含稀土元素的矿渣纳米晶玻璃陶瓷的光谱学研究

利用白云鄂博矿资源废弃物中有价元素以共伴生形成存在的特点制备了高性能的矿渣纳米晶玻璃陶瓷。本文采用电感耦合等离子发射光谱（ICP）、X射线衍射（XRD）、拉曼光谱（Raman）、扫描电子显微镜（SEM）等测试方法对样品的成分和结构进行了深入分析。ICP和XRD、SEM实验结果表明,我们制备的玻璃陶瓷是主晶相为透辉石,晶粒尺寸在45～100nm范围含稀土元素的纳米晶玻璃陶瓷,SEM面扫所显示的元素与ICP成分分析结果较为一致。Raman分析表明,其非晶相主要由具有不同非桥氧键的硅氧四面体结构单元构成的三维网络结构,进一步分析发现稀土微量元素对网络结构有十分明显的影响。我们把矿渣纳米晶玻璃陶瓷与相似成分的玻璃陶瓷的拉曼光谱对比,发现矿渣纳米晶玻璃陶瓷的拉曼谱带普遍比玻璃陶瓷对应的拉曼谱带波数低。相似成分的玻璃陶瓷与矿渣纳米晶玻璃陶瓷的成分差别主要是稀土元素等微量元素。本文的研究方法为研究玻璃陶瓷的成分与结构、性能之间的关系提供了一种研究思路。     

xCaSiO3·LiBO2固溶体中硅氧四面体微结构形态的拉曼光谱研究

本文测定了xCaSiO3*LiBO2(重量比,x=0, 0.25, 0.33, 0.50)系列的拉曼光谱,分析了硅氧四面体的微结构形态及其随SiO2 浓度的变化.结果表明,在所研究的浓度范围内,其微结构单元,即Qi ( i = 0～4) 均以孤立的硅氧四面体存在,且随SiO2 浓度的增加, Q2, Q4 的丰度有明显增加;此外,硅氧四面体的伸缩振动谱峰的积分强度总和与SiO2 浓度呈线性相关,为采用拉曼光谱直接分析矿物、炉渣、玻璃和土壤中的SiO2 提供了可能.     

GeO_2-PbO-ZnO红外玻璃的Raman光谱和结构

用Ｒａｍａｎ光谱研究了ＧｅＯ２ ＰｂＯ ＺｎＯ玻璃结构,结果表明,这种三元系统红外玻璃主要以［ＺｎＯ４］单元和含两个非桥氧的［ＧｅＯ４］四面体单元共同构成三维网络。网络中含两个非桥氧的［ＧｅＯ４］四面体数量随ＰｂＯ含量增加而增加,而低含量的ＺｎＯ则能提高网络中［ＧｅＯ４］四面体单元的聚合度。     

锂铝硅磷酸盐玻璃结构与紫外透过性能的关系

利用傅里叶红外光谱仪(FT-IR)、紫外分光光度计(UVPC)和魔角变换核磁共振(MAS-NMR)等方法对锂铝硅磷酸盐玻璃的局部结构和紫外透过性能进行了研究和表征。添加适量Li2O替换P2O5构成新的玻璃网络。通过核磁共振光谱分析表明,玻璃中的硅和磷分别处于四配位和三配位的配位态,而铝则有四配位、五配位和六配位三种不同的配位态。随着Li2O含量的增加,铝的平均配位数逐渐降低,这表明体系中的铝从网络修饰体变成了网络形成体。通过红外光谱分析表明,铝氧四面体中的铝和硅形成了Si-O-Al键,也使P-O-Al键逐渐增多。这些提高了玻璃的联通性,使玻璃结构更加完整。因此,玻璃在200nm处的透过率逐渐升高,这得益于Al-O-T(T=Si,P)键由非桥氧键变成桥氧键。     

Ag掺杂对高重复频率飞秒激光诱导Gd2O3-MoO3-B2O3玻璃析晶

将800nm高重复频率250 kHz的飞秒激光分别聚焦到掺Ag和没有掺Ag的Gd2O3-MoO3- B2O3玻璃表面,研究掺Ag对飞秒激光诱导析晶的影响。对激光辐照的区域显微拉曼分析发现对于没掺Ag玻璃,诱导玻璃析晶需要的激光功率和辐照时间比掺了Ag的玻璃要大要长,这说明Ag的掺入促进了玻璃的析晶。其机理可能为飞秒激光的多光子吸收效应,导致玻璃基质中桥氧键断裂,产生非桥氧空穴和自由电子,玻璃中的Ag离子捕获电离出来的电子被还原成Ag原子,Ag原子在热动力的驱动下移动聚集形成银纳米颗粒,形成的银纳米团簇作为核促进了钼酸盐玻璃的析晶。     

