Some further observations on the systems cellulose/trifluoroacetic acid/CH2Cl2 and cellulose triacetate/TFA/CH2Cl2

There is little or no trifluoroacetylation of cellulose dissolved in TFA-CH₂Cl₂ admixtures. Both cellulose and cellulose triacetate (CTA)are slowly degraded in the solvent. Cellulose forms a mesophase as low as 4%(w/w)concentration, but CTA has a much higher critical concentration, 20% (w/w), in TFA-CH₂Cl₂. The cellulose behaves as a rigid rod in TFA-CH₂Cl₂ (70/30v/v) and its persistence length calculated using the lattice model approximates its chain length, presumably due to extensive interaction with the solvent. As expected, due to low polymer-solvent interactions, the persistence length of CTA in TFA-CH₂Cl₂ is only one-fourth the chain length.     

合成碳纳米管的镍基催化剂中镧的作用

CH4在Ni—Mg和Ni—La—Mg催化剂上裂筋制得两种碳纳米管，通过TKM,BKT，XRD，TG等方法对两种催化剂上所合成的碳纳米管进行检测比较，发现La的加入，使碳纳米管的管径变细，管壁变薄，碳纳米管管壁的石墨化程度更高，热稳定性更好，对碳纳米管的产量没有多大影响。     

Formation of molten metal films during metal-on-metal slip under extreme interfacial conditions

The present paper describes results of plate-impact pressure-shear friction experiments conducted to study time-resolved growth of molten metal films during dry metal-on-metal slip under extreme interfacial conditions. By employing tribo-pairs comprising hard tool-steel against relatively low melt-point metals such as 7075-T6 aluminum alloys, interfacial friction stress ranging from 100 to and slip speeds of approximately have been generated. These relatively high levels of friction stress combined with high slip-speeds generate conditions conducive for interfacial temperatures to approach the melting point of the lower melt point metal (Al alloy) comprising the tribo-pair.A Lagrangian finite element code is developed to understand the evolution of the thermo-mechanical fields and their relationship to the observed slip response. The code accounts for dynamic effects, heat conduction, contact with friction, and full thermo-mechanical coupling. At temperatures below the melting point the material is described as an isotropic thermally softening elastic-viscoplastic solid. For material elements with temperatures in excess of the melt point a purely Newtonian fluid constitutive model is employed.The results of the hybrid experimental-computational study provides new insights into the thermoelastic-plastic interactions during high speed metal-on-metal slip under extreme interfacial conditions. During the early part of frictional slip the coefficient of kinetic friction is observed to decrease with increasing slip velocity. During the later part transition in interfacial slip occurs from dry metal-on-metal sliding to the formation of molten Al films at the tribo-pair interface. Under these conditions the interfacial resistance approaches the shear strength of the molten aluminum alloy under normal pressures of approximately 1- and shear strain rates of . The results of the study indicate that under these extreme conditions molten aluminum films maintain a shearing resistance as high as .Scanning electron microscopy of the slip surfaces reveal molten aluminum to be smeared on the tribo-pair interface. Knoop hardness measurements in 7075-T6 Al alloy at various depths from the slip interface indicate that the hardness increases approximately linearly with depth and reaches a plateau at approximately from the surface.     

醋酸铅作为铅源合成CH3NH3PbBr3-xClx纳米晶体颗粒

Lead acetate, which is highly soluble in dimethylformamide, was used to synthesize mixed halide perovskite CH₃NH₃PbBr_3-xCl_x (MA = CH₃NH₃, 0 ≤ x ≤ 3) nanocrystals (NCs). This method provides an approach to address the low solubility of lead halides, especially lead chloride. Different Br/Cl ratios in MAPbBr_3-xCl_x lead to various optical properties. The photoluminescence emission peak can be tuned from 399 to 527 nm. Their full-widths at half-maxima (FWHM) are about 20 nm. MAPbBr_3-xCl_x NCs have an average diameter of ~(11 ± 3) nm and have uniform dispersion in toluene. The MAPbBr₃ NCs have a long average recombination lifetime (τ_ave = 97.4 ns) and a photoluminescence quantum yield (PLQY) of up to 73%.     

