Pr2O3对含Cr2O3辉石系矿渣微晶玻璃晶化行为的影响

以白云鄂博西尾矿和粉煤灰为主要原料,分别制备了添加0,2.0wt;,4.0wt;和6.0wt; Pr2O3的辉石系矿渣微晶玻璃;综合采用基于DSC/DTA结果的析晶活化能Ek、Avrami指数以及粘流活化能Eη和背散射电子SEM显微形貌分析研究了Pr2O3对析晶的影响.结果表明在所研究范围内,Pr2O3含量的提高在整体上抑制了辉石相的析出.其原因除了与富Pr颗粒相对辉石相在析晶过程中的“钉扎”有关外,还与Pr2O3含量提高后使基础玻璃网络聚合程度加大,从而增大了辉石相形成所需离子扩散的阻力有关.     

基础成分配比对白云鄂博尾矿微晶玻璃结构及性能的影响

以白云鄂博二次选后尾矿和粉煤灰为主要原料,采用熔融法制备得到了CaO-MgO-Al2O3-SiO2系尾矿微晶玻璃.制备流程包括熔融、退火、核化及晶化过程.其中玻璃熔融温度为1450℃,核化温度为720℃,晶化温度为850℃.利用XRD研究了基础玻璃成分配比对微晶玻璃结构的影响.结果表明基础玻璃成分配比直接决定微晶玻璃的主晶相形成.随着基础玻璃成分配比的变化,微晶玻璃可能形成辉石相、钙长石相、镁铁尖晶石相或磁铁矿相.当其他元素固定,CaO/MgO和CaO/Al2O3比值的减小会导致微晶玻璃由辉石相转变为镁铁尖晶石相和钙长石相.而当SiO2/CaO比值大于2时,主晶相则由辉石相转变为磁铁矿相.DTA测试结果表明CaO有利于析晶温度的降低,而MgO、Al2O3和SiO2相对提高了析晶温度.力学性能测试表明抗折强度、密度、耐酸碱度与微晶玻璃主晶相有直接关系.主晶相为辉石相的微晶玻璃具有更高的抗折强度、密度和耐酸性.     

不同冷却方式黄磷炉渣微晶玻璃析晶动力学研究

以水淬黄磷炉渣和自然冷却态黄磷炉渣为研究对象,采用熔融法制备CaO-Al2O3-SiO2系微晶玻璃.通过差热分析、X射线衍射和扫描电镜,并利用修正后的Johnson-Mehl-Avrami (JMA)方程和Augis-Bennett方程,分析了不同冷却方式下黄磷炉渣制备微晶玻璃的析晶规律.结果表明:不同冷却方式对微晶玻璃的析晶行为有所不同,水淬黄磷炉渣微晶玻璃的析晶活化能E为352.609 kJ/mol,自然冷却黄磷炉渣微晶玻璃的析晶活化能E为405.685kJ/mol;两种不同冷却方式的黄磷炉渣微晶玻璃的晶化机制均为三维体积晶化.水淬黄磷炉渣微晶玻璃中主晶相为硅灰石(CaSiO3)并含有少量的石英矿物;自然冷却黄磷炉渣微晶玻璃中主晶相为钙蔷薇辉石类(Ca(Mn2,Ca)Si2O6)和含铁硅灰石类固溶体((Ca,Fe) SiO3).以自然冷却渣制备的微晶玻璃性能优于水淬渣制备出的微晶玻璃.     

