全文获取类型
收费全文 | 1222篇 |
免费 | 290篇 |
国内免费 | 277篇 |
专业分类
化学 | 1144篇 |
晶体学 | 55篇 |
力学 | 49篇 |
综合类 | 8篇 |
数学 | 6篇 |
物理学 | 527篇 |
出版年
2024年 | 1篇 |
2023年 | 2篇 |
2022年 | 14篇 |
2021年 | 22篇 |
2020年 | 46篇 |
2019年 | 27篇 |
2018年 | 21篇 |
2017年 | 28篇 |
2016年 | 46篇 |
2015年 | 45篇 |
2014年 | 58篇 |
2013年 | 137篇 |
2012年 | 93篇 |
2011年 | 74篇 |
2010年 | 70篇 |
2009年 | 64篇 |
2008年 | 90篇 |
2007年 | 100篇 |
2006年 | 94篇 |
2005年 | 108篇 |
2004年 | 79篇 |
2003年 | 85篇 |
2002年 | 89篇 |
2001年 | 41篇 |
2000年 | 71篇 |
1999年 | 52篇 |
1998年 | 47篇 |
1997年 | 29篇 |
1996年 | 32篇 |
1995年 | 27篇 |
1994年 | 10篇 |
1993年 | 13篇 |
1992年 | 25篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有1789条查询结果,搜索用时 31 毫秒
91.
采用水热法并经氨气保护热处理制备了双过渡金属氮化物Co3W3N/CNTs复合材料,得到了价格低廉且拥有良好氮电化学还原性能(NRR)的催化剂。通过调节已经预氧化的CNTs与过渡金属氮化物前驱体CoWO4的比例以及氨气热处理温度,实现了Co3W3N在CNTs表面的均匀负载。扫描电子显微镜(SEM)及透射电子显微镜(TEM)测试结果显示该电化学活性纳米微粒均匀地分散于CNTs表面,表明经预氧化的CNTs由于表面富集了较多的活性基团,有利于双过渡金属氮化物的分散生长。热处理后CNTs表面的Co3W3N微粒尺寸约为20 nm,相较于无载体的Co3W3N尺寸(100 nm)有明显减小。室温条件下,在N2饱和的0.01 mol·L^-1 H2SO4溶液中测试了该纳米复合材料在不同过电位下的NRR,该材料在-0.3 V(vs RHE)时的产氨率及法拉第效率分别可达12.73μg·h^-1·cm-2和13.59%,对比同样条件下,纯相Co3W3N的产氨率及法拉第效率仅为1.08μg·h^-1·cm^-2和1.76%。结果表明,通过水热反应和氨气保护热处理的Co3W3N/CNTs纳米复合材料具有良好的NRR性能。 相似文献
92.
通过简便的两步直接固相反应,即在室温下的固相自组装反应制备Ni席夫碱配合物前驱体,然后通过高温固相热解碳化和硒化反应,原位制备了N,Se共掺杂碳限域的NiSe纳米晶复合物。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)和热重分析(TGA)等表征技术分别对其物相、形貌结构、组分和含量等进行分析,并通过循环伏安、恒电流充放电和电化学阻抗谱等方法测试其电化学储钠性能。研究结果表明,复合物中NiSe粒子的平均尺寸为100 nm,被均匀限域在N,Se共掺杂的碳基体中;得益于该结构的优势,复合物作为钠离子电池负极材料时,在0.1 A·g~(-1)的电流密度下充放电循环100次后仍保持291 mAh·g~(-1)的可逆充电比容量,保持了首圈充电比容量的88%。同时,在5 A·g~(-1)的电流密度下,可逆充电比容量为197 mAh·g~(-1)。 相似文献
93.
Aleksei S. Pronin Spartak S. Yarovoy Yakov M. Gayfulin Aleksey A. Ryadun Konstantin A. Brylev Denis G. Samsonenko Ilia V. Eltsov Yuri V. Mironov 《Molecules (Basel, Switzerland)》2020,25(24)
Compounds based on new cyanide cluster anions [{Mo6I8}(CN)6]2–, trans-[{Mo6I8}(CN)4(MeO)2]2– and trans-[{W6I8}(CN)2(MeO)4]2− were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands. 相似文献
94.
95.
Mami Miyairi Tsuyoshi Taniguchi Tatsuya Nishimura Katsuhiro Maeda 《Angewandte Chemie (International ed. in English)》2020,59(35):14772-14780
An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism. 相似文献
96.
