丙烯腈γ辐射聚合的NMR研究

用¹H NMR、¹³C NMR谱、自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）研究了丙烯腈在⁶⁰Co γ射线辐射聚合后的大分子结构变化与大分子链的运动. 结果表明随着辐射剂量增大，在单体形成聚合物的过程中，聚合物主链上出现了少量的-OH基团，继续增大辐射剂量， -OH部分被氧化. 对聚合物溶液的变温氢谱的研究表明，溶剂中的残余水与上述-OH形成氢键，且随着温度升高氢键被破坏，同时H₂O与-OH之间还存在着质子交换. 利用¹³C NMR谱对丙烯腈辐射聚合的产物进行了序列结构分析. 对T₁和T₂的研究表明，辐射剂量的增大并未影响到聚丙烯腈的链运动，证明了在丙烯腈的辐射聚合过程交联反应未发生.     

EACVD中用氢原子谱线测定电子平均能量

采用蒙特卡罗方法，对EACVD中氢原子的发射过程进行了模拟。给出了由氢原子谱线测定电子平均能量的方法，结果对EACVD生长金刚石薄膜过程中实时监测电子平均能量，进而可以有效地控制工艺条件，生长出高质量的金刚石薄膜具有重要意义。     

Au deposits on graphite: On the nature of high temperature desorption peaks in CO thermal desorption spectra

Due to the discovery of Au as a catalyst for low temperature CO oxidation, the adsorption of CO on Au surfaces has attracted a lot of attention recently. On stepped and rough single crystal surfaces as well as on deposited particles two characteristic desorption states above 100 K have been observed via TPD. We have studied Au deposits on graphite in order to elucidate the nature of these desorption peaks in more detail. For this purpose, Au was deposited at 100 K and 300 K on HOPG as a weakly interacting support. In analogy to other supports, we obtain two desorption states (∼140 K and ∼170 K) whose relative intensities depend strongly on the deposition temperature with the high temperature peak being much more pronounced for the 100 K deposits. After annealing to 600 K, both states drastically lose intensity. XP spectra, on the other hand, show virtually no decrease of the Au 4f intensity as would be expected for desorption or significant changes of the particle morphologies. We conclude that both desorption peaks are defect-related and connected with under-coordinated Au atoms that are lost for the most part upon annealing. These sites could be located at the perimeter of dendritic islands or on small, defect-rich particles in addition to larger particles not adsorbing CO at 100 K. Preliminary STM results are in favour of the second interpretation.     

Effect of hydrogen on interatomic bonds in austenitic steels

Mössbauer spectroscopy was used to investigate the influence of dissolved hydrogen on the interatomic bonds in austenitic steels. It was carried out to prove the decohesion mechanism of hydrogen embrittlement (HE). It is shown that hydrogen increases Debye temperature, i.e., the interatomic bonds in hydrogenated austenitic steel becomes stronger.     

Parameter determination of a thermal desorption model

A new method for the analysis of thermal desorption spectra is presented, based on the experimental peak maximum functions for temperatureT _m(β) and pressureP _m(β) and a rigorous mathematical treatment. The resonant heating rate β_r is determined, satisfyingT _m(β_r)=T _r, whereT _r is the resonant temperature defined byA exp(−E _d/(RT _r))=1. Desorption energyE _d and frequency factorA can be determined simultaneously with relatively high robustness towards statistical experimental errors as demonstrated by computer-simulated thermal desorption spectra.     

Influence of intrachain hydrogen bonding on the cyclization of a polystyrene chain

Cyclization of a polystyrene chain (M_n = 10,600; M_w/M_n = 1.09) both ends labeled with 4-(1-pyrenyl)butanoamide groups was studied in cyclohexane between 25 and 95°C. The amide groups (peptide bonds) at both ends can form an intrachain hydrogen bond between the amide hydrogen at one chain end and the carbonyl oxygen at the other. The presence of two sets of conformers, random coils, and chains cyclized through hydrogen bonding, complicates the data analysis. The pyrene excimer kinetics of this polymer is well described by a model composed of two monomers (hydrogen bonded and nonbonded chains) and one excimer, in equilibrium. The cyclization rate constant for hydrogen-bonded chains is larger than the one for nonhydrogen-bonded chains. The pyrene excimer binding energy (ca. 1.6 kcal/mol) is lower than the published value for nonhydrogen-bonded chains (～ 9 kcal/mol), suggesting that intrachain hydrogen bonding hinders the stabilization of the excimer. © 1994 John Wiley & Sons, Inc.     

基于遗传算法构建巴耳末公式

基于遗传算法构建了巴耳末公式．通过建立合适的拟合数学模型，用计算机对数学模型进行优化，使之尽可能反映氢原子实际谱线分布，并求出经验常量和拟合公式，最后分析了所得结果．