首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1415篇
  免费   139篇
  国内免费   314篇
化学   677篇
晶体学   4篇
力学   597篇
综合类   35篇
数学   61篇
物理学   494篇
  2024年   4篇
  2023年   19篇
  2022年   52篇
  2021年   40篇
  2020年   60篇
  2019年   56篇
  2018年   33篇
  2017年   56篇
  2016年   59篇
  2015年   59篇
  2014年   63篇
  2013年   133篇
  2012年   79篇
  2011年   122篇
  2010年   86篇
  2009年   89篇
  2008年   96篇
  2007年   72篇
  2006年   103篇
  2005年   91篇
  2004年   64篇
  2003年   57篇
  2002年   57篇
  2001年   45篇
  2000年   36篇
  1999年   35篇
  1998年   39篇
  1997年   30篇
  1996年   33篇
  1995年   23篇
  1994年   17篇
  1993年   12篇
  1992年   12篇
  1991年   6篇
  1990年   9篇
  1989年   4篇
  1988年   2篇
  1987年   3篇
  1986年   2篇
  1985年   2篇
  1984年   2篇
  1983年   1篇
  1982年   4篇
  1978年   1篇
排序方式: 共有1868条查询结果,搜索用时 344 毫秒
1.
The inhibition efficiency of 2-Pyrrolidin-1-yl-1,3-thiazole-5-carboxylic acid (PTCA) against mild steel (MS) corrosion was investigated in acidic solution by using quantum chemical calculations based on Density Functional Theory (DFT) method and electrochemical measurements. The electrochemical impedance spectroscopy (EIS), potentiodynamic, potential zero charge (pzc) analysis and electrochemical noise (EN) measurements at various concentrations (from 0.1 to 10 mM) and immersion times were utilized in experimental part. The surface analysis was achieved scanning electron microscope (SEM) and contact angle measurements in the absence and presence of 10 mM PTCA. According to DFT results, PTCA exhibited 3.737 eV band gap and 8.130 Debye dipole moment which were a signal of potentially convenient corrosion inhibitor properties. PTCA has a remarkable corrosion inhibition capability to mild steel, which inhibited both anodic and cathodic corrosion rates, relying on it's physically adsorption on the metal solution interface and protection ability was increased with increasing PTCA concentration. The obtained adsorption equilibrium constant was 11.11 × 103 M-1 and calculated standard free energy of adsorption was ?33.03 kJ mol?1. The determined activation energy values were 55.58 kJ mol?1 and 96.86 kJ mol?1 in 0.5 M HCl in the absence and presence of 10 mM PTCA, respectively. PTCA demonstrated a strong inhibition efficiency of 98.3%, after 168 h immersion, according to the EIS results. As a consequently, we recommend that PTCA is a convenient inhibitor in 0.1 M HCl for mild steel protection against corrosion.  相似文献   
2.
This work is intended to examine the microbially influenced corrosion on galvanized steel (GS) caused by sulfate-reducing bacteria (SRB). The efficacy of Butea monosperma (palash) leaf extract to mitigate the corrosion caused by Desulfovibrio desulfuricans was investigated in modified Barr's medium. Weight loss and electrochemical analysis were performed to check the corrosion rate at regular time intervals. SEM images were performed to understand the level of deterioration of the metal surfaces. Image analysis of the unprotected sample showed the presence of pits. From the gravimetric study, the maximum inhibition efficiency (IE) of 98% was obtained with 500 ppm of Palash leaf extract for the fourth-week sample. With the addition of 500 ppm of palash extract, the sulfide concentration decreases to 0 ppm from 123 ppm. Outcomes of potentiodynamic polarization (PP) studies showed that the extract disturbs the cathodic reaction significantly and moves the corrosion potential to a more negative value and IE was about 71% from PP studies. FTIR and GC-MS analysis was performed to recognize the plausible chemical compounds present in Palash leaf powder. EIS results confirmed that the resistance to corrosion increases substantially with the addition of inhibitor. The mechanism for corrosion inhibition has been proposed based on the results obtained.  相似文献   
3.
