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41.
Measurement of the degree of crystallinity of the polymer matrix in a composite is complicated by the presence of the reinforcing additive. This is particularly the case in APC-2 in which as much as 70% can be carbon fibre. A First Law procedure, developed for determining the degree of crystallinity of PEEK, which involves direct measurement of the enthalpy changes associated with melting, crystallization and heat capacity changes, has found to be an effective method for the determination of the crystallinity of the PEEK matrix. The procedure has been applied to carbon fibre and glass fibre PEEK composites. 相似文献
42.
Yasuhiro Morisaki Dr. Yuko Ouchi Kensuke Naka Dr. Yoshiki Chujo Prof. Dr. 《化学:亚洲杂志》2007,2(9):1166-1173
A series of optically active P‐chiral oligophosphines (S,R,R,S)‐ 2 , (S,R,S,S,R,S)‐ 3 , (S,R,S,R,R,S,R,S)‐ 4 , and (S,R,S,R,S,R,R,S,R,S,R,S)‐ 5 with four, six, eight, and 12 chiral phosphorus atoms, respectively, were successfully synthesized by a step‐by‐step oxidative‐coupling reaction from (S,S)‐ 1 . The corresponding optically inactive oligophosphines 1′ – 5′ were also prepared. Their properties were characterized by DSC, XRD, and optical‐rotation analyses. While optically active bisphosphine (S,S)‐ 1 and tetraphosphine (S,R,R,S)‐ 2 behaved as small molecules, octaphosphine (S,R,S,R,R,S,R,S)‐ 4 and dodecaphosphine (S,R,S,R,S,R,R,S,R,S,R,S)‐ 5 exhibited the features of a polymer. Furthermore, DSC and XRD analyses showed that hexaphosphine (S,R,S,S,R,S)‐ 3 is an intermediate between a small molecule and a polymer. Comparison of optically active oligophosphines 1 – 5 with the corresponding optically inactive oligophosphines 1′ – 5′ revealed that the optically active phosphines have higher crystallinity than the optically inactive counterparts. It is considered that the properties of oligophosphines depend on the enantiomeric purity as well as the oligomer chain length. 相似文献
43.
We report a thermal analysis study of the effect of molecular weight on the amorphous phase structure of poly(phenylene sulfide), PPS, crystallized at temperatures just above the glass transition temperature. Thermal properties of Fortron PPS, having viscosity average molecular weights of 30000 to 91000, were characterized using temperature modulated differential scanning calorimetry (MDSC). We find that while crystallinity varies little with molecular weight, the heat capacity increment at the glass transition decreases as molecular weight decreases. This leads to a smaller liquid-like amorphous phase, and a larger rigid amorphous fraction, in the lower molecular weight PPS. For all molecular weights, constrained fraction decreases as the scan rate decreases.This research is supported by the U. S. Army Research Office through contract DAAH04-96-1-0009. The authors thank Hoechst Celanese for providing different molecular weight Fortron samples and Dr. George Collins for providing sample information. The authors acknowledge the assistance of Elizabeth Oyebode and Leonardo Grimaldi with sample preparation and MDSC work. 相似文献
44.
It is shown that insertion in methacrylic polymers of bulky electron donor/acceptor side-groups with taper-shaped flourinated tails promotes a self-organization of the respective side-chain polymers due to the space demands of the bulky D/A side-groups, leading to a columnar hexagonal mesophase. The presence of an Lc-phase is evidenced by DSC and identified by X-ray analysis. The orientation in the respective copolymers and polymer blends is additionally improved by the CT-interaction between the D/A side-groups. An increased packing effect due to this CT-orientation effect is evidenced in DSC by an increase of the respective transition temperatures. CT-interaction is responsible as well for a preferential polymerization of monomeric D/A-complexes leading to copolymers of alternating structures and for a zip-like arrangement along the main chain of the A/D-complexes between the interacting side-groups in polymer blends. Formation of mesophases is even observed in CT-interacting blends between the Lc-D/A side-chain polymethacrylates and the respective amorphous D/A side-chain polysiloxanes.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
45.
