稀土掺杂硼铝硅酸盐玻璃结构的NMR研究

在Sm2O3掺杂BaO-B2O3-Al2O3-SiO2-Sm2O3(BBASS)玻璃系统的形成性能的研究基础上,借助MAS NMR以及差热测试技术,研究了玻璃的结构特点以及玻璃组成、热处理条件等因素对玻璃结构的影响。研究表明,在未掺稀土的BBAS玻璃结构中,硼氧多面体主要以[BO3]、[BO4]存在,铝氧多面体主要以[AlO4]、[AlO5]、[AlO6]存在;随着BBAS中BaO含量的增加,硼氧三角体[BO3]逐渐向[BO4]转变,铝氧多面体中的[AlO5]、[AlO6]结构单元逐渐向[AlO4]转变;稀土Sm3+具有较强迫积聚作用,能促使玻璃结构中的硼氧多面体形成巨大的网络结构;热处理对玻璃结构中硼氧多面体和铝氧多面体的配位结构影响不大。     

高掺杂稀土PBA玻璃的制备及其化学稳定性研究

稀土掺杂磷酸盐玻璃具有优异的光学和光谱特性,在激光介质材料、有色滤光材料等领域中有着重要的应用。在研究P2O5-BaO-Al2O3-Sm2O3(PBAS)玻璃形成能力的基础上,借助NMR、红外吸收光谱等分析手段,研究了玻璃的结构特点以及在各种化学介质条件下玻璃的化学稳定性能、玻璃的组成和结构对化学稳定性的影响。结果表明:玻璃结构主要由磷氧四面体[PO4]3-和铝氧八面体[AlO6]3-构成;Al3+含量越高,玻璃结构越稳定,玻璃的耐水性和耐酸性也越好;玻璃结构中阳离子的极化能力越强,玻璃的耐酸性越好,侵蚀过程中玻璃表面形成的“缺碱层”在一定程度上减缓了化学介质的侵蚀程度;在碱性介质中,磷酸盐长链末节的金属离子被水化,产生P—O—P断键,形成正磷酸盐溶解到溶液中,稀土离子含量的增加,在一定程度上恶化了玻璃的耐碱性能。     

(CaO-SiO2)-xAl2O3三元系玻璃微结构的拉曼光谱定量研究

本文采用气动悬浮装置成功制备了(CaO-SiO_2)-xAl_2O_(3 )(x=0, 6, 12, 18, 24, 30)的一系列玻璃,并通过拉曼光谱技术结合量子化学从头计算方法、⁽²⁷⁾Al魔角旋转核磁共振技术((27)Al魔角旋转核磁共振技术(⁽²⁷⁾Al MAS-NMR)对其结构进行了定性及定量研究。研究结果表明,当碱度R(CaO/SiO_2)=1时,随着Al_2O_3的加入,硅酸盐结构转变为铝硅酸盐结构。当x≤18时,Al主要以[(27)Al MAS-NMR)对其结构进行了定性及定量研究。研究结果表明,当碱度R(CaO/SiO_2)=1时,随着Al_2O_3的加入,硅酸盐结构转变为铝硅酸盐结构。当x≤18时,Al主要以[^ⅣAlO_4]形式参与网络形成,并在x=18时达到最大,同时也观察到了[ⅣAlO_4]形式参与网络形成,并在x=18时达到最大,同时也观察到了[^ⅤAlO_5]、[ⅤAlO_5]、[^ⅥAlO_6]的存在;当x>18时,[ⅥAlO_6]的存在;当x>18时,[^ⅣAlO_4]相对含量减少,[ⅣAlO_4]相对含量减少,[^ⅤAlO_5]、[ⅤAlO_5]、[^ⅥAlO_6]增加。拉曼光谱精细解谱的结果表明,Al的加入大大增加了体系的复杂性和无序性,具体表现为精细结构Q_iⅥAlO_6]增加。拉曼光谱精细解谱的结果表明,Al的加入大大增加了体系的复杂性和无序性,具体表现为精细结构Q_i^(jklm)含量的无规律变化,但对初级结构Q_i含量的影响不大,并主要以Q_2形式存在。     

若干具有[(PO4)2Mo5O15]簇骼的化合物的光谱研究

本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。     

AlO2和Al2O分子的结构与解析势能函数

运用密度泛函理论的B3LYP方法在6-311 G**水平上,对AlO2,Al2O分子的结构进行了优化计算,得到AlO2,Al2O分子的稳定结构都为D∞h.构型.AlO2电子态为X1ПC,平衡核间距RAl-O=0.1661 nm、离解能De=8.9217 eV;Al2O电子态为X1∑,平衡核间距RO-Al=0.1731 nm、离解能De=10.5269 eV.用多体项展式理论推导了基态AlO2和Al2O分子的解析势能函数,其等值势能图准确再现了基态AlO2和Al2O分子的结构特征及势阱深度与位置.     