Fe2O3对CaO-Al2O3-MgO-SiO2系微晶玻璃析晶及断裂特性的影响

采用熔融法,利用纯化学试剂制备了CaO-A12O3-MgO-SiO2 (CAMS)系微晶玻璃,利用DTA、XRD、拉曼光谱仪等研究了Fe2O3对微晶玻璃析晶特性的影响规律,微晶玻璃的物化性能由抗折强度、杨氏模量、剪切模量、泊松比、维氏硬度等进行评价.结果表明,微晶玻璃的析晶特性随着Fe2 O3含量的增加而增强,对应母体玻璃中首先出现富铁相,进而促进辉石主晶相的析出.微晶玻璃的断裂特性及裂纹扩展方式均随析晶度的提高得到明显改善.但过量的Fe2O3添加则对微晶玻璃的析晶特性无明显影响,反而降低了玻璃相的致密性.微晶玻璃的耐酸性、抗折强度、杨氏模量及剪切模量均呈现先增加后降低的趋势,微晶玻璃的Fe2 O3含量为6.6wt;时综合性能最优.     

烧结法制备高炉渣CMAS系统微晶玻璃的研究

利用高炉渣及其它辅助原料制备基础玻璃,采用一步烧结法制备主晶相为辉石的CaO-MgO-Al2O3-SiO2(CMAS)微晶玻璃.综合运用DSC,XRD以及场发射扫描电子显微镜等测试手段,分析热处理制度对高炉渣CMAS微晶玻璃的析晶行为及性能的影响.结果表明:随着热处理温度上升,微晶玻璃的主晶相均为辉石,次晶相均为长石,晶相析出量增加,微晶玻璃的体积密度及抗折强度均呈现先增后减趋势.随着热处理时间增加,微晶玻璃的体积密度及抗折强度均呈现下降趋势.当热处理温度为1020 ℃,晶化时间30 min时,样品的机械性能最好,体积密度为2.690 g·cm-3,抗折强度为67.00 MPa.     

TiO2对自然冷却黄磷炉渣微晶玻璃析晶行为的影响

以自然冷却黄磷炉渣为主要原料,采用熔融法制备CaO-Al2O3-SiO2系微晶玻璃,并借助DTA、XRD、SEM等分析了TiO2作为晶核剂对微晶玻璃析晶及其性能的影响规律.利用修正后的Johnson-Mehl-Avrami(JMA)方程初步计算微晶玻璃样品的析晶活化能E及晶体生长指数n.结果表明:自然冷却黄磷炉渣中固有的晶核剂可有效的促进CaO-Al2O3-SiO2系统的析晶,炉渣固有的TiO2可促进大量晶核的形成,晶化指数达到4.84,随着TiO2的加入,系统的析晶活化能由126.1483 kJ/mol增加到363.8206 kJ/mol,而晶化指数变为3.24.晶化机制由体积析晶变为二维析晶.主晶相的种类没有随TiO2量的增加而改变,均为硅灰石(CaSiO3)和钙铁辉石((Ca,Fe) SiO3).     

超低膨胀微晶玻璃发展现状及应用

超低膨胀微晶玻璃是在Li₂O-Al₂O₃-SiO₂系玻璃的基础上经过严格的受控晶化，在母体玻璃中析出以β-石英固溶体为主晶相的微晶玻璃材料。由于具有极低的热膨胀系数，以及优异的热稳定性、化学稳定性和力学性能，超低膨胀微晶玻璃在诸多领域得到了广泛应用。本文综述了超低膨胀微晶玻璃的组成、制备方法、国内外研究历程及发展现状、应用，指出了目前生产超低膨胀微晶玻璃存在的问题和国产超低膨胀微晶玻璃与国际顶尖产品存在的差距，以及国产超低膨胀微晶玻璃今后的发展方向。     

