乙酸异丙酯的合成

以乙酸和异丙醇为原料,硫酸氢钠为催化剂,合成了乙酸异丙酯;考察了反应时间、酸醇比、催化剂用量、带水剂用量对酯化率的影响,确定了最佳酯化反应条件:反应时间60min,酸醇的物质的量的比1∶0.8,催化剂用量0.8g,带水剂用量8mL.在最佳反应条件下,酯化率最高可达84.3%.     

LD泵浦Nd:YAG 946 nm/1 064 nm双波长运转及腔内和频

用国产半导体激光二极管(LD)端面泵浦NdYAG晶体, 通过优化激光谐振腔反射膜系,调节1 064 nm谱线的线性损耗以达到与弱谱线946 nm的增益匹配,在室温下实现1 064 nm和946 nm双波长连续运转,并通过I类临界相位匹配LBO晶体腔内和频在国内首次实现500.8 nm青色激光连续输出.当泵浦注入功率为1.4W时和频青色激光最大输出达20 mW,光-光转换效率为1.4%,功率稳定性24 h内优于±3%.     

CVD金刚石薄膜探测器性能研究

通过实验测量和理论分析, 从载流子动力学角度研究了用于脉冲辐射探测的CVD金刚石薄膜探测器的适用结构、电荷收集效率和时间响应性能. 结果表明, CVD金刚石薄膜可以制成均匀型结构的探测器; 薄膜中的缺陷会降低探测器的电荷收集效率, 探测器的电荷收集效率随场强增大而增大直至饱和. 已研制的CVD金刚石探测器电荷收集时间可达719ps, 在2.5V/μm场强下达到饱和, 电荷收集效率 达60.5%; 晶格散射是影响探测器时间响应的主要因素, 选用大晶粒甚至单晶金刚石薄膜可以提高探测器时间响应.     

明胶接枝磺化缩聚物油井水泥分散剂的合成与性能

以动物明胶为原料,通过与甲醛、丙酮和焦亚硫酸钠发生磺化接枝反应,合成了一种新型的明胶接枝磺化缩聚物油井水泥分散剂.利用红外光谱分析测试技术证明了在明胶分子侧链上引入了磺化缩聚物.测试结果表明,当合成分散剂加入质量分数为1%时,水泥浆的流性指数、稠度系数和稠化时间比值(与未加水泥浆)分别为1.124、O.014和1.02,抗压强度比值均大于1.0,在18%NaCl、37%NaCl和2%CaCl,盐水水泥浆的流性指数分别为1.021、1.087和0.914、稠度系数分别为0.035、0.025和0.063.结果证明.明胶接枝磺化缩聚物的分散性能优异、耐盐性强并且无缓凝副作用,性能与常用的磺化醛酮缩聚物分散剂接近.是一种新型的预期可生物降解的油井水泥分散剂.     

Exact Radial Solution of the Non-relativistic Schr?dinger Equation for the Helium Atom with the Potential Harmonic Method

We proposed a simple potential harmonic(PH) scheme for calculating the non-relativistic radial correlation energies of atomic systems.The scheme was applied to the low-lying n1S(n=1,2) and n3S(n=2,3) states of the helium atom.The results exhibit a very stable convergence characterization in both the angular and radial directions with PH and generalized Laguerre functions(GLF) respectively,even though the method is non-variational one.The ninth significant figure of the non-relativistic radial energy(NRE) calculated for the ground state exactly agrees with that of the most accurate literature data from the modified configuration interaction method.The convergent NRE′s for the excited states 21S,23S and 33S with the similar accuracy were also obtained.     

具有性质cr+1=3,ar+1=3a+1或 4a的(a+1,3)型距离正则图

设г是直径为d且型为(a 1,3)的距离正则图,其中a≥2.用l(c,a,b)表示交叉阵列ι(г)中列(c,a,6)t的个数,记r=r(г)=l(c1,a1,b1),8=8(г)=l(Cr 1,ar 1,br 1)及t=t(г)=l(cr s 1,ar s 1,br s 1).那末,若Cr 1=3,ar 1=4a或3a 1,则d=r t 2.     

