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.     

Fe2O3对纳米晶尾矿微晶玻璃结构及性能的影响

以铁尾矿和金尾矿为主要原料,采用熔融法制备了添加0 ～ 20wt; Fe2O3的CaO-MgO-Al2O3-SiO2(CMAS)系纳米晶尾矿微晶玻璃,利用差示扫描量热分析(DSC)、X射线衍射分析(XRD)、红外光谱(IR)、扫描电镜(SEM)和综合力学性能仪等测试手段,研究了Fe2O3含量对该体系微晶玻璃显微结构及性能的影响.实验结果表明:随着Fe2O3含量的增加,样品的晶化温度和玻璃化转变温度逐渐降低;且Fe2O3可促进主晶相透辉石相(Mg0.6Fe0.2Al0.2) Ca(Si1.5Al1.5)O6的形成;同时Fe2O3能够有效减小透辉石相平均晶粒尺寸;另外,微晶玻璃的密度、显微硬度和耐碱性随晶粒尺寸的减小而增加,而抗折强度和耐酸性随晶粒尺寸的减小而降低.     

微波加热制备含稀土(La2O3)矿渣微晶玻璃研究

利用矿渣制备微晶玻璃是提高矿产资源利用率的主要形式之一。本文以白云鄂博尾矿为原料,采用微波一步法制备了CaO-MgO-Al₂O₃-SiO₂(CMAS)系辉石相矿渣微晶玻璃。选择835 ℃作为晶化温度,研究了微波加热对微晶玻璃析晶行为和微观组织的影响。以La₂O₃作为研究变量探讨了La₂O₃添加对矿渣微晶玻璃析晶行为的作用。与传统的热处理制度相比,微波加热可以在较短的时间内达到较高的析晶效果。同时La₂O₃的添加促进了晶粒细化。由拉曼光谱分析,La离子添加会导致玻璃网络中桥氧的增多,促进了辉石相析晶。在La的添加量为4%(质量分数)时硬度最高,达到了829.22 MPa。     

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.     

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.     

Fe2O3掺杂对MgO-Al2O3-SiO2系玻璃析晶和性能的影响

采用高温熔融法和两步法微晶热处理制备了MgO-Al2O3-SiO2系堇青石微晶玻璃和铁尖晶石微晶玻璃.利用DSC分析、X射线衍射、FTIR和扫描电子显微镜等手段研究了Fe2O3对玻璃的析晶性能、显微结构和物理性能的影响.结果表明,Fe2 O3的加入可有效降低析晶活化能,促进晶体的析出.当Fe2O3含量达到7.44;时,主晶相由堇青石变为铁尖晶石.Fe2O3掺杂使样品的介电常数由3.2增大至5.8、热膨胀系数由1.941× 10-7增大至7.74×10-6、维氏硬度由7.131GPa增大至11.655 GPa,同时介电损耗由0.05降低至0.015.     

晶核剂对白云鄂博东尾矿微晶玻璃析晶及性能的影响

以白云鄂博东尾矿及粉煤灰为主要原料,采用熔融法制备得到了CaO-MgO-Al2O3-SiO2 (CMAS)系特种微晶玻璃.制备流程包括熔融、退火、核化及晶化过程.基于X射线衍射和拉曼光谱研究了微晶玻璃的晶相结构及分子振动模式、借助于扫描电子显微镜及原子力显微镜对微晶玻璃的耐磨及断裂特性进行了表征;利用差热分析研究了共生晶核剂对微晶玻璃核化及晶化过程的作用机理.结论表明:随着尾矿含量的逐渐降低,微晶玻璃的析晶特性及性能先增强后减弱.微晶玻璃的耐磨性主要由晶相决定,其断裂特性属于沿晶断裂,热膨胀系数的变化规律与析晶特性相一致.     

CaO-MgO-Al2O3-SiO2系微晶玻璃复合晶核剂的优化及其对结构与性能的影响

以化学纯试剂CaO、MgO、Al2 O3和SiO2为主要原料,采用熔融法制备添加复合晶核剂Cr2 O3、Fe2 O3和CaF2的CaO-MgO-Al2 O3-SiO2 (CMAS)系微晶玻璃.采用正交试验的方法,确定复合晶核剂的相对最优配方.利用DTA、XRD、SEM和综合力学性能仪等手段,研究了复合晶核剂对该系微晶玻璃显微结构及性能的影响.结果表明,复合晶核剂的相对最优配方是Cr2 O3、Fe2 O3和CaF2的含量分别为0.5;、10;和8;,且复合晶核剂总含量的增加可以细化晶粒,随着晶粒细化,CMAS系微晶玻璃的维氏硬度增加.     

