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71.
R. G. Rinaldi M. C. Boyce S. J. Weigand D. J. Londono M. W. Guise 《Journal of Polymer Science.Polymer Physics》2011,49(23):1660-1671
The evolution in the hard/soft domain microstructure of an elastomeric‐like polyurea during different tensile loading histories was studied using in situ small‐ and wide‐angle X‐ray scattering (SAXS/WAXS). The nonlinear stress–strain behavior is initially stiff with a rollover yield to a more compliant response; unloading is highly nonlinear showing substantial hysteresis while also exhibiting significant recovery. Reloading reveals a substantially more compliant “softened” behavior and dramatically reduced hysteresis. WAXS peaks monitor characteristic dimensions of regular features within the hard domains; the peak location remains unchanged with tensile deformation indicating no separation of the internal structure within a domain, but the peak intensity becomes anisotropic with deformation evolving in a reversible manner consistent with orientation due to stretch. The SAXS profiles provide information between major hard domains. SAXS peaks are found to shift with tensile loading in a relatively affine manner up to a tensile true strain of ~0.4, which, using a Bragg reduction to aid interpretation, reveals an axial increase and a transverse decrease in interdomain spacings; this evolution is reversible for strains less than ~0.4. Increasing axial strain beyond a true strain of ~0.4 is accompanied by a dramatic, progressive, and irreversible reduction in axial Bragg spacing, indicating a breakdown in the hard domain aggregate network structure. A four‐point pattern is seen to develop during stretching. The breakdown in networked structure during a first load cycle gives a new structure for subsequent load cycles, which is seen to evolve in a reversible manner for strains less than or equal to the prior maximum strain. However, for strains exceeding the prior maximum strain excursion, additional breakdown is found. These SAXS results show that a breakdown in the hard domain aggregate network structure is a governing mechanism for the large dissipation (hysteresis) loops of the first load cycle and are also responsible for the softened reloading response. The absence of structure breakdown during subsequent load cycles corresponds to the substantially reduced hysteresis loops as well as the stable softened behavior. DMA data on pristine and previously deformed samples show a more compliant storage modulus in the predeformed sample, supporting the softened cyclic stress–strain data and the structural breakdown observed in the SAXS; the loss modulus was unchanged with deformation, which correlates with the lossy features measured in DMA with time‐dependent viscosity rather than losses due to structural breakdown. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 相似文献
72.
73.
A simple analytical approximative solution was given for calculating the time dependent development of the ice-layers at the cooled walls inside a parallel plate channel. By ignoring the effect of acceleration, resulting from converging ice-layers in the axial direction, an analytical solution for the variation of the ice-layer thickness with time and axial position could be obtained. The approximative solution was checked by numerical calculations and good agreement was found.Es wurde ein analytisches Näherungsverfahren entwickelt, das es ermöglicht, die zeitliche Entwicklung der Erstarrungsfronten im gekühlten, ebenen Kanal zu bestimmen. Die Methode liefert unter Vernachlässigung der Beschleunigungsterme durch die konvergenten Eisschichten eine exakte Lösung der Phasengrenzbeziehung. Das Näherungsverfahren wurde mittels numerischer Berechnungen überprüft und stimmt bis zu Wandunterkühlungsverhältnissen vonB=10 sehr gut mit der numerischen Lösung überein. 相似文献
74.
A simple numerical model is presented to predict the steady-state ice layers on the cooled walls inside a parallel plate channel for arbitrary entrance velocity profiles. The effect of two different entrance velocity distributions (a parabolic velocity distribution and a slug flow) on the shape of the ice-layers are examined. The quality of an approximative solution given in literature was checked by comparing with the numerical results. For the case of a fully developed parabolic velocity distribution at the entrance of the cooled channel the results are compared with experimental findings of Kikuchi [8]. A generally good agreement was found.Es wurde ein einfaches numerisches Modell entwickelt, das es ermöglicht, die stationären Erstarrungsfronten an den Kanalwänden für beliebige Verteilungen des Eintrittsgeschwindigkeitsprofils zu berechnen. Als Beispiele wurden ein voll ausgebildetes Parabelprofil und ein Pfropfenprofil am Eintritt in die Kühlstrecke untersucht. Mit Hilfe der numerischen Lösung konnte die Güte einer aus der Literatur bekannten Näherungslösung zur Berechnung der Erstarrungsfronten überprüft werden. Für den Fall des Parabelprofils am Kanaleintritt wurde die Rechnung mit Meßwerten von Kikuchi [8] verglichen. Es zeigte sich eine gute Übereinstimmung zwischen Theorie und Experiment. 相似文献
75.