Proton Transfer Isomerization of Pyrazole in the Ground State:σν sπ Mechanism and Water Assisting Effect

The proton transfer isomerization of pyrazole and the water assisting effect by looping 1 to 4 water molecules on the singlet state potential energy surface have been investigated by using hybrid density functional theory method (B3PW91) with a 6-311++G** basis set. Two mechanisms were proposed to explain the mono- and multi-water assisting effects, respectively. The reactants and products of all groups have been characterized on their potential energy surfaces. For the isomerization of monomolecule pyrazole, the isomerization energy barrier is 46.4 kcal·mol-1. For the monohydration assisting mechanism, the reactant complex is connected to the product complex via two saddle points. The corresponding isomerization barriers are 46.7and 23.0 kcal(mol-1, respectively. As to the multihydration assisting mechanism, the isomerization barriers are 12.0, 10.9 and 13.14 kcal(mol-1 accordingly, when the number of water molecules is 2, 3 and 4, respectively. The multihydration assisting isomerization can occur in water-dominated environments, for example, in the organism, and thereby is crucial to energy transference. The deproton and dehydrogen energies of monomolecule pyrazole and various hydrated pyrazoles were calculated and then found much bigger than the isomerization barriers of their relative complexes, suggesting the impossibility of deprotonation or dehydrogenation. The isomerization of pyrazole is a proton-coupling-electron-migration process, but two different mechanisms are noticed, viz.σ- and π-type mechanisms. The π-bond of pyrazole participates in isomerization in the π-type mechanism, whereas only σelectron takes part in isomerization in the σ-type mechanism.     

利用激光诱导击穿光谱原位在线检测褐煤及煤烟

褐煤是我国现阶段的主要用煤,但因为其较低的煤化程度,使用时会产生污染环境的二氧化碳和黑灰,而且烟尘中含有的金属离子会危害人体健康,所以开展对褐煤烟尘的研究非常有意义。而激光诱导击穿光谱技术(LIBS)具有快速、多元素同时分析的特点,适合用于煤烟的原位在线探测。实验制备了含铅浓度不同的三种褐煤样本(O, H, L),其中O为原始无铅样本,利用LIBS对褐煤及煤烟进行原位在线探测。实验仪器主要由激光器,反射镜,聚焦透镜,触发装置,载物平台和分析系统组成。用高纯度铅块校准实验中的的波长漂移。分析了褐煤样本O, H, L的元素成分。发现褐煤O中含有C, Si, Fe, Mg, Al, Ca, Sr, Na等元素,同时检测到空气中的元素N,O,H_α和H_β等,且含铅褐煤光谱中多出了8条铅元素的谱线,最后给出了褐煤中主要元素的光谱鉴别表。然后使用447 nm的连续光点燃褐煤,将1 064 nm的脉冲光聚焦在煤烟上,对褐煤煤烟进行了原位在线检测。发现煤烟中含有Mg, Ca, Al, Sr, Pb等金属离子,说明了褐煤中的一些金属离子会随着煤烟排放到空气中并危害人体健康。经褐煤及煤烟的光谱比较,发现煤烟的信噪比更差,且所有元素的谱线强度都比在褐煤中弱很多,另外发现在烟尘中碳原子谱线的相对强度是所有元素中最高的（无明火）,这说明LIBS可以有效探测CO₂。分析了实验中的CN分子谱,给出了CN分子的具体波长,并利用LIFBASE软件拟合了CN分子的转动温度和振动温度,分别为6 780和7 520 K。最后对样本H和L两种煤烟中的铅浓度进行分析,选取参考线(Ca Ⅱ 363.846 nm)归一化之后比较了铅元素在363.956, 368.346和405.780 nm处的相对强度,发现这三条特征谱线的相对强度与自身实际所含的铅浓度呈很好的线性关系,验证了LIBS技术应用于煤烟中重金属元素半定量分析的可行性。     

Ni-Mg复合催化剂催化裂解CH_4制氢动力学研究

基于定温热重实验,建立了甲烷催化裂解反应动力学模型和催化剂表面积炭失活动力学模型。其中,甲烷催化裂解动力学模型将初始产氢速率视为催化剂未积炭条件下的动力学基础数据;催化剂表面积炭失活动力学则基于甲烷催化裂解速率的降低。实验使用Ni-Mg复合催化剂,分别在535、585、635℃,甲烷分压10~4、2×10~4、3×10~4Pa条件下展开甲烷催化裂解动力学特性研究。结果表明,甲烷催化裂解的反应级数为0.5,活化能为82 k J/mol;Ni-Mg复合催化剂反应失活级数为0.5,催化剂失活活化能为118 k J/mol。实验条件下均制得了多壁碳纳米管。     

高分子电致发光材料研究进展

综述了近几年来国内外关于高分子聚合物在电致发光材料领域的研究进展,重点介绍了聚苯撑乙烯、聚芴类、聚噻吩类聚合物及其衍生物的相关研究成果,并讨论了当前高分子电致发光材料存在的关键问题及应用前景.