Ranjit Bag Sourav Kar Suvam Saha Suman Gomosta Beesam Raghavendra Thierry Roisnel Sundargopal Ghosh 《化学:亚洲杂志》2020,15(6):780-786
Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe2(CO)9] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl4] (Cp*=η5‐C5Me5) and [LiBH4?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ3‐BH)2H2{Cp*W(CO)2}2{Fe(CO)2}] ( 1 ) and bis‐borylene, [(μ3‐BH)2{Cp*W(CO)2}2{Fe(CO)3}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru3(CO)12]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ3‐BH)2{WCp*(CO)2}2{Ru(CO)3}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co2(CO)8] with nido‐[(RhCp*)2(B3H7)], which afforded triply‐bridging bis‐borylene species [(μ3‐BH)2(RhCp*)2Co2(CO)4(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; 1H, 11B, 13C NMR spectroscopy; IR spectroscopy and mass spectrometry. 相似文献
97.
梯度纳晶金属由于其微观组织的梯度分布,力学属性也呈现梯度变化,这使得其表现出不同于传统均匀材料的断裂行为.利用材料力学参数的梯度分布来表征梯度纳晶金属中晶粒尺寸的梯度变化,并编写ABAQUS和MATLAB脚本程序建立分层有限元模型.通过数值模拟计算了含有初始中心裂纹的梯度纳晶金属在受远端均匀拉应力作用下的裂尖J积分,分别研究了屈服应力梯度、裂纹角度和裂纹长度对金属材料断裂韧性的影响,并与传统粗晶进行了对比.结果表明梯度纳米结构的存在导致梯度纳晶金属内部的中心裂纹两端表现出不同的断裂韧性,小晶粒一侧裂尖的抗裂韧性优于大晶粒一侧裂尖,且屈服应力梯度绝对值越大,两者差距越大.梯度纳晶金属的断裂韧性受中心裂纹角度和长度变化的影响与传统粗晶金属基本一致,同时在晶粒尺寸梯度的作用下梯度纳晶的裂尖J积分略低于粗晶,即整体上拥有更好的抗裂韧性. 相似文献
98.
为研究高硬度钢板抗不同着角钨球的侵彻性能及破坏模式,通过弹道枪进行了?8 mm、?11 mm钨合金球形破片以0°、20°、40°着角撞击厚度为6 mm、8 mm的高硬度钢板试验,得到了极限贯穿速度v50;分析了钨球轴向径向变形及靶板失效模式与撞击速度的关系,发现高硬度钢板失效模式主要为压缩开坑破坏和沿厚度方向剪切破坏。采用有限元方法对试验进行了模拟,验证了数值模型及参数的合理性,并运用数值模拟方法研究了撞击着角对靶板吸能模式影响,结合试验数据,修正已有极限贯穿速度计算公式。结果表明:随侵彻着角增大,极限贯穿速度提高,且着角越大,极限贯穿速度增长越快;随着角增大,靶板吸能模式逐渐由压缩开坑向剪切冲塞过渡,且着角大于50°时,剪切冲塞耗能将超过压缩开坑耗能;修正后极限贯穿速度计算公式适用范围更广、精度更高,具有较好工程应用价值。 相似文献
99.
B. Goldstein 《辐射效应与固体损伤》2013,168(3-4):229-237
Single crystal silicon, both with and without oxygen, has been diffused with lithium to concentrations ~1017/cm2, irradiated with 1 to 1.5 MeV electrons, and the ensuing defects studies by EPR measurements. The presence of oxygen strongly affects the properties of these defects. Measurements have indicated the presence of two new defects which involve Li-one in O-containing material and one in O-free material. The defects are observed in their electron-filled state, and indicate a net electron spinof ½. The defect spectra disappear (with time) at room temperature, and can be explained by the formation of other Li-involved defects which lie deeper in the energy bandgap and are not visible by EPR. Electron irradiation at 40 °K followed by annealing at higher temperatures show that both EPR defects described above begin to form at about 200 °K and begin to decrease at about 275 °K-just as does the 250 °K reverse annealing observed generally for n-type Si. Based on these data, and the work of others, it is suggested that both defects form as a result of the motion of Si interstitials which produce a (Li-O-interstitial) complex in O-containing Si, and a (Li-interstitial) complex in O-free Si. 相似文献
100.
Nguyen Huy Dan Pham Thi ThanhNguyen Hai Yen Nguyen Thi Thanh Huyen Duong Dinh Thang Luu Tien Hung 《Journal of magnetism and magnetic materials》2012,324(7):1435-1439
We have observed magnetic anisotropy in bulk Nd55−xCoxFe30Al10B5 (x=10, 15 and 20) alloys prepared by copper mold suction casting method with a presence of external magnetic field (quenching field) μ0H=0.25 T. By changing direction of the measuring field from perpendicular to parallel one in comparison with that of the quenching field, coercive force of the alloys slightly decreases while remanent magnetization and squareness of hysteresis loop increase more clearly. It is also found that the higher Co-concentration in the alloys the larger magnetic anisotropy is induced. The structure analyses manifest nanocrystalline particles embedded in residual amorphous matrix of the alloys. The size of the particles is in range of 10-30 nm and their crystalline phases consist of Nd2(Fe,Co)14B, Nd3Co, Nd3Al, NdAl2 and Nd. 相似文献