Recovery performance and characteristics in shape memory effects of aliphatic polyether urethane

The analysis on the recovery performance and characteristics in shape memory effects is helpful for the optimal design and engineering applications of shape memory polymers and their composites. To investigate the relationships among recovery performance, material parameters, and loading conditions, by taking aliphatic polyether urethane as an example, the researchers simulate the shape memory behaviors numerically using a three‐dimensional viscoelastic model. The material parameters for this model are taken from stress relaxation tests, rather than dynamic mechanical analysis tests. Both the unconstrained and the constrained recovery behaviors during strain‐controlled shape memory processes are analyzed. The results reveal that the unconstrained recovery occurs at the same temperature regardless of the applied strain values. Another interesting result is that the shape recovery temperature in unconstrained recovery situations increases and the maximum recovery stress under constrained recovery conditions decreases with the increase of heating rates. Copyright © 2013 John Wiley & Sons, Ltd.     

Fe2O3/Al2O3氧载体用于甲烷化学链燃烧：负载量与制备方法的影响

以不同方法制备了系列Fe₂O₃/Al₂O₃氧载体,采用XRD、H₂-TPR、CH₄-TPR、O₂-TPD和BET等分析技术对氧载体进行了表征。研究了不同Fe₂O₃负载量氧载体的甲烷化学链燃烧性能,考察了不同制备方法对Fe₂O₃/Al₂O₃氧载体结构、反应性和产物选择性的影响。结果表明,Fe₂O₃负载量对氧载体活性及产物中CO₂选择性的影响较大,负载量较低时氧载体活性较低且引起甲烷部分氧化产物CO含量增加。制备方法亦对氧载体与甲烷的反应活性有所影响,整体上共沉淀法制备的质量分数60％Fe₂O₃/Al₂O₃氧载体具有较高的氧化活性和化学链循环稳定性。其在反应温度850℃、反应时间15 min、30次循环后甲烷转化率及产物中CO₂选择性均未见明显降低。     

Mechanistic Insights into Copper‐Catalyzed Sonogashira–Hagihara‐Type Cross‐Coupling Reactions: Sub‐Mol % Catalyst Loadings and Ligand Effects

An efficient catalytic system for Sonogashira–Hagihara‐type reactions displaying ligand acceleration in the copper‐catalyzed formation of C(sp²)? C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub‐mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations.     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

Loading characteristics and chemical stability of headgroup‐functionalized poly(ethylene glycol)‐lipid ligand tethers on polypropylene capillary‐channeled polymer fibers

Polypropylene capillary‐channeled polymer fibers have been modified by adsorption of headgroup‐functionalized poly(ethylene glycol)‐lipids to generate a species‐specific stationary phase. In order to study ligand binding characteristics, a fluorescein‐labeled poly(ethylene glycol)‐lipid was used as a model system. Breakthrough curves and frontal analysis were employed to characterize the surface loading characteristics across a range of lipid concentrations and mobile phase flow rates. Efficient mass transfer and fluid transport yield a linear adsorption isotherm up to the maximum loading concentration of 3 mg/mL, at a linear velocity of 57.1 mm/s. Under these conditions, the dynamic binding capacity was found to be 1.52 mg/g of fiber support. Variation of the linear velocity from 8.6 to 57.1 mm/s showed only small changes in breakthrough volume. The maximum capacity of 1.8 mg/g is found under conditions of a load velocity of 34.2 mm/s and a concentration of 3 mg/mL lipid. Exposure of the lipid modified fibers to several challenge solvents reveals a chemically robust system, with only 50% acetonitrile and hexanes able to disrupt the lipid adsorption. The straightforward capillary‐channeled polymer fiber surface modification with headgroup‐functionalized lipids provides both a diverse yet practically robust ligand tethering system.     

高分散还原态Pt基催化剂的制备及其NO氧化的催化性能

Pt⁰被认为是NO氧化的活性物种,而催化剂的制备方法对活性物种的含量起着决定性作用。本文采用非惰性气氛保护的改性醇还原-浸渍法(MARI)合成了高分散高Pt⁰含量的1% (w, 质量分数) Pt/SiO₂-Al₂O₃催化剂(MA-Pt/SA)。X射线粉末衍射(XRD)、CO-漫反射傅里叶变换红外吸收光谱(CO-DRIFTS)和透射电镜(TEM)表征证实在550 ℃焙烧3 h后催化剂的Pt颗粒仅有3.8 nm。同时,X射线光电子能谱(XPS)和H₂-程序升温还原(H₂-TPR)结果表明催化剂具有高Pt⁰含量(60.3%)。模拟柴油车尾气气氛进行活性测试,并与传统浸渍法制备的1% (w) Pt/SiO₂-Al₂O₃催化剂(C-Pt/SA)对比,结果显示MA-Pt/SA具有优异的催化氧化性能,其NO最大转化率高达74%,比C-Pt/SA的NO转化率高了23%。经670 ℃高温老化15 h后,老化的MA-Pt/SA的NO转化率仍然高达69%。此外NO + O₂共吸附原位漫反射傅里叶变换红外吸收光谱(in situ DRIFTS of NO + O₂ co-adsorption)表明高的Pt分散度和高Pt⁰含量能够促进中间物种桥式硝酸盐的生成及分解,进而导致了优异的NO氧化活性。最后,利用同样方法将Pt的负载量降低至0.5% (w)制备催化剂,NO转化率仍达64%。这种制备方法能够获得低贵金属高性能的Pt基催化剂。     

