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271.
Enthalpies of solution in molten 2 PbO · B2O3 at 974 K were measured for four spinelloids, phases I (0.75 NiAl2O4 · 0.25 Ni2SiO4), II (0.60 NiAl2O4 · 0.40 Ni2SiO4), III and IV (0.50 NiAl2O4 · 0.50 Ni2SiO4) in the system NiAl2O4 · Ni2SiO4. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl2O4 and Ni2SiO4 spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl2O4 and Ni2SiO4 spinels were estimated (in cal mol?1 K?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist. 相似文献
272.
Enthalpies of solution in 2PbO · B2O3 at 981 K have been measured for glasses in the system albite-orthoclase-silica and along the join Na1.6Al1.6Si2.4O8-K1.6Al1.6Si2.4O8. The join KAlSi3O8-Si4O8 shows zero heat of mixing similar to that found previously for NaAlSi3O8-Si4O8 glasses. Albite-orthoclase glasses show negative heats of mixing symmetric about Ab50Or50 (Wn = ? 2.4 ± 0.8 kcal). Negative heats of (Na, K) mixing are also found at Ternary excess enthalpies of mixing in the glassy system Ab-Or-4Q are positive but rarely exceed 1 kcal mol?1.Using earlier studies of the thermodynamic properties of the crystals, the present calorimetric data and the “two-lattice” entropy model, the albite-orthoclase phase diagram is calculated in good agreement with experimental data. Attempts to calculate albite-silica and orthoclase-silica phase diagrams reveal complexities probably related to significant (but unknown) mutual solid solubility between cristobalite and alkali feldspar and to the very small heat and entropy of fusion of SiO2. 相似文献
273.
Alexandra Navrotsky Hans D Zimmermann Richard L Hervig 《Geochimica et cosmochimica acta》1983,47(8):1535-1538
High temperature solution calorimetry of glasses in the system CaMgSi2O6 (Di)-CaAl2SiO6 (CaTs) show them to have negative enthalpies of mixing with a regular enthalpy parameter, WH, of -11.4 ± 0.7 kcal. Negative heats of mixing between alumina-rich and alumina-poor glasses seem to be a general phenomenon in aluminosilicates and are not confined only to glassy systems containing anorthite as a component. The thermodynamic behavior of glasses in the system SiO2-Ca0.5;AlO2-CaMgO2 appears to vary in a smooth fashion, with small positive heats of mixing near SiO2 and substantial negative heats of mixing for other compositions. The exothermic behavior with increasing may be related to local charge balance of M2+ and Al3+. The negative heats of mixing in MgCaSi2O6-CaAl2SiO6, MgCaSi2O6-CaAl2Si2O8 and NaAlSi3O8-CaAl2Si2O8 glasses are in contrast to the positive heats of mixing found in MgCaSi2O6-CaAl2SiO6 (pyroxene) and NaAlSi3O8-CaAl2Si2O8 (high plagioclase) crystalline solid solutions. 相似文献
274.
Summary The stilpnomelane minerals in the epimetamorphic series of the Romanian Carpathians are divided into four genetic groups. Some ferrostilpnomelanes from metamorphic iron-, manganese- and sulfide-ores have been studied optically, chemically, by differential thermal analysis, thermogravimetric analysis, X-ray diffraction, and IR absorption spectroscopy. Several conclusions on the chemical constitution and the widespread occurence of ferrostilpnomelane in the metamorphic ores of the Carpathians are given.
Mit 5 Figures 相似文献
Über Stilpnomelan in einigen kristallinen Formationen in den rumänischen Karpaten
Zusammenfassung Die Stilpnomelanvorkommen aus dem epimetamorphen Kristallin der rumänischen Karpaten werden in vier genetische Gruppen eingeteilt. Einige aus metamorphosierten Eisen-, Mangan- und Sulfiderzen stammende Ferrostilpnomelane wurden optisch, chemisch, mit Differentialthermoanalyse, Thermogravimetrie, Röntgenbeugung und Ultrarot-Absorptionsspektroskopie untersucht. Als Schlußfolgerungen ergeben sich einige allgemeine Hinweise über die Zusammensetzung des Ferrostilpnomelans in den Kristallinerzen der Karpaten.
Mit 5 Figures 相似文献
275.
High temperature solution calorimetry of synthetic quartz, coesite and stishovite provides enthalpies of transition. ΔH9750 for quartz-coesite and ΔH2980 for coesite-stishovite transition are 320 ± 70 and 11700 ± 410 cal mol?1, respectively. The present transformation enthalpy data represent a small but significant revision of those of Holm et al. Using the published phase equilibrium data, thermal expansivity, compressibility and heat capacity data, ΔS9750 for the quartz-coesite and ΔS2980 for the coesite-stishovite transition are ?1.2 ± 0.1 and ?1.0 ± 0.4 cal K?1 mol?1, respectively. These thermochemical data are used to calculate phase boundaries of the transitions. The calculated quartz-coesite transition boundary agrees well with the one determined experimentally by Bohlen and Boettcher. The calculated coesite-stishovite boundary is generally consistent with data by Yagi and Akimoto and by Suito. 相似文献
276.
Paul McMillan Bernard Piriou Alexandra Navrotsky 《Geochimica et cosmochimica acta》1982,46(11):2021-2037
Aluminosilicate glasses with compositions along the joins silica-calcium aluminate, silica sodium aluminate and silica-potassium aluminate have been prepared by conventional and solar melting techniques and studied by Raman spectroscopy. The Raman spectra of crystalline calcium aluminate, anorthite and silica polymorphs are discussed in relation to their crystal structures, and compared with the spectra of the corresponding glasses. The glass and crystal spectra are generally comparable, suggesting similar vibrational structures. These crystals have structures based on tetrahedral aluminosilicate frameworks, and a similar molecular structure is suggested for the glasses, although it is noted that the Raman spectra do not directly characterize the aluminate polyhedra. Within the three glass series, our interpretation of the unresolved high-frequency bands shows the appearance of discrete bands near 1120, 1000, 930 and 890 cm?1 as the silica content is decreased. This is compared with the behaviour of high-frequency bands in simple silicate systems, and used to suggest that the four bands in the aluminosilicate systems are due to stretching vibrations of silicate tetrahedra bound to one, two, three and four aluminium atoms. The spectra of calcium, sodium, potassium and lithium aluminosilicate glasses with similar silica contents are compared, and interpreted by the above model. This is used to construct a simple model for the effect of metal cation on aluminosilicate molecular groups in the glass structure, consistent with the results of calorimetric studies on similar systems. 相似文献