铁含量及价态对白云鄂博尾矿微晶玻璃析晶特性及性能的影响

以白云鄂博尾矿及粉煤灰等固体废弃物为主要原料,采用熔融法、经退火、核化及晶化热处理制备得到了以辉石为主晶相的CaO-MgO-Al2O3-SiO2 (CMAS)系尾矿微晶玻璃.利用化学分析方法测定了不同氧化铁及碳含量对微晶玻璃中Fe3+/Fe2+的影响;利用XRD、DTA、SEM等研究了不同氧化铁及碳含量对微晶玻璃结构及析晶特性的影响.结果表明,不同氧化铁添加量对微晶玻璃中Fe3+/Fe2影响很小,因此对微晶玻璃的析晶特性无本质影响.而随着还原碳粉的加入,Fe3+/Fe2与未加碳粉相比减小明显,微晶玻璃中FeO质量分数的增加极大地提高了微晶玻璃的析晶特性.但过量的碳粉加入导致单质铁的析出,反而降低了微晶玻璃的析晶能力.上述析晶特性的变化直接影响到微晶玻璃的耐酸度及抗折强度.     

La3+和Ce4+对尾矿微晶玻璃显微结构及性能的影响

选用白云鄂博尾矿及粉煤灰为主要原料,采用熔融法制备得到了CaO-Al2 O3-MgO-SiO2(CAMS)系尾矿微晶玻璃.借助差热分析、X射线衍射以及扫描电子显微镜、维氏硬度仪等研究了La2 O3和CeO2对尾矿微晶玻璃析晶行为、显微结构及性能的影响.结果表明,添加La2 O3和CeO2后尾矿微晶玻璃的主晶相均未发生改变,但稀土的添加会诱导微晶玻璃内产生元素集聚体.聚集体内Si元素分布均匀,稀土元素以及Al、Na聚集,元素Ca和Fe缺失.聚集体的形成致密化玻璃网络结构,从而增加裂纹扩展阻力,消耗裂纹扩展过程中的能量,抑制裂纹的扩展并最终提高材料的维氏硬度.     

稀上元素(镧、铈)掺杂TiO2复合材料的制备及其光催化性和抑菌性的研究

以钛酸丁酯(C₁₆H₃₆O₄Ti)、蒸馏水、无水乙醇、冰乙酸、氧化镧(La₂O₃)和氧化铈(CeO₂)为原料,采用溶胶-凝胶法制备了纳米TiO₂和稀土元素掺杂的TiO₂复合材料.利用X射线衍射仪、扫描电子显微镜、ICP-OES等离子体发射光谱元素分析、紫外-可见光谱仪和培养基扩散法对样品进行了表征和性能研究.实验结果表明:本实验成功制备了锐钛矿晶型的TiO₂粉末和镧掺杂的二氧化钛粉末(La/TiO₂),因氧化铈微溶于酸,没有溶解到溶液中,Ce基本没有掺入到二氧化钛中,所制备的粉末主要是锐钛矿型二氧化钛和氧化铈的混合物,对TiO₂的性能基本没有影响.La/TiO₂粉末中La元素的含量为8.24;,在300 min内La/TiO₂光催化罗丹明B溶液的脱色率提高达到91.2;,对金黄色葡萄球菌有良好的抑制作用.     

Phase relations around langasite (La3Ga5SiO14) in the system La2O3–Ga2O3–SiO2 in air

Phase relations around langasite (LGS, La₃Ga₅SiO₁₄) were studied on the basis of phase assemblage observed during calcination and crystallization process of samples of various compositions in the ternary system La₂O₃–Ga₂O₃–SiO₂. A ternary compound of apatite structure, La₁₄Ga_xSi_9–xO_39–x/2 was found for the first time. Crystallization of this compound was observed in the cooling process of molten samples of stoichiometric LGS as well as LGS single crystal, demonstrating that LGS is an incongruent-melting compound. A phase diagram was established primarily based on the crystallization sequence in the cooling process.     