A simple and quite flexible numerical model is presented to predict the steady state ice-layer formation inside a cooled two dimensional channel or a tube containing a turbulent flow. The effects of arbitrary entrance velocity distributions upon the shape of the ice-layers are examined. The presented numerical scheme is verified by comparing the predicted ice-layers with measurements and generally good agreement was found. 相似文献
76.
Felix Brück Jörg Glatthaar Harald Weigand 《International journal of environmental analytical chemistry》2013,93(14-15):1499-1511
Large-scale groundwater contamination by arsenic (As) requires economical yet reliable analytical procedures to monitor the quality of well water and the effluent of As elimination processes. The silver diethyldithiocarbamate (AgDDTC) method provides the basis of a series of colourimetric tests used as a compromise between semi-quantitative field-test kits and expensive instrumental analytics. This study aimed at understanding the significant As overestimation by the AgDDTC method observed in landfill leachate samples. Results of the AgDDTC test were up to threefold the levels obtained by reference analyses. Overestimation broadly agreed with the time course of chemical oxygen demand and total phosphorus in the leachate. We hypothesised that the interference was caused by reduced P species or humic acid (HA), respectively. To test this, As-AgDDTC determinations from As standards were conducted with phosphonic (H3PO3) and phosphinic acid (H3PO2) as well as two commercial HA as matrix components. While H3PO3 showed no effect, H3PO2 in concentrations of 0.06 to 28 mg P L?1 yielded As recoveries of up to 130%. This was probably due to the evolution of phosphine (PH3) as suggested by the absorption spectra recorded after reacting pure PH3 with AgDDTC in pyridine. The HA in concentrations of 0.6–320 mg dissolved organic carbon L?1 gave As recoveries of up to 600%, possibly due to a chromophoric reaction of volatile HA digestion products formed during the reduction step. Significant As overestimation in the presence of the above-named compounds may require pre-oxidation of the samples. To recognise interference effects, the acquisition of full absorbance spectra may be recommendable in lieu of fixed wavelength analyses. 相似文献
77.
78.
Clemens Taube Kai Schwedtmann Medena Noikham Ekasith Somsook Felix Hennersdorf Robert Wolf Jan J. Weigand 《Angewandte Chemie (International ed. in English)》2020,59(9):3585-3591
[LCRP((PhP)2C2H4)][OTf] ( 4 a,b [OTf]) and [LCiPrP(PPh2)2][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [LCRP(pyr)2][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; LCR=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P?N/P?P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph2P)2(LCMeP)2][OTf]2 ( 7 a [OTf]2) is observed when reacting 3 a [OTf] with diphosphane P2Ph4. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH3CN)4]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLCiPr)Au}4][OTf]4 ( 9 [OTf]4) was unexpectedly formed as a result of a chloride‐induced P?P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH3CN)3][OTf]2 (M=Cu, Ag) ( 10 [OTf]2, 11 [OTf]2). 相似文献
79.
Khaled Shawakfeh Mohammad El-khateeb Deeb Taher Helmar Görls Wolfgang Weigand 《Transition Metal Chemistry》2008,33(3):387-391
A synthetic study of ruthenium complexes containing pentafluorobenzenethiolato ligand is presented. The bis(triphenylphosphine)
complex CpRu(PPh3)2SC6F5 (1) is prepared from CpRu(PPh3)2Cl and C6F5S− in high yield. This complex is readily reacted with CO gas to give the mixed carbonyl-phosphine complex CpRu(PPh3)(CO)SC6F5 (2) and with NOBF4 at room temperature to give [CpRu(PPh3)(NO)SC6F5]BF4 (3). The one-pot reaction of CpRu(PPh3)2Cl, dppa ligands, and C6F5S− produces CpRu(dppa)SC6F5 [dppa = bis(diphenylphosphino)methane: dppm (4); bis(diphenylphosphino)ethane: dppe (5)]. Complexes (1)–(5) have been characterized by spectroscopic techniques (i.r., 1H-n.m.r., 31P-n.m.r.) and by elemental analysis. The X-ray structural analysis of (5) is reported.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
80.
Jan J. Weigand Andreas Decken Neil Burford 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(2):o64-o66
In the molecular crystal of hexaphenylhexaphosphinane benzene solvate, C36H30P6·C6H6, representing the trigonal form of phosphobenzene as a solvate, the six‐membered ring of P atoms adopts a chair conformation wherein the six phenyl groups are located in equatorial positions. The molecules [molecular symmetry (C3i)] are stacked infinitely along the c‐axial direction. 相似文献