高热膨胀Na2O-MgO-Al2O3-SiO2微晶玻璃的制备及性能研究

采用传统熔体冷却法制备了Na2O-MgO-Al2 O3-SiO2玻璃并采用整体析晶工艺制备了微晶玻璃.利用DSC、XRD、SEM等测试手段研究了微晶玻璃的析晶行为和显微结构,探讨了热处理制度对该体系微晶玻璃热膨胀系数、密度、抗弯强度、显微硬度等性能的影响.研究结果表明,当晶化温度为800℃时该体系微晶玻璃主晶相为颗粒状霞石晶体(NaAlSiO4);当晶化温度达到900℃时玻璃中开始析出镁橄榄石(Mg2SiO4)晶体;延长保温时间可显著促进析晶但对晶体种类没有影响.析晶后微晶玻璃的密度、热膨胀系数、抗弯强度和显微硬度值显著增加,其最高热膨胀系数可达14.1×10-6℃-1.所制备的微晶玻璃具有很好的机械性能,当热处理温度为1000℃时,其抗弯强度和显微硬度分别达160 MPa和7.8 GPa.     

Fe2O3对MgO-Al2O3-SiO2系微晶玻璃介电性能的影响

以化学纯试剂为原料采用高温熔融法制备MgO-Al2O3-SiO2 (MAS)系微晶玻璃,利用差热分析仪(DSC)、X射线衍射(XRD)、电子扫描显微镜(SEM)以及介电检测等手段对Fe2O3在MAS系微晶玻璃中介电性能的影响进行探究.结果表明:Fe2O3有降低微晶玻璃核化和晶化温度的作用;随着Fe2O3的加入,试样的主晶相由堇青石向镁铝尖晶石转变,试样的介电常数和介电损耗逐渐减小并且电阻率增高;当Fe2O3的添加量大于6;时,微晶玻璃的介电性能变化不大,趋于稳定.     

Gd3+/Eu3+掺杂羟基磷灰石的自燃烧法制备与性能研究

以尿素为燃料,采用自燃烧法制备Gd3 +/Eu3+掺杂羟基磷灰石(HAp∶ Gd-Eu),并用X射线衍射仪、扫描电子显微镜、荧光分光光度计和振动磁强计等对所得样品进行表征.结果表明,自燃烧法获得的产物由不规则形貌和长条状的颗粒组成,平均粒径为216.2 nm.HAp∶ Gd-Eu在紫外光(255 nm)和可见光(464 nm)激发下,具有较强的红光发射.Gd3掺杂摩尔分数X(Gd3+)为5;,Eu3+掺杂摩尔分数X(Eu3+)为2;时,Gd3+敏化Eu3+发光,HAp∶Gd-Eu发光强度最大.增大X(Gd3+)为10;,由于浓度淬灭,Eu3+发光强度减小.HAp∶ Gd-Eu发光强度随引燃温度升高,逐渐增大.HAp∶ Gd-Eu具有一定的磁响应性.     

Na+,Dy3+,Eu3+掺杂YAG荧光粉的光学性能

本文用高温固相法制备了Na⁺,Dy³⁺,Eu³⁺掺杂YAG系列荧光粉。通过改变掺杂的Dy³⁺浓度、激发波长、掺杂Na⁺,研究其对发光的影响。X射线衍射结果显示,硼酸、Na⁺、Dy³⁺、Eu³⁺掺入基本不影响YAG的立方晶相,且随Na⁺、Dy³⁺、Eu³⁺浓度增加,样品衍射峰位置向小角度偏移。用λ_em=590 nm监测Dy³⁺,15%Eu³⁺共掺YAG粉体,随Dy³⁺浓度增加,Eu³⁺和Dy³⁺的激发强度均先增大后减小。当用λ_ex=366 nm激发Dy³⁺,15%Eu³⁺共掺YAG粉体,此时存在Eu³⁺→Dy³⁺的能量传递,计算得到Eu³⁺→Dy³⁺的能量传递效率为84.23%。相比10%Dy³⁺,15%Eu³⁺共掺YAG,掺入0.5%Na⁺后,样品中Dy³⁺发光增强1.5倍,色坐标(0.348 1,0.397),色温5 010 K,接近标准白光。用λ_ex=394 nm激发Dy³⁺,15%Eu³⁺共掺YAG粉体,此时存在Dy³⁺→Eu³⁺的能量传递,计算得到Dy³⁺→Eu³⁺的能量传递效率为88.9%。相比10%Dy³⁺,15%Eu³⁺共掺YAG,掺入0.5%Na⁺后,Eu³⁺发光增强1.8倍,色坐标(0.466 7,0.416 8),色温2 650 K,达到商用暖白光标准。     

Energy transfer between Tm3+ and Er3+ in borate and phosphate glasses

A study of the energy transfer process between thulium and erbium is presented. From our measurements of fluorescence emissions and decay times the energy transfer efficiencies and probabilities were calculated. In this work the energy transfer which occurs between the upper levels in the UV and VIS regions of the two ions was especially studied. In the Tm-Er system, a mutual migration of energy occurs. The energy transfer from thulium to erbium is a multichannel process in which the energy is transferred from all the metastable levels of thulium to the matching energy levels of erbium. In addition, backtransfer of energy from erbium to thulium occurs by crossrelaxation of respective erbium transitions. The efficiency of energy transfer from thulium to erbium is independent of the levels between which the transfer occurs, but is dependent on the matrix. It is concluded that the energy is transferred via the phonons of the host glass.     