XAS study of lanthanum coordination environments in glasses of the system K2O---SiO2---La2O3

The La L₁ and L₃ XANES and L₃ EXAFS have been investigated for the series of glasses 10K₂O---50SiO₂---x La₂O₃ (x = 1, 5, 10) and (10 − x)K₂O---40SiO₂−(x/3)La₂O₃ (x = 7.5, 5, 2.5) and model compounds La₂O₃, LaAlO₃, LaPO₄, La₂NiO₄, La₂CuO₄ and La(OH)₃. An edge resonance at 25 eV above the L₁ edge in the glass spectra is concentration-dependent, decreasing in intensity with increasing lanthanum concentration. The 2s → nd forbidden transition increases with La₂O₃ concentration, indicating a reduction in the ‘average’ site symmetry of the first coordination shell of La. Mapping _X(k) space, which is a new and promising technique, was employed to extract bond distance, coordination number and thermal parameters from the EXAFS. By this method, one calculates the complete _X(k) space a function of all physically reasonable values of the adjusted parameters in all possible combinations. The advantage in this method is the assurance of a global minimum. Bond lengths were comparable to those obtained by Fourier transforming the phase corrected EXAFS. The values are 2.42 Å (± 0.03 Å) for La---O. The coordination numbers (N ≤ 7 ± 1.5) were derived by mapping and comparison to the published structures for other La compounds. _X(k) mapping is compared with least-squares fitting the data, and the correlation between the Debye-Waller factor and coordination number is also discussed.     

Synthesis and characterization of a novel non-linear optical material La2SrB10O19

A novel compound with the chemical formula of La₂SrB₁₀O₁₉ has been successfully synthesized from the La₂O₃--- SrO---B₂O₃ system via a solid state reaction. The powder X-ray diffraction data is reported. It is found that the data show little difference from that of La₂CaB₁₀O₁₉ which demonstrate that they are isostructural. The powder second harmonic generation effect of La₂SrB₁₎O₁₉ is about twice that of KH₂PO₄(KDP). The investigation of crystal growth is in progress.     

纳米级SnO2或Yb2O3对熔融石英陶瓷析晶性能的影响

通过XRD分析和热膨胀率实验,从析晶角度探讨了添加纳米级SnO₂或Yb₂O₃对熔融石英陶瓷析晶性能的影响。结果表明:熔融石英陶瓷高温析晶的主要晶化产物为方石英,方石英析出量随烧结温度的提高而逐渐增多;纳米级SnO₂或Yb₂O₃的引入可通过抑制熔融石英中方石英的析出,有效地降低熔融石英材料在升温过程中的热膨胀率,并且随着烧结温度升高需要不断调整添加剂用量,纳米级SnO₂和Yb₂O₃的最佳用量(质量分数)分别为1%和2%。     

Precipitation of In2O3 nano-crystallites from glasses in the system Na2O/B2O3/Al2O3/In2O3

Glasses in the system Na₂O/B₂O₃/Al₂O₃/In₂O₃ were melted and subsequently tempered in the range from 500 to 700 °C. Depending on the chemical composition, various crystalline phases were observed. From samples without Al₂O₃, In₂O₃ could not be crystallized from homogeneous glasses, because either spontaneous In₂O₃ crystallization occurred during cooling, or other phases such as NaInO₂ were formed during tempering. The addition of alumina, however, controlled the crystallization of In₂O₃. Depending on the crystallization temperature applied, the crystallite sizes were in the range from 13 to 53 nm. The glass matrix can be dissolved by soaking the powdered glass in water. This procedure can be used to prepare nano-crystalline In₂O₃-powders.     

Diffraction studies of rare-earth phosphate glasses

A series of lanthanide oxides was incorporated in a vitreous phosphate host network. Molar constituents of the glasses were typically (La₂O₃)₁₀(R_xO_y)₁₀(Al₂O₃)₅(P₂O₅)₇₅. Each glass had a different lanthanide (R atom) from the series; La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er and the values of x and y depended on the valency of the rare-earth atom. Both X-ray and neutron diffraction were employed in examining their structures. The results indicate that the basic PO₄ tetrahedral unit remains unaltered with an average P–O distance of and predominant Q² linkages to its neighbouring units so as to form a continuous network while accommodating the included lanthanides. In accordance with this model, the average distance of rare-earth (comprising La and a second type of R atom) to oxygen decreased from 2.44 to 2.26 , a trend to be expected from the lanthanide contraction. The average oxygen coordination around the rare-earth was found to vary in the range of 6–8. With these average parameters, a small (74 atom) hand-built model was made to check the feasibility of constructing a continuous random network. Optical transmission measurements show all these glasses to absorb strongly in the UV region and to have marked absorption resonances in the visible region of 400–1000 nm except for the La, Ce, Eu, Tb containing glasses which have low or negligible absorption in the latter range.     

