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61.
The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. For oversteps in temperature (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H2O, such as chlorite‐consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H2O, such as the chlorite‐free staurolite‐consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30 °C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite‐bearing precursor rock and ~70 °C overstepping was required for the growth of Al2SiO5 from a staurolite‐bearing, chlorite‐free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid‐catalysed ‘cascade effect’ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite‐consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.  相似文献   
62.
吐哈盆地低熟气评价的化学动力学方法及其应用   总被引:2,自引:0,他引:2  
针对目前尚无公认的有效方法评价低熟气生成量的难题,本文从低熟气的(低温)热成因机理出发,认为被广泛、成功应用于成熟的热成因天然气生成量评价的化学动力学理论仍然应该是评价低熟气生成量的有效方法。在此基础上,建立并标定了吐哈盆地代表性泥岩、煤岩干酪根成气的化学动力学模型,与可能部分成为低熟气先质的非烃、沥青质的化学动力学模型一起,构成了评价低熟气生成量的方法。标定结果表明,盆地内有机质成气的平均活化能低于其成油的活化能,而且成气过程中低活化能组分的含量也高于成油过程。这可能正是吐哈盆地的有机质在大量生油之前的低成熟阶段,能开始规模性地生成低熟气、从而导致工业性的低熟气聚集的内因所在。应用表明,吐哈盆地低熟气的总生成量可观,达到632.15×10^11 m^3,而且生气强度较高,最高达到100×10^8m^3/km^2以上。吐哈盆地低熟气资源量约为3.16×10^11~12.62×10^11 m^3。可见,盆地内低熟气具有可观的勘探潜力。本文所建立的方法应该可被推广应用到其他含低熟气盆地的低熟气的评价当中。  相似文献   
63.
爱沙尼亚干酪根催化降解生烃过程及动力学研究   总被引:2,自引:0,他引:2  
以爱沙尼亚油页岩干酪根为对象,利用热模拟实验方法和化工催化原理,考察了不同介质对干酪根热解生烃过程的影响,从热解生烃量、生烃组成特征及生烃动力学等方面进行了探讨。结果表明:膏岩对干酪根的生烃具有明显催化作用,碳酸盐岩对干酪根的生烃具有一定反催化作用,各种盐类对干酪根的生烃量影响较小。干酪根热解动力学研究表明,生烃动力学参数表观活化能E与视频率因子A两者之间不是独立变化的,而是具有一定的关系,即:E与lnA之间服从直线关系(R=0.99),这些认识对于深入探讨爱沙尼亚油页岩干酪根的化学结构、建立热解动力学模型具有一定的参考价值。  相似文献   
64.
碳酸氢钠(NaHCO_3)俗称小苏打,其产品质量取决于颗粒的大小,晶体的形貌和样品的纯度等诸多因素。本论文基于连续稳态MSMPR结晶器原理,研究了不同停留时间下,碳酸氢钠从碳酸钠溶液中冷却结晶过程动力学。利用实验数据建立了NaHCO_3的结晶动力学操作模型。实验和计算结果表明,随停留时间的增加,NaHCO_3过饱和度降低,晶体生长速率和成核速率均减小,相应的平均粒径增加,细颗粒含量减小;适当延长停留时间是制取高品质小苏打产品的有效途径。冷却结晶过程可有效增加小苏打产量,小苏打收率维持在55%左右。此外,一定Na_2CO_3存在下冷却结晶碳酸氢钠晶体形态由细长的针状变为规整的片状。  相似文献   
65.
东营凹陷民丰地区天然气生成机理与化学动力学研究   总被引:3,自引:0,他引:3  
民丰地区天然气存在源岩热解和原油裂解成因的争议。本文采用高压釜封闭体系对该区烃源岩和原油样品分别进行了热模拟实验,从烃类气体生成过程、气态烃与部分单体烃生成动力学特征讨论了二者的生气机理,认为原油裂解比源岩热解生气活化能高30~40 kJ/mol,原油比源岩生气需要更高的热力学条件。模拟实验证实,成熟阶段源岩热解气与原油裂解气相比,以环烷烃和芳烃相对含量低为特征,与民丰地区产出的天然气组成更接近,据此认为该区天然气主要为源岩热解成因。  相似文献   
66.