The effectiveness of 1H?pyrazole?3,5?dicarboxylic acid 5?benzyl ester 3?phenyl ester (PCBPE) as a preventer for deterioration of IS 513 Gr. D steel in 1 M HCl medium is evaluated via weight loss, electrochemical impedance, and polarization techniques. Kinetic and thermodynamic parameters assessed the feasibility of the adsorption process at diverse temperatures. The inhibition action on mild steel has been enhanced with increasing PCBPE concentration. It is found from the polarization studies that PCBPE behaves as mixed type inhibitor in HCl medium. The adsorption process of PCBPE on mild steel surface from acid environment is favoured Langmuir adsorption isotherm. The shielding efficiency of PCBPE has been enhanced at elevated concentrations, and it has been diminished at amplified temperatures. The Atomic Force Microscope (AFM), Scanning Electron Microscope (SEM), and Energy Dispersive Spectrum (EDS) were used to establish a surface characterization of metal specimens. A quantum chemical analysis of electron density distributions in the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) demonstrated how the inhibitor undergoes adsorption on mild steel in 1 M HCl. All experimental findings substantiate the corrosion mitigation performance of PCBPE on mild steel in acidic environments.  相似文献   
4.
Natural-based corrosion inhibitors have gained great research interest thanks to their low cost and higher performance. In this work, the chemical composition of the methanolic extract of Ammi visnaga umbels (AVU) was evaluated by gas chromatography (GC) coupled with mass spectrometry (MS) and applied for corrosion inhibition of carbon steel (CS) in 1.0 mol/L HCl using chemical and electrochemical techniques along with scanning electron microscope (SEM) and theoretical calculations. A total of 46 compounds were identified, representing 89.89% of the overall chemical composition of AVU extract, including Edulisin III (72.88%), Binapacryl (4.32%), Khellin (1.97%), and Visnagin (1.65%). Chemical (Weight loss) and electrochemical (potentiodynamic polarization curves (PPC), and electrochemical impedance spectroscopy (EIS)) techniques revealed that investigated extract can be used as an effective corrosion inhibitor for carbon steel in 1.0 mol/L HCl solution. At a low dose of 700 ppm, the inhibitory action of AVU extract reached an inhibition efficiency of 84 percent. According to polarization tests, the investigated extract worked as a mixed inhibitor, protecting cathodic and anodic corrosion reactions. The EIS test showed that upon the addition of AVU extract to HCl solution, the polarization resistance increased while the double layer decreased. SEM images showed a protected CS surface in the inhibited solution. Quantum chemical calculations by Density Functional Theory (DFT) for the main components confirmed the major role of heteroatoms and aromatic rings as adsorption sites. Molecular dynamics (MD) simulation was used to study the adsorption configuration of the main components on the Fe(1 1 0) surface. Outcomes from this study further confirmed the significant advantage of using plant-based corrosion inhibitors for protecting metals and alloys.  相似文献   
5.
In this research, we investigated the synthesis of a novel water-soluble bis azo pyrazolin-5-one (ABP) which was synthesized efficiently via the regioselective reaction of hydrazine with coumarin hydrazone (CMH). Also, we evaluate their anti-corrosion and anti-bacterial behavior. The inhibition efficiency of ABP in an acidic medium (1.0 M HCl) was evaluated using various electrochemical and surface morphology measurements. The novel bis pyrazole-based azo dye ABP (16 × 10?6 M) demonstrated a higher protection capacity (93.3 %). Tafel curves revealed that ABP was a mixed-type inhibitor. The adsorption of ABP on the C-steel (CS) surface is proven by the alteration in (Rct and Cdl) impedance characteristics and obeyed the Langmuir isotherm model. SEM/EDX, AFM, and XPS surface examinations confirmed the enhancement of an adsorbed film protects the CS surface from acid corrosion at the appropriate dose. Furthermore, theoretical calculations using DFT and MC simulations were performed to identify the active sites on ABP molecules in charge of the adsorption and surface protection of the CS. The adsorption of bis pyrazole-based azo dye on the metal surface explained the protection mechanism. Moreover, the ABP screened for its antimicrobial activity against sulfate-reducing bacteria (SRB), and the calculated inhibition efficiency was 100 %. The current work presents significant results in manufacturing and producing novel water-soluble bis pyrazole-based azo dye derivative with high anti-corrosion and anti-microbial efficiency.  相似文献   
6.
