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J. P. Luongo H. Schonhorn 《Journal of polymer science. Part A, Polymer chemistry》1975,13(6):1363-1372
A variety of techniques were used to follow the thermal degradation of a poly(parabanic acid) (PPA-M). The kinetic data associated with the weight loss as a function of time at elevated temperatures indicates a random initiation process followed by depolymerization. Infrared and mass spectral techniques further confirmed the kinetic data by showing the presence of isocyanate and amide groups in addition to CO, CO2, and nitric oxide gases being evolved. Incipient gelation occurs simultaneously with the formation of the amide. A reverse Hoffman rearrangement mechanism has been proposed which appears to be consistent with the available experimental data. 相似文献
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Several new constitutive models are formulated for the planar interface of a soft body sliding on a rigid soil, describing stick-slip phenomena due to friction, and wear due to abrasion. Attention is focused on damage at the interface, by neglecting any interaction with damage of body and any propagation of damage inside the body. Models are formulated in the general framework of the Thermodynamics of the irreversible processes and account for suitable defined internal variables of phenomenological type, namely gap, isotropic friction hardening and wear. The main feature of the new presented models is that the formulation of the wear process at the interface is obtained in the contest of Damage Mechanics, and it is based on the formal analogy between abrasion of a soft body and ductile damage of an elastic-plastic material. By following this approach, a scalar wear field, an effective stress and appropriate state and dissipation potentials are defined, able to describe a tangential isotropic wear process due to stick-slip and to hardening mechanism. Both cases of linear and nonlinear friction hardening are formulated; moreover, wearable and no-wearable bodies are considered. Numerical results relevant to one-dimensional problems are illustrated for monotonic, forward-backward and cyclic displacement time-histories, showing evolution for stress, gap and wear. Results furnished by different models are compared and discussed. 相似文献
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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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Giovanna Luongo Gunnar Thorsén Conny Östman 《Analytical and bioanalytical chemistry》2014,406(12):2747-2756
A production process in which the use of various types of chemicals seems to be ubiquitous makes the textile industry a growing problem regarding both public health as well as the environment. Among several substances used at each stage, the present study focuses on the quinolines, a class of compounds involved in the manufacture of dyes, some of which are skin irritants and/or classified as probable human carcinogens. A method was developed for the determination of quinoline derivatives in textile materials comprising ultrasound-assisted solvent extraction, solid phase extraction cleanup, and final analysis by gas chromatography/mass spectrometry. Quinoline and ten quinoline derivatives were determined in 31 textile samples. The clothing samples, diverse in color, material, brand, country of manufacture, and price, and intended for a broad market, were purchased from different shops in Stockholm, Sweden. Quinoline, a possible human carcinogen, was found to be the most abundant compound present in almost all of the samples investigated, reaching a level of 1.9 mg in a single garment, and it was found that quinoline and its derivatives were mainly correlated to polyester material. This study points out the importance of screening textiles with nontarget analysis to investigate the presence of chemicals in an unbiased manner. Focus should be primarily on clothing worn close to the body. 相似文献
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The effects of a tuned added mass on the aeroelastic stability of a single degree of freedom bluff body exposed to a steady flow are investigated. The model captures the essential aspects of the behaviour of flexible structures equipped with Tuned Mass Dampers undergoing galloping oscillations. The system exhibits simple as well double Hopf bifurcations, of non-resonant and 1:1 resonant type. Postcritical behaviour of the system in the neighbourhood of the 1:1 resonant type bifurcation is investigated. Employing the Multiple Scale Method, a second order bifurcation equation in the complex amplitude of motion is obtained. Analytical solutions are used to describe the bifurcation scenario in the cases of both undercritical and supercritical aerodynamic behaviour of the bluff body. The effectiveness of the Tuned Mass Damper even in the postcritical range is proved. 相似文献
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Angelo Luongo 《Nonlinear dynamics》1996,10(4):317-331
Two perturbation methods for nonlinear autonomous discrete-time dynamical systems are presented. They generalize the classical Lindstedt-Poincaré and multiple scale perturbation methods that are valid for continuous-time systems. The Lindstedt-Poincaré method allows determination of the periodic or almost-periodic orbits of the nonlinear system (limit cycles), while the multiple scale method also permits analysis of the transient state and the stability of the limit cycles. An application to the discrete Van der Pol equation is also presented, for which the asymptotic solution is shown to be in excellent agreement with the exact (numerical) solution. It is demonstrated that, when the sampling step tends to zero the asymptotic transient and steady-state discrete-time solutions correctly tend to the asymptotic continuous-time solutions. 相似文献