa, and Kissinger) it is not necessary to have a prior knowledge of the reaction mechanism of the degradation
behaviour for this system. In the other ones (Coats and Redfern, Horowitz and Metzger, and Van Krevelen et al.) it is necessary
to know this reaction mechanism, besides Criado et al. method was used for determining it.
The results have shown that good agreement between the activation energies obtained from all methods can be achieved if it
is assumed that the degradation behaviour of this system is of sigmoidal-rate type.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
49.
A complexing process is developed to prepare Y-Ba-Cu-O superconducting fibers. The process is not identical to typical sol-gel processes; here the resulting gel network is built up by hydrogen bonding linkage among complexing species in non-aqueous solution. Cu acetate, [Cu(OAC)2], Ba methoxyethoxide [Ba(ORE)2] and Y acetate [Y(OAC)3] are used as precursors for preparing homogeneous gels while -methacrylic acid (HOAA) and diethylenetriamine (DETA) as complexing agents, and methoxyethanol (REOH) as solvent. Fibers drawn from a sol obtained through reduced pressure present no or little deformation at 80°MoC via adjusting the amount of DETA and HOAA. Cu(OAC)2, Ba(ORE)2 and Y(OAC)3 in the complexing process have been demonstrated to form gels without hydrolysis and condensation at ambient atmosphere. The relationships between the drawing behavior of sols and gel structure with different amounts of DETA and HOAA are suggested. The concentration region of drawing the gel fibers with no or little deformation heated at 80°MoC is also found. 相似文献
50.
以含铈铝锂合金为研究对象,研究了磁场对含稀土铝锂合金时效过程的影响,从断裂特征及微观组织两方面分析了磁场作用规律。实验结果表明:未加磁场时,合金的断裂特征以理断裂为主;扁平晶粒厚度不匀,在磁场作用下,此合金的断裂特征与微观组织发生明显改观,随磁感应强度增强,合金主断裂面上准解理断裂特征减弱,同时二次裂纹增多,分层比较升高;扁平晶粒厚度变薄,尺寸趋于均匀。用少体物理理论,探讨了磁场对含稀土合金原子扩散过程的影响,为进一步研究稀土元素在磁场中的行为及其局域效应提供了一定的实验依据。 相似文献