Time-resolved fluorescence measurements on Dy3+ and Sm3+ doped glasses

Various fluoride, phosphate and borosilicate glasses with known properties and global structure have been doped with Dy³⁺ (4f⁹) and Sm³⁺ (4f⁵) between 10¹⁸ and 10²¹ cm^?3 and their time resolved fluorescence in the visible range in combination with characteristic physical properties were studied. Different fit procedures were carried out. Although both ions differ in their intrinsic fluorescence lifetime, with 1.5 ms for Dy³⁺ and 6.5 ms for Sm³⁺, their dependence on glass matrix is remarkable similar. Fluoroaluminate glasses with varying phosphate content between 0 and 20 mol% (FPx), a pure phosphate glass (P100), and two borosilicate glasses with low (DURAN^®-like) and high optical basicity (NBS1) were used for investigations. A strongly ionic surrounding by fluorine ligands, as in fluoroaluminate glass samples, provides the longest fluorescence lifetime. It decreases with increasing phosphate content by increasing oxygen surrounding and with increasing RE³⁺ doping. Large differences were detected in the two borosilicate glasses depending on their optical basicity mainly due to differences in the Na₂O/B₂O₃ ratio. Duran-like samples with low Na₂O content have shown phase separation with higher doping concentration. The RE³⁺ ions are accumulated in the borate-rich droplets. Surprisingly only very low concentration-quenching effects were observed. In the opposite of NBS1 samples with high Na₂O content this generated extremely high quenching effect.     

Gd3+、Co3+共掺杂铁酸铋薄膜多铁性增强及带隙调谐

多铁功能材料在现代生产生活中有举足轻重的作用。本文采用溶胶-凝胶法以硝酸铁、硝酸铋、硝酸钆、硝酸钴为原料,乙二醇甲醚为溶剂,柠檬酸作螯合剂制成前驱体溶液,通过旋涂法在Pt/Ti/SiO₂/Si及ITO衬底上合成Bi_0.85Gd_0.15Fe_1-xCo_xO₃ (x=0, 0.04, 0.08, 0.12)薄膜,研究了Gd³⁺、Co³⁺共掺杂对薄膜铁电性能、磁学性能及光学带隙的影响。XRD结果表明所有薄膜均呈(111)方向的菱形结构,SEM结果表明共掺杂可以细化晶粒。根据铁电性和漏电流测试分析结果可知在Co³⁺掺杂量为8%时最大剩余极化值达到2P_r=15.71 μC/cm²,所有样品的漏电流传导机制均为欧姆传导机制。根据磁学性能测试分析结果可知,共掺杂可以有效增强薄膜的饱和磁化强度,且在Co³⁺掺杂量为8%时最大饱和磁化强度达到37.78 emu/cm³。根据吸收光谱及Tauc公式拟合结果可知共掺杂可以有效减小薄膜的光学带隙且随着掺杂量的增加光学带隙逐渐减小,在Co³⁺掺杂量为12%时光学带隙减小到1.96 eV。     

铽-铕共掺杂的SrMoO4荧光体的制备与发光性质

本文以Na2MoO4、Eu2O3 、Tb4O7和SrCl2为主要原料,通过共沉淀法制备了Sro.95 MoO4∶xEu3+∶(0.05-x)Tb3+荧光粉.通过X-射线衍射仪(XRD)、扫描电子显微镜(SEM)、荧光光谱分析(PL)对样品进行了表征.XRD分析结果表明产物为纯白钨矿型纯四方相SrMoO4,5;的总掺杂量没有引起基质结构的变化.样品在800℃时,发光性能最好,在223 nm紫外光的激发下,Tb3+在486 nm、543 nm、583 nm、617 nm处有一组发射峰,分别对应于Tb3+的5 D4→+7F6、5D4→7F4、5D4→7F4、5D4→7F3的跃迁.Eu3+、Tb3+共掺杂时,发射光谱中Eu3+主发射峰位于611 nm附近,归属于5D0-7F2能级跃迁发射,而位于583 nm附近的弱发射峰归属于5D0-7 F1跃迁.     

