Li4SiO4陶瓷小球水解吸行为实验研究

采用程序升温热解吸（TPD/TDS）方法对Li4SiO4陶瓷小球的水解吸行为进行了实验研究。结果表明：水解吸过程中主要存在四个解吸峰;其中100 ℃附近的峰可解释为物理吸附水;150,250,400 ℃附近的峰可分别解释为以氢键、Li－OH和Si－OH配位键形式存在的化学吸附水。氚的释放与水的解吸几乎同步进行,且氚的释放形式主要为氚水（HTO）,据此推测,氚水可能存在三种释放机制：（1）－OT+H2O－OH+HTO;（2）－OH+－OHH2O,－OT+H2O－OH+HTO;（3）－OT+－OHHTO。     

LiAlO2陶瓷小球的堆外放氚行为

将LiAlO2陶瓷小球置于裂变反应堆中辐照,采用热解吸技术研究该类产氚材料的堆外放氚特性,考察了升温速率、载气组分、催化活性元素和提氚温度对氚释放行为的影响;采用电子自旋磁共振（ESR）实验技术研究了辐照缺陷的顺磁特征。结果表明:LiAlO2中氚的扩散速度慢,热解吸活化能高,氚释放主要分布在750~1000 K;表面氢同位素交换反应贡献大,释氚形态受载气条件的影响较大,当氦气中添加H2时,会增大HTO转化成HT的比例;中子辐照会在LiAlO2中诱生F+,O-和O2-等缺陷色心,其退火湮灭行为与氚释放过程存在一定关系。     

Eu2+掺杂P2O5-BaO-Na2O-K2O与Na2O-TeO2-ZnO系统玻璃的制备与光谱性质

用高温熔融法,把Eu₂O₃掺入到P₂O₅-BaO-Na₂O-K₂O与Na₂O-TeO₂-ZnO系统玻璃中。测定了玻璃的荧光光谱与激发光谱。结果表明,Eu离子在P₂O₅-BaO-Na₂O-K₂O玻璃中呈现出Eu³⁺态。然而在Na₂O-TeO₂-ZnO系统玻璃中,尽管在空气气氛下,大部分的Eu离子在玻璃中以二价的状态存在。从玻璃的结构及化学组分解释了产生Eu²⁺的原因。在磷酸盐玻璃配料中加入适量的硅粉(Si)作还原剂,能有效地把玻璃中的极大部分Eu³⁺还原成Eu²⁺,获得含Eu²⁺的优质透明磷酸盐玻璃。     

Li2B4O7晶体及其熔体结构的拉曼光谱研究

采用高温原位拉曼光谱技术,研究了Li₂B₄O₇从常温至1 373 K温度范围内的拉曼光谱。在升温过程中,晶体的拉曼光谱出现展宽和红移现象,且强度降低。晶体熔化时,由2个[BO₄]和2个[BO₃]组成的[B₄O₉]环状结构转变成(B₃O₆)3- 六元环和[BO₃]结构,[BO₄]结构减少直至消失。基于密度泛函理论,计算了Li₂B₄O₇晶体的拉曼光谱,对其振动模式进行了分析归属。利用量子化学从头计算法计算了由[B₃O₆-BO₃]为基础相互连接形成的x(Li₂B₄O₇)(x=2, 3, …, 9)的环状团簇模型的拉曼光谱,对Li₂B₄O₇熔体的结构进行了模拟分析。计算结果表明Li₂B₄O₇熔体的阴离子基元为三个(B₃O₆-BO₃)组成的大三元环超级结构。     

柔性ITO衬底电化学沉积制备Cu/Cu2O薄膜

研究了使用电化学沉积法于碱性条件下在柔性ITO衬底上制备Cu/Cu₂O薄膜的方法。循环伏安曲线表明Cu₂O与Cu的阴极峰分别位于-500 mV(vs Ag/AgCl)和-800 mV(vs Ag/AgCl)附近。利用循环伏安法考察了生长温度和电解液pH值等对Cu₂O与Cu阴极峰电位的影响,阴极峰随生长温度的升高以及pH值的降低而略向阳极移动,沉积电流也随之相应增大。与弱酸性条件相比,上述两个阴极峰随pH值升高而移动的程度明显减小,这可能与碱性条件下C₃H₆O电离程度增大以及C₃H₆O根作为配体的过量程度有关。通过X射线衍射光谱和扫描电子显微镜的表征证实,在所研究的生长温度区间和pH值内可利用电化学沉积法在柔性ITO衬底上制备Cu/Cu₂O纳米混晶薄膜。在相同的生长温度和pH条件下,电化学沉积电位对样品表面形貌和晶体性质具有较大影响。     