Al2O3-P2O5-H2O反应体系产物以及高温产物的光谱特征

以磷酸和氢氧化铝为原料,选取不同工艺合成了系列磷酸铝。用FTIR,XRD,Raman和SEM研究了相关产物阴离子基团的红外图谱变化和三聚磷酸二氢铝的热变化过程的光谱性质以及颗粒形貌的变化。当改变P2O5/Al2O3摩尔比或者缩合温度时,可以看到磷酸根形式H2PO4-,PO34-,H2P3O130-和PO3-的红外光谱特征的变化,P—O键的振动峰随着聚合程度的增加向短波长方向移动,而且峰宽增加。当三聚磷酸二氢铝经高温处理后,拉曼和红外光谱显示了聚合磷酸根中微结构间的相互作用引起P—O键伸缩振动频率增大以及结晶水的变化趋势,随着组成变化的同时,其颗粒的层状结构层厚度增加,层边界趋于模糊,直至呈现熔体状态。     

稀土掺杂硼铝硅酸盐玻璃结构的NMR研究

在Sm₂O₃掺杂BaO-B₂O₃-Al₂O_3-SiO_2-Sm₂O₃(BBASS)玻璃系统的形成性能研究的基础上,借助MAS NMR以及差热测试(DTA)技术,研究了玻璃的结构特点以及玻璃组成、热处理条件等因素对玻璃结构的影响. 研究表明,在未掺稀土的BBAS玻璃结构中,硼氧多面体主要以[BO₃]、[BO₄]存在,铝氧多面体主要以[AlO₄]、[AlO₅]、[AlO₆]存在;随着BBAS中BaO含量的增加,硼氧三角体[BO₃]逐渐向[BO₄]转变,原先[AlO₄]、[AlO₅]、[AlO₆]共存的铝氧多面体结构逐渐转变为大量[AlO₄]和少量[AlO₅]共存的结构;稀土Sm³⁺具有较强的积聚作用,其能促使玻璃结构中的硼氧多面体形成巨大的网络结构;热处理对玻璃结构中硼氧多面体和铝氧多面体的配位结构影响不大.     

CaO-SiO_2-Al_2O_3渣系连铸保护渣结构的拉曼光谱研究

在高铝钢连铸过程中,钢水中的Al与CaO-SiO2基连铸保护渣中的SiO2反应导致保护渣中SiO2含量降低而Al2O3含量大幅增加,CaO-SiO2基转变为CaO-SiO2-Al2O3基连铸保护渣而影响高铝钢连铸,所以研究CaO-SiO2基向CaO-SiO2-Al2O3基保护渣转变过程中结构上发生的变化有助于开发出满足高铝钢连铸需求的保护渣。本文利用拉曼光谱研究了CaO-SiO2基和CaO-SiO2-Al2O3基连铸保护渣的结构特点。研究结果表明,CaO-SiO2基保护渣主要由Q0,Q1,Q2和Q3等微结构单元构成的硅酸盐网络结构;当转变为CaO-SiO2-Al2O3基保护渣后,渣样中的网络破坏体优先用于破坏硅酸盐网络结构,当渣中SiO2含量较低时,部分网络破坏体会促进Al 3+形成[AlO4]四面体结构。渣中生成的[AlO4]四面体会进入硅酸盐网络结构形成铝硅酸盐网络结构,以Al-O-Al或Al-O-Si等方式连接,导致渣样结构变得复杂多变。使用Li2O对Na2O和CaO对MgO等摩尔替代研究表明相同价态离子之间的替换能够改变[AlO4]四面体在硅酸盐网络结构上的连接方式,导致CaO-SiO2-Al2O3基保护渣渣样结构易受成分变化而改变;CaF2对CaO等摩尔替代研究发现,当渣中CaF2小于13mol%,CaF2促进渣样网络结构解体,当高于13mol%时,CaF2又会导致渣样聚合度增加。由此可见,在设计CaO-SiO2-Al2O3基保护渣时,既要考虑不同种类离子对渣样结构产生的影响,又要考虑离子含量的影响。     