Effect of Al2O3 on phase separation and crystallization in ZnO---Al2O3---B2O3---SiO2 glasses

The effect of alumina on the phase separation and the crystallization of the glasses of composition (mol%) 18ZnO·30B₂O₃·52SiO₂ and O-40 Al₂O₃ was studied using an electron microscope and IR spectroscopy. The main crystalline phase appears in the microphase for which the compositions are not nearer to the crystal stoichiometry than the mean. The addition of Al₂O₃ suppresses the immiscibility but enhances the crystallizability.     

纳米氧化镱对熔融石英析晶动力学机制的影响

本文研究引入纳米氧化镱对熔融石英析晶机制及动力学过程的影响。通过X射线衍射仪(XRD)测试结果分析了纳米氧化镱的引入对熔融石英陶瓷析晶率的影响,采用动力学方法分析了纳米氧化镱的引入对熔融石英陶瓷析晶机制的影响,同时探讨了其等温析晶动力学过程。研究表明,熔融石英陶瓷的晶粒向二维兼有一维及三维的方式生长,引入纳米氧化镱的熔融石英陶瓷的晶粒则向二维兼有三维的方式生长;试样B和试样Y的析晶活化能E分别为874 kJ/mol和1 188 kJ/mol。在熔融石英陶瓷中引入纳米氧化镱能够大幅度减少SiO₂玻璃脱玻为方石英的“活性成核点”,增加玻璃表面结构稳定性,提高析晶活化能,大大降低熔融石英的析晶率。     

Surface crystallization of rare-earth aluminosilicate glasses

Surface crystallization in a rare-earth aluminosilicate glass (Nd₂O₃–Al₂O₃–SiO₂–TiO₂) was studied using an isothermal method and the crystal growth rate of the glasses was evaluated as a function of the composition. For measuring the surface crystal growth rate, two different methods: measurement of the crystal layer in the longitudinal and lateral growth direction. It was found that crystallization proceeded by surface crystallization only and TiO₂ did not act as a nucleating agent. The growth rate was strongly dependent on the viscosity of glass and agreed with prediction from the Preston model using the known viscosity and melting temperature. As the Si/Nd and Si/Al ratios decreased, the crystal growth rate increased. TiO₂ and Nd₂O₃ played the role of network modifier, which decreased the viscosity of the glass, facilitating crystallization of the rare-earth aluminosilicate glass.     

Crystallization of lithium metasilicate from lithium disilicate glass

The crystallization behavior of lithium disilicate glass powder heated in molten LiNO₃ salt was investigated using X-ray diffraction techniques. Heat treatment at 500°C with LiNO₃ molten salt caused a lithium metasilicate, Li₂SiO₃, crystal phase to appear after 5–96 h. By contrast, glass powder heat-treated in air at 500°C remained amorphous after 5 h and turned into lithium disilicate, Li₂Si₂O₅, crystal after 40 h. Qualitatively similar results were obtained at 400°C. Glass powder heat-treated at 575°C in both molten salt and in air turned into lithium disilicate crystal. Metasilicate crystallization occurs with LiNO₃ molten salt at 500 and 400°C due to the incorporation of lithium into the sample glass powder from the melt during crystallization. An increase in lithium content in the sample after molten salt heat treatment was confirmed by chemical analysis using dc plasma emission spectroscopy.