Summary Low density polyethylene film is drawn at room temperature four times the original length and subjected to thermal annealing at 60, 80, and 100 °C keeping the film length constant. Long spacing measured by SAXS increased with increasing temperature of annealing; the increase of the long spacing is presumed to be due to the decrease of the number of micelles through relaxation during the annealing. Simultaneous measurement of the changes of the long spacing and the film length by stretching is carried out and stress-extension curves are obtained. The values of the initial moduli of the long spacingE
1 and the film lengthY are very near to each other. Elastic modulus of the crystal latticeE
c is known to be 235 GN/m2 and that of the amorphous regionE
a is found to be 0.15 GN/m2. When higher stress is applied than in the case of the initial modulus, the percentage of extension of film is much greater than that of the long spacing. The discrepancy is explained by the increase of the number of micelles through stress crystallization.Dedicated to Professor Dr. K. Ueberreiter on the occasion of his 70th birthday. 相似文献
46.
W. Swiatkowski 《Journal of Thermal Analysis and Calorimetry》1995,45(3):491-499
The transformation of the chains in the amorphous sulphur was investigated by calorimetric method at the temperature range from 288 to 303 K. The results satisfy the equationX=1?exp [?(kt)2] (X-transformation degree,t—time,k andz—constants). It was found that thez values increasevs. the temperature The activation energy is equal toE=21 kJ/mol with standard deviation 5 kJ/mol. The results were explained on the basis of the theory of the nucleation and the growth of the nuclei. 相似文献
47.
离子交换树脂负载Ni—B无定形合金催化剂的制备与性能 总被引:2,自引:0,他引:2
制备了一种新型离子交换树脂负载的Ni-B无定形合金催化剂.用3种树脂作为催化剂载体,即弱酸型阳离子树脂D152,强酸型阳离子树脂D72及强碱型阴离子树脂D261.用XPS、TEM和ICP等技术对催化剂进行了表征.结果表明,催化剂上镍与带有功能基的载体树脂之间有着很强的相互作用,但其强度与所带的功能基有关.3种催化剂Ni2p3/2的XPS谱图上,NiB/D152催化剂的氧化态峰最小,而NiB/D261的氧化态峰最大.异丙醇脱氢反应活性实验证实了这一结果. 相似文献
48.
Poly(L -lactide-co-β-malic acid) was obtained after the hydrogenolysis of the copolymer of L -lactide (L-LA) and β-benzyl malate (MA). 1H-NMR demonstrated that the composition of the copolymer was identical to the feeding dose. Thermal property study revealed the morphology of the copolymer could be changed from semi-crystalline to amorphous with increasing hydrophilic β-malic acid content. The copolymers with 8 and 13 mol% β-malic acid content possessed enough mechanical property for fabricating cell scaffold. Degradation result demonstrated that most of the hydrophilic β-malic acid units broke down from the copolymer within 1 week and the ester bond between L -lactide and β-malic acid hydrolyzed prior to the inner ester bond of poly(L -lactide) (PLLA). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
49.
A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (χ
c, χ
MA, χ
RA, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared
by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110°C, then briefly
heated to 136°C, then re-annealed at 110°C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow
the devitrification of the rigid amorphous fraction to be examined.
We observe a lower endotherm, termed the ‘annealing’ peak in the non-reversing heat flow after annealing at 110°C. By brief
heating above this lower endotherm and immediately quenching in LN2-cooled glass beads, the glass transition temperature and χ
RA decrease substantially, χ
MA increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification
of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110°C causes the glass transition and χ
RA to increase, and χ
MA to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal
reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid
amorphous fraction.
Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid
amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show
the homogeneous stack model is the correct one for Nylon-6. The cooperativity length (ξA) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of
some of the RAF leads to the broadening of the glass transition region and shift of T
g. 相似文献
50.
Shingo KomatsuYouichi Sakamoto Toshiyasu Suzuki Shizuo Tokito 《Journal of solid state chemistry》2002,168(2):470-473
Perfluoro-1,3,5-tris(p-quaterphenyl)benzene (PF-13Y) and perfluoro-1,3,5-tris(p-quinquephenyl)benzene (PF-16Y) have been synthesized and characterized. They showed higher glass transition temperatures compared with perfluoro-1,3,5-tris(p-terphenyl)benzene (PF-10Y). Organic light-emitting diodes were fabricated using these materials as the electron-transport layers. PF-13Y and -16Y are better electron transporters than PF-10Y. The electron mobilities of PF-10Y and Alq3 were measured by the time-of-flight technique. PF-10Y showed higher electron mobilities (10−4 cm2/V s) and weaker electric field dependence compared with Alq3. 相似文献