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71.
F. Gugumus 《Polymer Degradation and Stability》2006,91(6):1346-1355
Most products formed on polyethylene oxidation result from hydroperoxide decomposition. The product yields can be calculated for various mechanisms of hydroperoxide decomposition. This work concerns the reaction of a hydroperoxide with an alcohol group thought to be dominant in the advanced stages of polyethylene processing in the high temperature range (170-200 °C). Besides hydrogen abstraction by caged alkoxy radicals already envisaged previously, the possibility of β-scission is taken into account. This additional reaction introduces significant complexity into the reaction schemes. This is especially so because additional caged radical pairs must be included into the schemes and the calculations. It becomes possible to calculate the yields of aldehyde and vinyl groups that do not result from hydroperoxide decomposition in the absence of β-scission. The yields of the main oxidation products such as alcohols and ketones are not much affected by taking into account β-scission. The yield of aldehydes is important in the whole temperature range and increases considerably if the temperature is raised from 170 to 200 °C. It becomes more important than the ketone yield. The vinyl groups are formed in amounts corresponding roughly to 10-15% of the trans-vinylene groups in the temperature range of 170-200 °C. 相似文献
72.
L. Hernandez M. Rudolph R. Lammertink J. Kornfield C. Zurita F. A. Gomez 《Chromatographia》2007,65(5-6):299-303
Vancomycin (Van) from Streptomyces orientalis has been derivatized with polyethylene glycol [PEG; PEG-550 (1), 750 (2), 1,100 (3), 2,000 (4), 5,000 (5), and 8,000 (6) g mol−1] at the N-terminus of the glycopeptide backbone and their binding to d-Ala-d-Ala terminus peptides assessed using affinity capillary electrophoresis (ACE). Utilizing ACE, a plug of Van-PEG and non-interacting
standards are injected and electrophoresed. Analysis of the change in the relative migration time ratio of the Van-PEG species,
relative to the non-interacting standards, as a function of the concentration of peptide, yields a value for the binding constant
(K
b). Values of K
b for N-acetyl-d-Ala-d-Ala, 7 to the Van-PEG derivatives are weaker than those for N
α,N
ε-diacetyl-Lys-d-Ala-d-Ala, 8 (for example, values of K
b for 7-1 and 8-1 are 1.8 and 47.7 × 103 M−1, respectively). These results demonstrate that derivatization of Van with PEG has little effect on the affinity of d-Ala-d-Ala peptide ligands to it. The findings further prove the versatility of ACE and its ability to estimate binding parameters
of ligands to antibiotics. 相似文献
73.
F. Gugumus 《Polymer Degradation and Stability》2007,92(1):125-142
The rate of acid formation at high temperature is constantly increasing but temperature independent. Two main mechanisms can account for this behavior in the advanced stages of polyethylene processing. The first mechanism is based on free radical induced oxidation of aldehyde pairs that are formed on acid-catalyzed decomposition of allylic hydroperoxides. The last will be formed essentially on mechanical stress-induced oxygen addition to trans-vinylene groups. Peroxidation of one of the aldehydes might yield an acyl-peroxy radical that is likely to abstract the labile hydrogen atom from the second aldehyde. The acyl radical formed in the reaction will abstract a hydroxyl group from the peracid formed in the same reaction. This yields an acid and an acyl-oxy radical that will give a primary alkyl radical on decarboxylation. The second mechanism involves oxidation of ketones and alcohols that accumulate in the oxidizing melt. Acid-catalyzed decomposition of the α-keto-hydroperoxides yields simultaneously an acid and an aldehyde. Formal kinetics based on each mechanism shows that they do not involve significant activation energy, as it is required by the experimental data. The dependency on the oxygen concentration deduced from the formal kinetics for the oxidation of aldehyde pairs is in agreement with the experiments. 相似文献
74.
《Microchemical Journal》2004,78(1):71-76
Thiamine (vitamin B1) was determined in human serum and urine by HPLC with fluorimetric detection of its oxidation product, thiochrome. The samples were injected directly into the chromatographic system without previous treatment or dilution. A column filled with an ultra-high molecular weight surface-modified polyethylene (PE) was able to separate matrix components from analyte and also to allow a good chromatographic resolution of thiamine. The interaction of thiamine, thiocrome and both matrices (serum and urine) with PE was studied off- and on-line to determine the optimal procedure for vitamin B1 determination. When carried off-line, matrix adsorption yield was 49 mg serum proteins/g polymer and components of 1000 μl urine/g polymer. In an on-line arrangement, the yield dropped to 10 mg/g and 150 μl/g, respectively. The matrix/analyte separation was carried out in an on-line procedure on a 50×4.6-mm, 25-μm PE column, using a water-sodium phosphate-methanol gradient elution. Part of the matrix was eluted within the first 2 min and thiamine after 3.8 min. The rest of the matrix retained on the column was eluted after thiamine at the last step of the gradient elution. Analysis time was 12 min. The within-day and day-to-day precision gave C.V. varying from 3.6% to 14.5% and recoveries from spiked samples were in the range of 84.8-98.8%. 相似文献
75.