极端条件下6Li2O的热力学性能与电子结构

采用密度泛函理论与准谐振德拜模型研究了面心立方相的6Li2O在极端条件下的热力学性质与电子结构。结果表明: 6Li2O的热膨胀系数在任何温度下都随压强增加明显降低,但仅当压强较低(低于40 GPa)时,温度对6Li2O的热膨胀系数的影响才明显;O原子半径随压强增大而迅速降低,而随温度的变化并不明显;在低压条件下(低于40 GPa),带隙随温度的升高缓慢降低;而在高压条件下(高于40 GPa),温度对带隙宽度的影响几乎可以忽略;无论在什么温度条件下,带隙宽度均随压强的增大而迅速增加。     

xNa2O·yB2O3玻璃的融熔态结构

本文应用变温核磁共振技术研究了xNa₂O·yB₂O₃二元玻璃体系的融熔态结构。结果表明,R≤0.5的熔体中存在两种较为稳定的结构:在730—780℃温度区域形成了B原子间以双桥氧连接的网状结构;在880—920℃温度区域形成了B原子间含三桥氧的链状结构。当R>0.5时熔体中只存在第一种结构。 关键词：     

Ca2Li2BiV3O12∶Eu3+荧光粉的制备和发光性能

采用高温固相法成功合成了一种可用于白光LED的Ca₂Li₂BiV₃O₁₂∶Eu³⁺新型红色荧光粉,使用X射线衍射仪和荧光分光光度计对合成样品进行了表征,研究了合成温度和Eu³⁺含量对合成样品相组成和发光性能的影响。结果表明,采用高温固相法在650~700 ℃能合成纯度较高、结晶度好的Ca₂Li₂BiV₃O₁₂∶Eu³⁺荧光粉,合成样品激发带覆盖200~400 nm,发射光谱的线状发射峰可归属于Eu³⁺的⁵D₀→⁷F_J(J= 1, 2, 3,4)特征锐线发射,Eu³⁺摩尔分数为14%时荧光粉的发光强度最大。     

LiAlO_2陶瓷小球的堆外放氚行为

将LiAlO2陶瓷小球置于裂变反应堆中辐照,采用热解吸技术研究该类产氚材料的堆外放氚特性,考察了升温速率、载气组分、催化活性元素和提氚温度对氚释放行为的影响;采用电子自旋磁共振(ESR)实验技术研究了辐照缺陷的顺磁特征。结果表明:LiAlO2中氚的扩散速度慢,热解吸活化能高,氚释放主要分布在750~1000K;表面氢同位素交换反应贡献大,释氚形态受载气条件的影响较大,当氦气中添加H2时,会增大HTO转化成HT的比例;中子辐照会在LiAlO2中诱生F+,O-和O2-等缺陷色心,其退火湮灭行为与氚释放过程存在一定关系。     

Li_4SiO_4陶瓷小球水解吸行为实验研究

采用程序升温热解吸(TPD/TDS)方法对Li4SiO4陶瓷小球的水解吸行为进行了实验研究。结果表明:水解吸过程中主要存在四个解吸峰;其中100℃附近的峰可解释为物理吸附水;150,250,400℃附近的峰可分别解释为以氢键、Li-OH和Si-OH配位键形式存在的化学吸附水。氚的释放与水的解吸几乎同步进行,且氚的释放形式主要为氚水(HTO),据此推测,氚水可能存在三种释放机制:(1)-OT+H2O→-OH+HTO;(2)-OH+-OH→H2O,-OT+H2O→-OH+HTO;(3)-OT+-OH→HTO。     

Effect of Li2O doping on electrical properties of CoFe2O4

The solid–solid interactions between cobalt and ferric oxides to produce CoFe₂O₄ were followed up using XRD investigation. The effect of Li₂O-doping on the ferrite formation was also studied. The electrical and dielectric parameters of pure and doped mixed solids precalcined at 1273 K were measured using d.c and a.c instruments.The dopant concentration was varied between 0.5 and 6 mol% Li₂O. The results obtained revealed that Li₂O doping much enhanced the ferrite formation due to an increase in the mobility of the reacting species.

The addition of the smallest amount of Li₂O (0.5 mol%) resulted in measurable variations in the electrical constants (ρ, E_a, ′, ″ and tan δ). Resistivity increased upon increasing the dopant concentration up to 1.5 mol% exceeding the values measured for the undoped sample. Furthermore, the presence of 6 mol% Li₂O brought about a significant decrease of electrical resistivity. Also, the activation energy decreased with increasing the dopant concentration. The dielectric constant behaves according to ε=const. 1/ρ^1/2.

The Li₂O-doping modified the values of different dielectric constants, the change in these constants was found to be strongly dependent on the amount of Li₂O added.These results have been discussed in terms of the potentiality of Li₂O in increasing the mobility of the reacting species involved in the ferrite formation.     

Formation of Li2O in a chemically Li-intercalated V2O5 xerogel

We studied the electronic structure of a chemically Li-intercalated V₂O₅ xerogel. The technique used in the study was V 2p and O 1s X-ray absorption spectroscopy (XAS). The V ions in the as-prepared V₂O₅ xerogel are mostly in a pentavalent V⁵⁺ state. The spectra show that the V ions are partially reduced to V⁴⁺ and V³⁺ states upon Li intercalation. The results also show that low Li intercalation (x<1) affects mostly O 2p–V 3d mixed states, whereas for higher Li intercalation (x>1), this mechanism saturates and leads to Li₂O formation.     