Ag掺杂对高重复频率飞秒激光诱导Gd_2O_3-MoO_3-B_2O_3玻璃析晶的影响

将800nm高重复频率250kHz的飞秒激光分别聚焦到掺Ag和没有掺Ag的Gd2O3-MoO3-B2O3玻璃表面,研究掺Ag对飞秒激光诱导析晶的影响.对激光辐照的区域显微拉曼分析发现对于没掺Ag玻璃,诱导玻璃析晶需要的激光功率和辐照时间比掺了Ag的玻璃要大要长,这说明Ag的掺入促进了玻璃的析晶.其机理可能为飞秒激光的多光子吸收效应,导致玻璃基质中桥氧键断裂,产生非桥氧空穴和自由电子,玻璃中的Ag离子捕获电离出来的电子被还原成Ag原子,Ag原子在热动力的驱动下移动聚集形成银纳米颗粒,形成的银纳米团簇作为核促进了钼酸盐玻璃的析晶.     

Na_2O-Al_2O_3二元系团簇微结构与特征拉曼振动波数的相关性

针对含铝四配位Na_2O-Al_2O_3二元系熔体团簇结构,构建了九种团簇模型,并对其拉曼振动波数和散射活性进行了密度泛函理论(DFT)计算。微结构的命名参考了硅酸盐体系的命名规则~([1]),其中Al-O四面体简记为Qi(i为桥氧数)。分析表明,Na_2O-Al_2O_3二元系团簇中Q_2和Q_3微结构单元中Al-O_(nb)(non-bridging oxygen,即非桥氧)键对称伸缩振动波数随其键长呈现线性相关性。Q_2和Q_3微结构中铝氧键长随着参与成环铝氧四面体的数目的增加而增加,这些相关性有助于Na_2O-Al_2O_3二元系熔体中铝氧四面体连接方式及团簇的诊断和鉴别。     

用XPS研究高灰熔融温度煤灰的矿物结构转化

高灰熔点X煤通过添加钙镁复配(W_CaO/W_MgO=1)助熔剂降低灰熔点,在模拟煤气化过程中制备灰渣,用X射线光电子能谱(XPS)分析不同温度点灰渣中O,Si,Al,Ca,Mg的存在形态及演化过程。认为钙镁复配助熔剂降低灰熔点主要是作用在硅、铝、氧结构变化上,表现为铝元素结构中铝氧配位方式的变化,即四配位的铝氧四面体[AlO₄]和六配位的铝氧八面体[AlO₆]随温度的变化而变化;硅元素结构中SiO₂链的破坏,Ca2+和Mg2+加入会破坏SiO₂链,使得桥氧硅变为非桥氧硅;以及氧元素结构中桥氧键断裂和非桥氧键形成。结合Factsage热力学分析软件,分析了添加钙镁复配助熔剂后,煤灰渣的高温相平衡组成,从矿物的结构变化研究助熔剂的助熔机理。结果表明,添加钙镁复配助熔剂后,Ca2+和Mg2+易与硅氧和铝氧四面体以及铝氧八面体中非桥氧键结合,生成低熔点的长石类矿物和镁质矿物,从而降低煤灰熔融温度。     

钠钛硅酸盐精细结构及其拉曼活性分子振动的量子化学从头计算研究

本文选取了Na_2O-TiO_2-SiO_2体系不同成分的团簇模型,采用量子化学从头计算方法计算其拉曼振动频率和相对散射活性。本文分析了钛硅酸盐中硅氧四面体([SiO_4])的局域环境变化对特征拉曼振动频率的影响,对硅氧四面体应力指数进行了拓展与修正,研究表明钠钛硅酸盐拉曼光谱高波数区硅氧四面体非桥氧对称伸缩振动频率随相应的硅氧四面体应力指数的增加而增加,并表现出良好的线性相关性。采用拉曼光谱和~(29)Si NMR对Na_2TiSiO_5玻璃进行解谱、定量分析和比较,并认为869 cm~(-1)处的谱峰归属为Q_(1(Si))中非桥氧的对称伸缩振动。     

NaF-AlF3二元系铝氟四面体团簇结构的拉曼光谱表征与量子化学从头计算

本文构建了一系列NaF-AlF3二元系铝氟四面体团簇结构模型, 应用量子化学从头计算方法, 采用Restricted Hatree-Fock(RHF)自洽场方法和6-31G(d)基组对结构进行优化, 并用相同的方法和基组进行分子振动模式的模拟计算。考虑相邻铝氟四面体的影响, 引入四面体应力指数(SIT)的概念分析和讨论该二元系高频区非桥氟对称伸缩振动及中频区桥氟对称弯曲振动模式。研究表明, 高频区铝氟四面体非桥氟对称伸缩振动频率与其铝氟四面体的种类(Qi)密切相关, 且铝氟四面体非桥氟对称伸缩振动频率的值随SIT值的增大而增大, 呈现较好的线性关系。同时, NaF-AlF3二元系团簇结构的中频区桥氟对称弯曲振动频率主要受桥氟角度的影响。并采用高温拉曼仪测定了分子比为NaF:AlF3 =1∶2体系的升温拉曼光谱, 随着温度的升高NaF:AlF3 =1∶2体系的主峰逐渐向低频移动, 观察到Q0、Q1、Q2峰位的变化。     