SrO/Al2O3比率对Sr2AlO4:Eu,Dy发光性能的影响

采用高温固相法合成稀土离子掺杂碱土铝酸盐发光粉,通过改变原料配比分别合成出富Sr和富Al的Sr2AlO4：Eu,Dy发光粉样品。XRD分析结果表明,SrO／Al2O3比率的微小变化不会影响样品的晶相组成。样品的发光性能和长余辉特性测试结果表明,富Al的Sr2AlO4：Eu,Dy发光粉具有较高的荧光强度及较长的余辉时间,说明Sr2AlO4晶格中SrO／Al2O3比率对Sr2AlO4：Eu,Dy发光性能和长余辉特性有很大的影响。激发与发射光谱、发射峰余辉衰减以及热释光谱分析表明,SrO／Al2O3比率的微小变化,导致晶格中发光中心Eu^2 浓度和陷阱的深度与密度发生改变。在富Sr体系中,稀土掺杂离子Eu^2 ,Dy^3 较难进入Sr^2 的晶格位置,晶格中发光中心Eu^2 浓度和陷阱密度都较低,使得粉体发光强度较低,余辉时间较短。     

Ta2O5对碲铋酸盐玻璃光学性能的影响

通过高温熔融法制备了一系列(90-x)TeO2-10Bi2 O3-xTa2 O5(x=0％,2％,4％,6％,8％)TBT玻璃样品.拉曼光谱和X射线光电子能谱测试结果显示,随着Ta2 O5的加入,玻璃网络中的[TeO3]与[TeO3+1]向[TeO4]转变,玻璃网络结构更加致密.这解释了差示扫描量热法测试中TBT玻璃的...     

稀土掺杂硼铝硅酸盐玻璃的析晶特性及其微观结构

借助差热分析测定了稀土掺杂BaO-Al2O3-B2O3-SiO2玻璃的热稳定性。采用XRD和TEM/EDS研究了在不同热处理条件下M玻璃样品的失透、析晶过程的微观结构。结果表明:随着稀土掺量的逐渐增加,玻璃的热稳定性是先提高后降低;玻璃的失透首先由分相造成,稀土离子大量富集在富硼铝相中,热处理温度越高,玻璃的分相和析晶越明显,玻璃的析晶产物为SmAl2.07(B4O10)O0.6晶体;热处理过程中铝氧多面体的稳定性优于硼氧多面体。     

Combined 17O NMR and 11B-31P double resonance NMR studies of sodium borophosphate glasses

17O enriched sodium borophosphate glasses were prepared from isotopically enriched NaPO3 and H3BO3. These glasses have been studied by 17O, 11B and 31P NMR including 17O and 11B multiple quantum magic angle sample spinning (MQMAS), 11B-31P heteronuclear correlation (HETCOR) NMR and 11B{31P} rotational echo double resonance (REDOR). For comparison, the crystalline borophosphates BPO4 and Na5B2P3O13 were included in the investigations. The latter compound shows three sharp 31P resonances at -0.2, -2 and -8 ppm and two BO4 sites that can only be resolved by MQMAS. The 17O NMR spectra were recorded using both the static echo method at medium magnetic field (9.4 T) as well as MAS and MQMAS methods at high field (17.6 T). In total, five oxygen sites were identified in these borophosphate glasses: P-O-P, Na...O-P, P-O-B, B-O-B, Na...O-B. However, these five sites are not present simultaneously in any of the glasses. The 17O MQMAS spectra prove that P-O-B links play a major role in borophosphate glasses. These results are confirmed by the complementary 11B MAS spectra that show the presence of asymmetric and symmetric trigonal groups BO3a and BO3s and two tetrahedral BO4 units. 11B{31P} REDOR NMR is used to give independent information to assign the 11B lines to structural units present in the glasses. These REDOR measurements reveal that B-O-P bonds are present for each borate unit, including the BO3 groups. Particularly, a structural proposal for the two different BO4 resonances is given in terms of a different number of bonded phosphate tetrahedra. The 31P MAS spectra are usually broad and not well resolved. It is shown by 11B-31P HETCOR NMR that a possible structural assignment of a 31P signal at about -20 ppm to Q2 units as in binary sodium phosphate glasses is wrong and that the phosphate tetrahedron belonging to this resonance must be connected to borate groups.     