Molecular dynamics study of the ternary compound Li3AlB2O6

A new compound with the stone cheinical composition as Li3AlB2O6 but with a different x-ray powder diffraction pattern as reported before was synthesized and studied experimentally by M. He, Chen X Let al （J. Solid State Chem. 163, 369 （2002））, but there lacks first principles study on the structure of it. Using conjugant gradient （CG） molecule dynamics （MD） simulation with a full relaxation of the atomic positions and of the shape and size of the cell, the structure of Li3AlB2O6 is studied from first principles. For the density functional, the local density approximation （LDA） and the generalized gradient approximation （GGA） forms are used respectively. Both the LDA and GGA results support the experimental structure of M. He et al. The result of MD simulation using GGA agrees with the experimental result much better. The energy bands are also studied, the band gap given by LDA and GGA are 5.65 eV, 5.34eV, respectively.     

Li修饰的C$lt;sub$gt;6$lt;/sub$gt;分子对H$lt;sub$gt;2$lt;/sub$gt;O的吸附研究

采用密度泛函理论中的广义梯度近似研究C₆Li吸附H₂O分子并将之进行分解的催化过程. 几何优化发现：Li原子最稳定的吸附位置是位于C 原子顶位上方. 研究表明,第一个H₂O 分子吸附在C₆Li上需要克服1.77 eV的能量势垒,然后分解为H和OH且与Li原子成键. 当吸附第二个H₂O分子时,第二个H₂O分子需要克服1.2 eV的能量势垒分解为H和OH,其中H与Li原子上的H原子结合成H₂,OH则替代Li 原子上的H结合在Li原子上. 因此C₆Li 可以作为催化剂将H₂O分子进行分解得到H₂. 分析可知：C₆Li主要是通过Li原子与H₂O之间形成的偶极矩作用来吸附H₂O 分子,与C₆₀Li₁₂ 的储氢机制类似. 研究结果可为储氢材料的制备提供一个新的思路. 关键词： 6')" href="#">C₆ Li 2O')" href="#">H₂O 密度泛函理论     

Optical absorption of isotopically enriched Li2B4O7 single crystals irradiated by thermal neutrons

Induced absorption spectra in the range 200–900 nm at 77 and 290 K for Li₂B₄O₇ single crystals, isotopically Li and B enriched are presented after irradiation of these crystals by thermal neutrons with fluence 1.8×10¹⁶ cm⁻². The dependence of induced absorption spectra on the isotope composition was revealed: for ⁶Li₂¹⁰B₄O₇ and ⁷Li₂¹⁰B₄O₇ crystals intensive band in the region of 280–294 nm was observed. Under substitution of ⁷Li isotope by ⁶Li in the lithium tetraborate lattice no changes in the absorption spectra were observed. The nuclear reaction ¹⁰B(n,)⁷Li is proposed to be the main mechanism of formation of the radiation defects.     

Fabrication of coaxial p-Cu2O/n-ZnO nanowire photodiodes

The authors report the deposition of Cu₂O onto vertically well aligned ZnO nanowires by DC sputtering. The average length, average diameter and density of these VLS-synthesized ZnO nanowires were 1 μm, 100 nm and 23 wires/μm², respectively. With proper sputtering parameters, the deposited Cu₂O could fill the gaps between the ZnO nanowires with good step coverage to form coaxial p-Cu₂O/n-ZnO nanowires with a rectifying current–voltage characteristic. Furthermore, the fabricated coaxial p-Cu₂O/n-ZnO nanowire photodiodes exhibit reasonably large photocurrent-to-dark-current contrast ratio and the fast responses.     

Electrical properties of pure and Li2O-doped CuO/Fe2O3 system precalcined at different temperatures

The electrical properties of pure and Li₂O-doped CuO/Fe₂O₃ solids were investigated. Pure and variously doped solids were subjected to thermal treatment at 1073–1273 K and the amount of dopant was varied between 0.84 to 3.36 mol%. The effect of precalcination temperature and amount of Li₂O added on the electrical conductivity σ, activation energy E_a and dielectric constant * were studied. The variation of ′ and ″ as a function of frequency for pure and variously doped solids precalcined at different temperatures was also investigated. The results obtained were discussed.     

Li2B4O7晶体生长及其二次谐波系数

用恰克拉斯基（Ｃｚｏｃｈｒａｌｓｋｉ）法特殊工艺生长出尺寸为Φ３０×３０ｍｍ的优质Ｌｉ２Ｂ４Ｏ７单晶，讨论了工艺参数对晶体宏观缺陷的影响。用Ｍａｋｅｒ条纹测量了晶体的二次谐波系数ｄ３１和ｄ３３，结果表明，Ｌｉ２Ｂ４Ｏ７的ｄ３３是石英晶体ｄ１１的三倍。