Orbital ordering in Mott-insulators La2O3Fe2Se2 and La2O3Co2Se2

The electronic structure and magnetic properties of new layered oxyselenide compounds La₂O₃Fe₂Se₂ and La₂O₃Co₂Se₂ are studied by first-principles calculations. Our results indicate that both compounds are Mott-insulators with orbital ordering. The ground states of both compounds are the checkerboard antiferromagnetic states, which are different from the iron pnictide superconductors, although their structures are similar to those of the Fe-As-based superconductors.     

Magnetic properties of NdCo2Ge2, ErCo2Ge2 and PrFe2Ge2 compounds

Magnetometric and neutron diffraction studies of polycrystalline NdCo₂GE₂, ErCo₂Ge₂ and PrFe₂Ge₂ compounds were carried out in the temperature range between 4.2 and 300 K. All samples are antiferromagnetic with Néel temperature 26.5, ～ 4.2 and 13 K, respectively. The RECo₂Ge₂ compounds have collinear antiferromagnetic order of +?+? type. For PrFe₂Ge₂ a sinusoidal magnetic structure is observed. Magnetic moment is localized on RE atoms only and is equal to that of RE³⁺ free ion value. In ErCo₂Ge₂ the magnetic moment of Er atoms is perpendicular to the c-axis, whereas for remaining compounds it is parallel to the c-axis.     

Structural study of the Lu2Si2O7-Sc2Si2O7 system

Different compositions in the Lu₂Si₂O₇-Sc₂Si₂O₇ system have been synthesized following the ceramic method. All XRD patterns are compatible with the thortveitite structure (β-RE₂Si₂O₇ polymorph). Unit cell parameters change linearly with composition, which indicates a complete solid solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇. ²⁹Si MAS NMR spectra show a decrease of the ²⁹Si chemical shift with increasing Sc content. A correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Sc₂Si₂O₇ and the results compare favourably with the values obtained experimentally. The FWHM values of the ²⁹Si MAS NMR curves indicate a random distribution of Lu and Sc in the structure of the intermediate members. Finally, the IR study of the system confirms the solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇, showing the splitting of several modes in the intermediate members and a linear shift of the frequency on going from one end-member to the other.     

Incommensurate modulations in Ba2TiSi2O8, Sr2TiSi2O8, and Ba2TiGe2O8

Incommensurate modulations in Ba₂TiSi₂O₈, Sr₂TiSi₂O₈, and Ba₂TiGe₂O₈ are compared based on their corresponding electron diffraction patterns. The dependence of the modulations on chemical composition provides a suitable model system for the investigation of incommensurations in framework structures using high-resolution transmission electron microscopy (HRTEM). A widening of quantitative HRTEM utilising the concept of rigid units is proposed allowing for a determination of atomistic displacements responsible for the formation of incommensurately modulated structures.     

Neutron diffraction study of magnetic ordering in PrCu2Si2, PrCu2Ge2, PrFe2Ge2 and NdFe2Ge2

A neutron diffraction study of polycrystalline PrCu₂Si₂ [1], PrCu₂Ge₂ [2], PrFe₂Ge₂ [3] and NdFe₂Ge₂ [4] intermetallics carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic order below T_N = 19 ± 1 K [1], T_N = 16 ± 1 K [2], T_N = 9 ± 1 K [3] and 13 ± 1 K [4]. Magnetic moment, parallel to the c-axis is localized on RE ions only. The magnetic structure of these compounds consists of ferromagnetic layers perpendicular to the c-axis coupled antiferromagnetically with sequence +-+- for PrCu₂Si₂ and PrCu₂Ge₂ and +--+ for PrFe₂Ge₂ and NdFe₂Ge₂. The RE moments amount close to the free ion values for Fe containing compounds but are smaller in those containing Cu suggesting a fairly strong influence of crystal field.     

Emission analysis of Dy and Pr:Bi2O3-ZnF2-B2O3-Li2O-Na2O glasses

In this paper, we present the spectral results of Dy³⁺ and Pr³⁺ (1.0 mol%) ions doped Bi₂O₃-ZnF₂-B₂O₃-Li₂O-Na₂O glasses. Measurements of X-ray diffraction (XRD), differential scanning calorimetry (DSC) profiles of these rare-earth ions doped glasses have been carried out. From the DSC thermograms, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The direct and indirect optical band gaps have been calculated based on the glasses UV absorption spectra. The emission spectrum of Dy³⁺:glass has shown two emission transitions ⁴F_7/2→⁶H_15/2 (482 nm) and ⁴F_7/2→⁶H_13/2 (576 nm) with an excitation at 390 nm wavelength and Pr³⁺:glass has shown a strong emission transition ¹D₂→³H₄ (610 nm) with an excitation at 445 nm. Upon exposure to UV radiation, Dy³⁺ and Pr³⁺ glasses have shown bright yellow and reddish colors, respectively, from their surfaces.     