含钒石煤是我国一种新类型钒矿资源,钒的氧化是石煤提钒的基础。本文对钒的氧化动力学作了初步工作,通过试验数据处理结果表明,采用Ерофеев综合动力学公式:描述石煤中钒的氧化过程:2VO2固+1/2O2=Y2O5固简明可行,较为适宜。 钒氧化反应初期阶段以动力学方式进行:n1=1,属一级反应过程;继之,n2=0.2,反应受扩散制约。测定了由动力学过程转换为扩散过程所需的反应时间及其钒氧化率,计算了这两种过程的速率常数和表观活化能。  相似文献   
67.
Serial sectioning and imaging with a flatbed scanner yielded the three-dimensional size and spatial distribution of garnet porphyroblasts in two garnet schists and one staurolite-bearing schist from the Everett Formation, north-west Connecticut. The dominant garnet-producing reaction in all samples was chlorite+quartz=garnet+H2O. The appearance of staurolite, and additional garnet growth in the staurolite-bearing sample, was due to the reaction chloritoid=garnet+staurolite+chlorite. Statistical measures of garnet spatial distributions, using the pair correlation function (PCF), indicate that garnet crystals are weakly to strongly clustered at length scales between 2 and 10 mm. Such clustered nucleation may reflect minor bulk compositional variations. Covariance measures between garnet size and nearest-neighbour distance, using the mark covariance function (MCF), suggest a very weak correlation between crystal size and nearest-neighbour distance for length scales of 2 mm or less. These statistical data suggest that if diffusional gradients were present around growing garnet crystals, they did not influence nucleation and growth patterns at length scales greater than c. 2 mm. Compositional maps, through the garnet centres, show that the smaller crystals have lower Mn core compositions relative to larger crystals, consistent with progressive nucleation during pro-grade metamorphism. Radius-rate plots calculated from compositional X-ray maps show similar growth rates for garnet crystals of different size, consistent with an interface-controlled growth model for garnet. The presence of minor diffusional gradients around growing garnet cannot be entirely dismissed, but the lack of observable reaction rims, the clustered spatial distribution and the radius-rate data are most consistent with an interface-controlled garnet growth model.  相似文献   
68.
Moringa oleifera (MO), also known as drumstick tree, has gained worldwide attention among researchers and policy makers, for showing its remarkable potential in environmental management. Recently, MO seed or press cake (a by-product of oil extraction industry) powder has also emerged as an alternative and promising coagulant for environmental remediation. In this view, attempts have been made in this study to evaluate the efficacy of MO seed and press cake powder (MSP & PCP) for the treatment of municipal wastewater. Both MSP and PCP are characterized by using swelling ratio, scanning and transmission electron microscopy analysis. The effect of various operational parameters such as coagulation–flocculation pH (2–10), coagulant dosage (0.1–1 g L−1), and sedimentation time (0–180 min), etc., is investigated to understand the potential of MSP and PCP. At optimized operational conditions, sedimentation kinetics is also performed suggesting that the treatment process is being governed by the second-order kinetic model. The chemical and biological oxygen demand removals at optimized conditions are observed as follows: ≈38 and ≈73% for MSP and ≈47 and ≈85% for PCP. Overall, the results of the present study elucidated that PCP can be employed as a promising alternative of MSP for municipal wastewater with improved treatment efficiencies.  相似文献   
69.
塔里木盆地库车坳陷中生界烃源岩生烃动力学参数研究   总被引:6,自引:4,他引:2  
根据封闭体系黄金管热模拟实验结果,应用Kinetics专用软件,研究了塔里木盆地库车坳陷中生界不同类型烃源岩的生烃特征与动力学参数。库车坳陷侏罗系煤、碳质泥岩、泥岩及三叠系湖相泥岩具有各自的活化能分布和频率因子,揭示出其生烃行为的差异性。利用GOR-IsotopeKinetics软件,推导了库车坳陷侏罗系煤、泥岩和三叠系湖相泥岩3类烃源岩的碳同位素动力学参数。上述参数的获取,为盆地模拟、烃源岩评价、生烃量计算及资源量预测提供了重要的基础地球化学数据。   相似文献   
70.
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