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
76.
Thermo-oxidative stability of HDPE/EVA blends can be considerably increased by combination of a high-molecular weight phenolic antioxidant and zinc stearate. In this work, the post-irradiation thermal stability of HDPE/EVA blends has been studied. High-density polyethylene and its blends with ethylene-vinylacetate copolymer in both pure form and mixed with Irganox 1010 and zinc stearate were exposed to electron beam radiation at doses between 80 and 150 kGy, at room temperature, in air. In order to evaluate the thermal stability of the samples, post-irradiation heat treatments were done in both hot water bath at 95 °C and in an oven at 140 °C. The mechanical properties and changes in the chemical structure were determined during thermal aging in hot water and oven. The gel content was enhanced by increasing EVA concentration in all applied doses. The stabilized blends have lower gel content than the unstabilized samples. From the results of heat aging treatments it was observed that the thermal stability of the unstabilized blend samples was lower than HDPE. Thermal stability of the samples has been improved by incorporation of Irganox 1010 and zinc stearate. Formation of hydroxyl group was insignificant for stabilized samples during heat aging in both conditions. Also, the changes in the value of oxidation induction time (OIT) for the stabilized samples were negligible after prolonged immersion in hot water. 相似文献
77.
78.
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
79.
F. Gugumus 《Polymer Degradation and Stability》2006,91(12):3416-3428
Aldehydes and acids can be formed in numerous reactions in oxidizing polyethylene melts. Significant amounts of aldehydes result from β-scission of alkoxy radicals that are formed on bimolecular hydroperoxide decomposition. There are also large amounts of aldehydes expected from acid-catalyzed decomposition of allylic hydroperoxides as soon as enough acids have accumulated for efficient catalysis. There are difficulties in explaining the formation of aldehydes at a constant rate in sufficient amount for explaining the experimental data. There are much less difficulties with the constant rate of carboxylic acid formation. The α,γ-keto-hydroperoxides that are formed on chain propagation might account for the bulk of the acids formed at a constant rate.The foremost problems with the acids pertain to their formation at increasing rates in the initial as well as in the advanced stages. Formation and decomposition of α,β-di-hydroperoxides and α,γ-di-hydroperoxides is a possibility in this respect. Similarly, α,β-keto-hydroperoxides might be formed on peroxidation in the α-position to ketone groups in the advanced stages. There are considerable difficulties in elucidating the exact role of the aldehydes that are usually seen as the main precursors of the acids. Although there are many possibilities for transformation of aldehydes into acids, the free radical mechanisms envisaged usually have considerable disadvantages. These disadvantages result essentially from fast decarbonylation of acyl radicals and even faster decarboxylation of acyl-oxy radicals. Direct transformation of peracids into acids on reaction with double bonds is always a possibility. Moreover, in the low temperature range (150-160 °C) where hydroperoxides are accumulating, direct reaction of aldehydes with primary and/or secondary hydroperoxides will also yield acids. 相似文献
80.
Konstantin P Bryliakov Nina V Semikolenova Vladimir A Zakharov Martin Ystenes Evgenii P Talsi 《Journal of organometallic chemistry》2003,683(1):92-102
Using 1H- and 13C-NMR spectroscopies, cationic intermediates formed by activation of L2ZrCl2 with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L2 are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)2ZrCl2 (R=Me, 1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4, Me5, n-Bu, t-Bu), rac-ethanediyl(Ind)2ZrCl2, rac-Me2Si(Ind)2ZrCl2, rac-Me2Si(1-Ind-2-Me)2ZrCl2, rac-ethanediyl(1-Ind-4,5,6,7-H4)2ZrCl2, (Ind-2-Me)2ZrCl2, Me2C(Cp)(Flu)ZrCl2, Me2C(Cp-3-Me)(Flu)ZrCl2 and Me2Si(Flu)2ZrCl2. Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)2ZrCl2/MAO (R=H, Me, 1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4, Me5, n-Bu, t-Bu) and rac-Me2Si(Ind)2ZrCl2 were established. The catalysts (Cp-R)2ZrCl2/AlMe3/CPh3+B(C6F5)4− (R=Me, 1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4, n-Bu, t-Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)2ZrMe+←Me−-Al≡MAO (IV) with different [Me-MAO]− counteranions have been identified in the (Cp-R)2ZrCl2/MAO (R=n-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L2Zr(μ-Me)2AlMe2]+[Me-MAO]− (III) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr=200-1000) for the systems (Cp-R)2ZrCl2/MAO (R=H, Me, n-Bu, t-Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)2ZrCl2/MAO (R=1,2-Me2, 1,2,3-Me3, 1,2,4-Me3, Me4) and rac-Me2Si(Ind)2ZrCl2/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems. 相似文献