EPR and magnetic properties of MgO-CaO-SiO2-P2O5-CaF2-Fe2O3 glass-ceramics

Glass-ceramics have been derived from 4.5MgO(45−x)CaO34SiO₂16P₂O₅0.5CaF₂xFe₂O₃ (x=5, 10, 15, 20 wt%) glasses by heat treatment. Room temperature electron paramagnetic resonance (EPR) spectra and temperature-dependent magnetic susceptibility (χ) of the glass-ceramics have been obtained. The EPR absorption line centered at g≈4.3 disappeared at higher concentrations of iron oxide. The intensity and line width of the EPR absorption line centered at g≈2.1 increased as the iron oxide concentration was increased. Temperature-dependent magnetization of samples with low iron oxide content revealed ferrimagnetic as well as paramagnetic contributions. Information about the structural changes involving iron ions, their valence state and the type of magnetic interactions between the Fe ions as a function of composition was obtained using EPR and χ studies.     

In vitro evaluation of bioactivity of CaO-SiO2-P2O5-Na2O-Fe2O3 glasses

Glasses with compositions 41CaO(52 − x)SiO₂4P₂O₅·xFe₂O₃3Na₂O (2 ≤ x ≤ 10 mol.%) were prepared by melt quenching method. Bioactivity of the different glass compositions was studied in vitro by treating them with simulated body fluid (SBF). The glasses treated for various time periods in SBF were evaluated by examining apatite formation on their surface using grazing incidence X-ray diffraction, Fourier transform infrared reflection spectroscopy, scanning electron microscopy and energy dispersive spectroscopy techniques. Increase in bioactivity with increasing iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of immersion time in SBF and glass composition.     

Electrical and electrochemical properties of glass-ceramic electrolytes in the systems Li2S-P2S5-P2S3 and Li2S-P2S5-P2O5

Electrical and electrochemical properties of the 70Li₂S·(30 − x)P₂S₅·xP₂S₃ and the 70Li₂S·(30 − x)P₂S₅·xP₂O₅ (mol%) glass-ceramics prepared by the mechanical milling technique were investigated. Glass-ceramics with 1 mol% P₂S₃ and 3 mol% P₂O₅ showed the highest conductivity of 5.4 × 10^− 3 S cm^− 1 and 4.6 × 10^− 3 S cm^− 1, respectively. Moreover, these glass-ceramics showed higher electrochemical stability than the 70Li₂S·30P₂S₅ (mol%) glass-ceramic. From the XRD patterns of the obtained glass-ceramics, trivalent phosphorus and oxygen were incorporated into the Li₇P₃S₁₁ crystal. We therefore presume that the Li₇P₃S₁₁ analogous crystals, which were formed by incorporating trivalent phosphorus and oxygen into the Li₇P₃S₁₁ crystal, improve the electrical and electrochemical properties of the glass-ceramics. An all-solid-state cell using the 70Li₂S·29P₂S₅·1P₂S₃ (mol%) glass-ceramic as solid electrolyte operated under the high current density of 12.7 mA cm^− 2 at the high temperature of 100 °C. The cell showed an excellent cyclability of over 700 cycles without capacity loss.     

Line emission of SrBe2Si2O7:Eu2+ and BaBe2Si2O7:Eu2+

The compounds SrBe₂Si₂O₇ and BaBe₂Si₂O₇ both have the barylite structure. With 254 nm excitation, the Eu²⁺-activated compounds give UV emission peaking at 360 nm (Sr) and at 375 nm (Ba). Maximum quantum efficiencies of 40% (Sr) and 65% (Ba) were measured. The emission consists of a 5d-4f band emission as well as 4f-4f line emission, in contrast to many other Eu²⁺-activated oxides which generally show only 5d-4f band emission. At 77°K, both compounds show only the 4f-4f line emission peaking at 360 nm. At higher temperatures, 5d-4f band emission shows up at the cost of the line emission. A thermal equilibrium is assumed between the lowest excited 5d and 4f levels. The energy difference between these levels, calculated from the variation in the line-band intensity ratio with temperature, was computed to be 0.15 eV (Sr) and 0.09 eV (Ba). The occurrence of the line emission in the barylites is correlated with the weakness of the crystal field at the Eu²⁺ ions and with the high quenching temperature of the 5d-4f band emission.