胡文伟  王蕊  赵晖  张力 《爆炸与冲击》2022,42(2):023102-1-023102-11
为研究火灾高温与撞击联合作用下钢管混凝土柱的力学性能,基于ABAQUS建立了高温作用下考虑轴力影响的钢管混凝土柱侧向撞击有限元模型。首先,对高温与撞击联合作用下考虑轴力影响的钢管混凝土柱的破坏模式与受力全过程进行了分析,探讨了高温下钢管混凝土柱的抗撞性能与工作机理;其次,重点研究了受火时间、材料强度、含钢率以及撞击能量对抗撞性能的影响,并给出了相关设计建议。研究结果表明:高温与撞击联合作用下,钢管混凝土柱主要发生受弯破坏;受火15 min后,构件抗撞性能明显降低。轴压力对构件抗撞性能产生不利影响,轴压比从0增加到0.2,受火60 min构件抗撞性能下降了7.8%;混凝土强度对高温下钢管混凝土柱抗撞性能有显著影响,受火90 min后,混凝土强度由30 MPa增加到50 MPa,构件抗撞性能提高约85%;外钢管强度与含钢率对高温下抗撞性能影响不大。  相似文献   
7.
张健  徐豫新  刘铁磊  张鹏 《爆炸与冲击》2022,42(2):023302-1-023302-12
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   
8.
传统的正交异性钢桥面板疲劳损伤评估常采用确定性和可靠性分析方法,忽略了疲劳裂纹扩展的随机性影响,针对这一问题,提出钢桥面板细节疲劳随机扩展分析方法。本文以南溪长江大桥为工程背景,基于长期车辆荷载监测数据,建立了车辆荷载非齐次复合Poisson过程模型。建立钢桥面板有限元模型,采用瞬态分析方法将随机车辆荷载转化成细节疲劳应力,基于线弹性断裂力学理论推导U肋-顶板焊接细节疲劳裂纹扩展时变微分方程,实现宏观关系式疲劳应力幅次数-疲劳损伤至微观表达式应力时间序列-疲劳损伤转换,讨论了车载次序及超载对疲劳裂纹扩展的影响。研究结果表明,非齐次复合泊松过程模型能够较好描述随机车流运营状态,车辆荷载的次序对疲劳裂纹扩展速率的影响不可忽略,重车排序靠前时能够促使疲劳裂纹扩展增速,南溪长江大桥细节点的车辆超载迟滞效应修正系数取值0.804。  相似文献   
9.
在消费者低碳偏好和产品残值变化下,研究制造商的碳减排、生产及定价联合决策、以及对销售商的销售激励契约设计问题。不同于以往的研究假设残值不变,本文考虑残值依赖于清仓期库存以及碳减排问题。提出委托代理模型,求解模型并从理论上分析残值的变化和碳减排成本对双方决策和收益的影响。研究表明,残值变化率的增加只导致制造商的收益和生产量下降,不影响制造商的碳减排、定价、销售契约及零售商的决策和收益,但碳减排成本将导致制造商的收益和双方决策变量的下降。最后通过算例分析验证了结论,对供应链的运营实践有指导意义。  相似文献   
10.
通过电弧熔炼制备了Fe75B16.67Si8.33非晶合金,通过真空钎焊获得了钨/低活化钢接头。通过对钎焊接头表面形貌、微观组织、成分和力学性能的表征,发现在1250℃保温10min下所获得的钎焊接头界面无孔洞、裂纹等宏观缺陷,接头组织中生成了Fe固溶体、Fe3B和FeWB金属间化合物,拉伸强度高达450MPa。  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号