A 125Te and 23Na NMR investigation of the structure and crystallisation of sodium tellurite glasses

125Te static nuclear magnetic resonance (NMR) and 23Na and 125Te magic angle spinning (MAS) NMR have been used, in conjunction with X-ray diffraction, to examine the structure and crystallisation behaviour of glasses of composition xNa2O.(1-x)TeO2 (0.075 x 0.4). The MAS NMR 23Na spectra from the glasses are broad and featureless but shift by approximately +5 ppm with increased x, i.e. as the system becomes more ionic. The static 125Te NMR spectra show an increase in axial symmetry with increasing x, indicating a shift from predominantly [TeO4] to [TeO3] structural units. The 23Na and 125Te spectra from the crystallised samples have been fitted to obtain information on the sites in the metastable crystal phases, which are the first to form on heating and which are therefore more closely related to the glass structure than thermodynamically stable crystal phases. New sodium tellurite phases are reported, including a sodium stabilised, face centred cubic phase related to delta-TeO2; a metastable form of Na2Te4O9 containing 3 sodium and 4 tellurium sites; and a metastable form of Na2Te2O5 containing 2 sodium sites. There is evidence of oxidation of TeIV to TeVI occurring in glasses with high values of x and, at x=0.40 and 0.50 (outside the glass forming range), some sodium metatellurate (Na2TeO4) is formed at the same time as sodium metatellurite (Na2TeO3). The 125Te shift is very sensitive to environment within the sodium tellurite system, covering more than 320 ppm, with anisotropies varying from 640 to 1540 ppm. The lack of features in the 125Te spectra of the glass phases, combined with the large shift range and high but variable anisotropy, means than it is not possible to obtain a unique fit to any presumed species present. Furthermore, the chemical shift anisotropy parameters for three of the four Te sites in the Na2Te4O9 phase are found to lie outside the range used for previous simulations of glass spectra.     

Li_2O-(LiCl)_2-B_2O_3-Al_2O_3系玻璃的红外光谱

本工作系统地测量和分析了Li_O-(LiCl)_2-B_2O_3-Al_2O_3系玻璃的红外光谱,据此研究了玻璃中硼的配位数和硼酸盐结构基团随组成的变化以及Al~(3+)和Cl~-离子在结构中所起的作用,并对光谱中某些吸收峰机理作了定性探讨。     

用相图原理研究玻璃性质与结构(Ⅰ)核磁共振谱研究Na_2O-B_20_3-SiO_2玻璃结构

本文用电子计算机计算Na_2O-B_2O_3-SiO_2玻璃系统的NMR数据,并根据实验结果,应用相图原理,提出了一种新的玻璃结构模型.本文认为组份简单的玻璃与相同成分化合物的结构相似,而多组份玻璃则是由相图中最邻近的同成份熔融化合物组成的混合物.     

Non-bridging oxygens in borate glasses: characterization by 11B and 17O MAS and 3QMAS NMR

The concentrations of non-bridging oxygens (NBO) in oxide glasses has major effects on their properties and on those of their precursor glass melts. In borate and borosilicate glasses, the presence of NBO bonded to boron has generally been inferred from 11B NMR spectra and mass balance considerations. Here we report the direct observation of such NBO using 17O MAS and 3QMAS techniques, and compare estimates of their populations with those derived from high-resolution 11B MAS spectra. For the latter, two independent methods are used, based on the ratios of trigonal to tetrahedral boron and on the concentrations of trigonal boron sites with large quadrupolar asymmetry parameters. We include data on crystalline sodium pyroborate (Na4B2O5) and sodium metaborate (NaBO2), and several sodium and barium borate glasses. 17O chemical shifts and quadrupolar coupling constants for NBO bonded to boron vary considerably depending on their coordination environment. In borosilicates, peaks for this species may be hidden by overlap with B-O-Si or Si-O-Si resonances.     

A high-resolution 19F NMR spectroscopic study of barium fluorozirconate glasses and related crystals

Fluorozirconate glasses have attracted considerable attention not only for their transparency in the infrared, but also due to their high fluorine ion conductivities and extreme fragility in the viscosity-temperature relationship. We report on structural studies of binary BaF2-ZrF4 glasses with 58-78 mol% ZrF4 using high-resolution magic-angle-spinning 19F NMR. High-speed 19F MAS NMR allows us to resolve at least three unique fluorine environments in these binary glasses. These fluorine environments are attributed to one type of bridging fluorine, between corner-sharing Zr-F coordination polyhedra, and two types of non-bridging fluorine (NBF), one of which is bonded to one Zr and one Ba atom while the other is bonded to one Zr and two Ba atoms. The concentration of the first type of NBF increases with decreasing ZrF4 concentration, while that of the second type is essentially independent of glass composition. These assignments have been made on the basis of detailed 19F NMR studies of a wide variety of crystalline fluorozirconates with known crystal structures. A comparison between the glass and crystal 19F NMR spectra rules out any significant concentration of edge-shared Zr-F polyhedra in these binary glasses. The Zr atoms in all glasses are found to be coordinated to approximately 7.8+/-0.2F atoms.