基于氮掺杂活性炭催化氧化合成氮甲基氧化吗啉的研究

以三聚氰胺为氮源,商用活性炭为研究对象,通过“浸渍吸附+高温热处理”的方式制得系列氮掺杂活性炭,并用于催化氧化合成氮甲基氧化吗啉（NMMO）。采用N₂吸附/脱附、Raman、XPS等对氮掺杂活性炭的孔结构和表面性质进行了表征。结果表明：随着三聚氰胺负载量的增大,氮掺杂活性炭的表面碱性含氮官能团含量增大,进而体现出更好的催化氧化合成NMMO活性。最佳催化剂（ACO850-20N）在催化剂加量为0.02 wt%,反应温度70 ℃和反应时间4 h的工艺条件下,氮甲基吗啉的转化率和NMMO收率可达99.76%和94.31%。      

Robust nickel silicate catalysts with high Ni loading for CO2 methanation

CO₂ is the main component of greenhouse gases and also an important carbon source. The hydrogenation of CO₂ to methane using Ni-based catalysts can not only alleviate CO₂ emissions but also obtain useful fuels. However, Ni-based catalysts face one major problem of the sintering of Ni nanoparticles in the process of CO₂ methanation. Thus, this work has synthesized a series of efficient and robust nickel silicate catalysts (NiPS−X) with different nickel content derived from nickel phyllosilicate by the hydrothermal method. It was found that the Ni loading plays a critical role in the structure and catalytic performance of the NiPS−X catalysts. The catalytic performance gradually increases with the increase of Ni loading. In particular, the highly dispersed NiPS-1.6 catalyst with a high Ni loading of 34.3 wt% could obtain the CO₂ conversion greater than 80%, and the methane selectivity was close to 100% for 48 h at 330 °C and the GHSV of 40,000 mL g⁻¹ h⁻¹. The excellent catalytic property can be assigned to the high dispersion of Ni nanoparticles and the strong interaction between the active component and the carrier, which is derived from a unique layered silicate structure with lots of nickel phyllosilicate and a large number of Lewis acid sites.     

爆轰波对碰驱动平面锡飞层的动力学及动载行为特征研究

强冲击下的物质变形、破坏及诱发的轻重介质混合问题,是内爆压缩科学和工程应用领域的研究重点.本文针对爆轰波对碰条件下的复杂加载动力学过程及其动载破坏形态特征,开展数值模拟研究与极曲线理论分析.设计了爆轰波对碰驱动平面锡飞层的计算模型,获得了爆轰加载动力学过程及波系相互作用物理图像,分析了锡飞层对碰区自由表面速度历史的典型特征.给出了锡飞层中折射激波对碰发生马赫反射的临界条件,解读了三波结构的传播行为,阐明了对碰区内存在"一维正冲击"区域,一维区外存在单次斜冲击向两次斜冲击过渡的复杂加载动力学过程,提出了对碰区冲击动力学模型,揭示了影响对碰区动载行为特征的机理.数值模拟结果与极曲线理论分析结果相互印证,符合较好.本文的研究成果,将为深入理解和解读对碰区特殊的物质破坏及混合现象提供重要的理论支撑.     

An axial flow cyclone to remove nanoparticles at low pressure conditions

In this study, the axial flow cyclone used in Tsai et al. (2004) was further tested for the collection efficiency of both solid (NaCl) and liquid (OA, oleic acid) nanoparticles. The results showed that the smallest cutoff aerodynamic diameters achieved for OA and NaCl nanoparticles were 21.7 nm (cyclone inlet pressure: 4.3 Torr, flow rate: 0.351 slpm) and 21.2 nm (5.4 Torr, 0.454 slpm), respectively. The collection efficiencies for NaCl and OA particles were close to each other for the aerodynamic diameter ranging from 25 to 180 nm indicating there was almost no solid particle bounce in the cyclone. The 3-D numerical simulation was conducted to calculate the flow field in the cyclone and the flow was found to be nearly paraboloid. Numerical simulation of the particle collection efficiency based on the paraboloid flow assumption showed that the collection efficiency was in good agreement with the experimental data with less than 15% of error. A semi-empirical equation for predicting the cutoff aerodynamic diameter at different inlet pressures and flow rates was also obtained. The semi-empirical equation is able to predict the cutoff aerodynamic diameter accurately within 9% of error. From the empirical cutoff aerodynamic diameter, a semi-empirical square root of the cutoff Stokes number, , was calculated and found to be a constant value of 0.241. This value is useful to the design of the cyclone operating in vacuum to remove nanoparticles.