掺铕铽钨酸锶荧光粉的制备与发光性质分析

通过化学共沉淀法制备了Sr0.95WO4∶xEu3+∶(0.05-x)Tb3+荧光粉.采用X射线粉末衍射仪、扫描电子显微镜和荧光光谱仪对样品材料的结构、形貌和发光性能进行了表征.分别讨论了在不同反应温度下及稀土离子Eu3+和Tb3+共掺比例变化对荧光粉的发光性能和形貌的影响.结果表明:所得SrWO4∶xEu3+∶(0.05-x)Tb3样品是由无规则棒组成的发光材料,它们在800℃时,发光性能最好;样品在223 nm紫外光的激发下,在543 nm和614 nm处,呈现出两个主要发光中心,分别归属于5D4→7F5和5D0→7F2跃迁,说明稀土离子Eu3+和Tb3具有良好的发光性能,同时随着Eu3和Tb3+掺杂比例的改变,荧光体的发光色度也在不断改变.     

Time-resolved fluorescence measurements on Eu3+- and Eu2+-doped glasses

Various fluoride, phosphate and borosilicate glasses with known properties and global structure have been doped with Eu³⁺ (4f⁶) at doping concentrations between 10¹⁸ and 10²¹ cm^?3. By applying reductive melting conditions Eu³⁺ could partially be transformed to Eu²⁺ (4f⁷). Four fluoroaluminate glasses with varying phosphate content between 0 and 20 mol% (FPx), a pure phosphate glass (P100) and two borosilicate glasses with low (DURAN^®-like) and high optical basicity (NBS1) have been used for these investigations. The time-resolved fluorescence in the visible range has been studied for both ions. Although static and dynamic fluorescence of Eu³⁺ and Eu²⁺ are dramatically different (f–f-transitions for Eu³⁺; d–f-transitions for Eu²⁺), glass structure changes have a similar influence on the dynamic fluorescence behavior of both ions. A strongly ionic surrounding due to fluorine ligands as in fluoroaluminate glass samples provides the longest fluorescence lifetime (about 7 ms for Eu³⁺; about 1.3 μs for Eu²⁺). Increasing phosphate content decreases the fluorescence lifetime due to more oxygen ligands. Interesting differences have been found for the two borosilicate glasses due to the difference in their optical basicity (Na₂O/B₂O₃ ratio). Measurements indicate a homogeneous distribution of europium ions in most FP samples. NBS1 measurements suggest that two different local europium sites are formed. For Duran-like samples only one specific europium site was found, although these samples show phase separation at high doping concentrations into a SiO₂-rich phase and borate- and europium-rich droplets. Fluorescence quenching due to energy transfer from Eu²⁺ to Eu³⁺ could be found for co-doped samples; Eu³⁺-doped samples show no fluorescence quenching.     

Energy transfer in Eu3+-Yb3+ and Tb3+-Yb3+ system in glasses

The behavior of the phonon-assisted energy transfer between trivalent rare-earth ions in glasses was investigated. The ions Eu³⁺ and Tb³⁺ as energy donors and Yb³⁺ as acceptor were selected. The energy gap between the levels of the donor and acceptor was estimated on the basis of the energy diagram of each ion determined from absorption and emission spectra. The probability for the transfers of (Eu, ⁵D₀-⁷F₆): (Yb, ${}^2\text{F}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{-}{}^2\text{F}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$) and (Tb, ⁵D₄-⁷F₀): (Yb, ${}^2\text{F}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}\text{-}{}^2\text{F}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$) in silicate, borosilicate, phosphate and germanate glasses was measured in the temperature range of liquid-nitrogen temperature - 650K. The probability of transfer was the smallest in phosphate glass and B₂O₃ had the effect of increasing it. In germanate glass the dependence of the probability of the energy gap was relatively weak. These results were correlated to the difference in the phonon energy and the strength of the electron-lattice coupling in each glass.     

水热法合成NaYF4:Yb3+-Er3+及其上转换发光性质

采用水热法合成了不同浓度Yb3+和Er3+共掺NaYF4上转换发光材料.利用X-射线粉末衍射技术鉴定了物相的纯度,结果表明,样品的XRD与NaYF4(JCPDS 28-1192)标准卡片一致,均为纯相,结晶度高.在扫描电镜的辅助下,对样品的形貌进行了表征分析,其微观形貌呈六方棱柱状,柱长7μm左右,直径3μm左右,且尺寸分布均匀.在此基础上,利用荧光分光光度计(激发光源为980 nm激光器)对样品的发光性能进行了测试,在980 nm激光器的激发下,得到了发射峰位分别位于525 nm、550 nm、660 nm组成的上转换光谱,可指认为Er3+的2 H11/2,4 S3/2→4 I15/2(绿光)和4 F9/2→4 I15/2(红光)跃迁.进一步讨论了样品发光强度和泵浦源功率之间的关系,发现绿光和红光发射均为双光子过程.