Ni掺杂对Ni/MgO体系中电荷分配影响

采用密度泛函理论(DFT)计算方法,研究了载体Ni掺杂对Ni/MgO催化剂的电子结构及其对CH_4/CO_2重整反应的影响。结果显示,随着载体Ni:Mg比的增加,CH_4解离吸附和CH_x氧化过程的反应能垒均会随之升高,CH也更容易产生热解C,从而导致催化剂的活性和稳定性的下降。通过分析重整过程的Hirshfeld电荷分配,发现金属载体之间电子转移的方向会随着载体中Ni含量的上升由载体向Ni金属转移变为由Ni金属向载体转移。当Ni金属富电子时,反应物活化时电子的转移主要发生在表层Ni原子与吸附物种之间,参与氧化的CH_x物种为CH_2;当Ni金属缺电子时,反应物活化时Ni簇的电子结构基本保持稳定,电子主要在载体表层的Ni原子与反应物之间转移,CH是主要参与氧化的CH_x物种。     

新型热作模具钢CH95的高温力学和抗磨性能研究

对比研究了CH95钢与H11钢的高温力学及抗磨性能,分析了2种模具钢的组成和微结构对其高温力学性能和抗磨性能的影响,采用透射电子显微镜观察分析了CH95钢试样中碳化物的形貌．结果表明：CH95钢与H11钢相比具有优异的高温力学性能;其优异的高温力学性能和抗磨性能归因于其特定的微观结构;CH95钢中细小且呈弥散分布的MC、M2C强化相的含量较高,使得其在高温下仍可保持优良的力学性能和抗磨性能;稀土可加速CH95钢表面致密氧化物层的形成,提高其强度、韧性、耐磨性和抗剥离能力;而经离子氮化处理后形成的细小且呈弥散分布的合金氮化物亦可起弥散强化作用,从而使得CH95钢在高温高载荷下的抗磨性能明显优于H11钢．     

13CH4分子v3振动带空气和氮气加宽系数温度依赖性研究

采用中红外波段连续可调谐二极管激光器和自行研制的低温吸收池, 测量了温度为296 K, 252 K, 213 K, 173 K时, 3.38 μm附近¹³CH₄分子的四条跃迁谱线的氮气和空气加宽光谱; 首次通过实验获得空气和氮气对¹³CH₄分子的碰撞加宽系数, 以及谱线加宽系数的温度依赖系数. 实验过程中, 利用Voigt线型对所测量的光谱进行拟合. 实验结果表明, 氮气和空气对¹³CH₄分子的碰撞诱导加宽系数随温度的降低而增大; 相同温度下, 氮气对¹³CH₄分子的碰撞加宽系数普遍大于空气加宽系数. 实验数据为地球和外星体大气遥感探测提供了依据.     

A DFT theoretical study of CH_4 dissociation on gold-alloyed Ni(111)surface

A density-functional theory(DFT)method has been conducted to systematically investigate the adsorption of CHx(x=0～4)as well as the dissociation of CHx(x=1～4)on(111)facets of gold-alloyed Ni surface.The results have been compared with those obtained on pure Ni(111)surface.It shows that the adsorption energies of CHx(x=1～3)are lower,and the reaction barriers of CH4 dissociation are higher in the first and the fourth steps on gold-alloyed Ni(111)compared with those on pure Ni(111).In particular,the rate-determining step for CH4 dissociation is considered as the first step of dehydrogenation on gold-alloyed Ni(111),while it is the fourth step of dehydrogenation on pure Ni(111).Furthermore,the activation barrier in rate-determining step is higher by 0.41 eV on gold-alloyed Ni(111)than that on pure Ni(111).From above results,it can be concluded that carbon is not easy to form on gold-alloyed Ni(111)compared with that on pure Ni(111).     

1-氟-1,1- 二氯乙烷与氟原子反应的理论研究

利用密度泛函理论研究了CH3CCl2F与F原子的反应机理.在MPW1K水平下计算了反应物、过渡态和产物的几何构型和频率,并进一步利用内禀反应坐标理论获得了反应的最小能量路径;在G3(MP2)水平下对所有驻点进行了单点能量校正.结果表明,CH3CCl2F与F原子的反应存在两个H迁移反应通道:CH2H′CCl 2F+F→C...