Bi2O3-B2O3-BaO系玻璃的光学折射率与带隙

研究了Bi2O3-B2O3-BaO三元系统的玻璃形成区,给出了该三元系统玻璃形成范围.采用熔融淬冷法制备了60Bi2O3-(40-x)B2O3-xBaO(x=5,10,15,20)和65Bi2O3-25B2O3-10BaO(以摩尔计)的5组高Bi2O3含量的Bi2O3-B2O3-BaO玻璃样品.测试了玻璃样品的折射率和吸收光谱,根据经典的Tauc方程计算了间接允许光学带隙和直接允许光学带隙,计算了样品的能量带隙,并估算了它们之间的关系.研究结果表明;随着BaO含量的增加,玻璃样品折射率逐渐增大,但Ba2 对玻璃折射率的影响要远小于Bi3 ;玻璃样品的紫外吸收增强,光学带隙和能量带隙逐渐减小,光学带隙和能量带隙的比值约为1:1.2.     

Bi2O3-B2O3-Ga2O3玻璃的光学折射率和带隙研究

采用传统熔融淬冷法制备了5组高Bi2O3含量的Bi2O3-B2O3-Ga2O3系统玻璃样品.测试了玻璃样品的密度,折射率和吸收光谱.利用经典的Tauc方程计算了样品的间接允许光学带隙Eopgi,直接允许光学带隙Eopgd和Urbach能量ΔE.根据Duffy等人提出的经验推导公式计算了样品的能量带隙Eg.研究了Ga2O3含量对玻璃样品的密度、折射率、摩尔折射度Rm、金属标准值Mm、光学带隙、能量带隙和Urbach能量的影响,并分析了它们之间的关系.结果表明:随着Ga2O3含量的增加,玻璃样品的密度和折射率逐渐增大,但Ga3+对玻璃折射率的影响要小于B3+;玻璃样品的紫外吸收增强,光学带隙和能量带隙逐渐减小,光学带隙和能量带隙的比值约为1:1.1;Urbach能量逐渐减小,即玻璃中带裂变和缺陷形成的趋势越小.     

Bi_2O_3-B_2O_3-WO_3系统微晶玻璃的制备

采用熔融法制备了0.97[x Bi2O3(1-x)B2O3]·0.03WO3(0.25≤x≤O.75)基础玻璃,通过差热分析确定玻璃的特征温度,经热处理制备微晶玻璃.结果表明所制备的玻璃中只有x =0.67和x=0.60两个组成经热处理生成了微晶玻璃,颜色为乳黄色,晶相分别为BiO2和Bi2WO6,在扫描电镜下观察两种晶体的形貌均为颗粒状,晶粒尺寸在0.8～1.0μm.该体系玻璃的密度较大而硬度较小,但热处理后的微晶玻璃的密度和硬度均大于处理前的基础玻璃.     

P2O5对Bi2O3-B2O3-ZnO体系玻璃结构及热性能的影响

采用传统的熔融冷却的方法制备了(40-x)Bi2O3-30B2O3-30ZnO-xP2O5(0≤x≤15mo1％)体系玻璃.使用红外光谱、拉曼光谱、DSC和热膨胀仪研究了封接玻璃的结构和热性能.红外光谱及拉曼光谱结果表明,P2O5作为网络形成体,以[PO4]进入到玻璃的网络结构中,玻璃的网络结构性增强.玻璃结构中[BO3]三角体结构单元相对含量有增多趋势,[BO4]四面体、[BiO3]三角体、[BiO6]八面体结构单元相对含量减少.随着P2 O5含量的增加,玻璃化转变温度和玻璃的初始析晶温度升高;玻璃的密度减小.Bi2O3-B2O3-ZnO-P2O5体系封接玻璃热膨胀系数减小,从8.289×10-6℃-1减小到6.354×10-6℃-1.玻璃的软化点逐渐增大,从416℃升高到524℃.     

Bi2O3–B2O3二元系统玻璃的网络结构形成与光学性能研究

采用高温熔融–退火法制备了一系列Bi2O3–B2O3二元系统玻璃,系统研究了不同Bi/B摩尔比下B2O3和Bi2O3在玻璃网络结构中的竞争机制,重点探讨了组成对铋酸盐玻璃光学和结构性能的影响。通过吸收光谱和Raman光谱分析了Bi2O3–B2O3二元系统玻璃的网络形成机理,测试了玻璃的密度和线性折射率。结果表明:Bi3+和B3+均为玻璃网络形成体,Raman光谱以600cm–1为中心,其附近的Raman信号强度发生的有规律性变化:低能量区的Raman峰与玻璃中引入的铋离子有关,而高能区的Raman峰与玻璃中的硼氧结构体有关。     

B2O3-K2O-Sb2O3系统玻璃的光学折射率及带隙

高折射率和非线性光学玻璃可以用于高速光开关、光学存储器、新型光纤和光学运算元件等,其研究受到各国科技工作者的高度重视,本文采用熔融淬冷法制备了组成为(85-x)B₂O₃-15K₂O-xSb₂O₃(x=70, 75, 80, 85)的4组玻璃,测试了玻璃样品的密度、折射率、热学性能、拉曼光谱和吸收光谱,利用玻璃样品的吸收光谱计算了其直接允许光学带隙、间接允许光学带隙及Urbach能量。结果表明：随着Sb₂O₃含量的增加,玻璃样品的密度从4.445g/cm³逐渐增加到4.767g/cm³,折射率从1.9438增加到2.0058,玻璃转变温度从291℃降低到260℃,玻璃析晶温度从463℃降低到370℃,直接光学带隙从3.2775eV降低到3.1379eV,间接光学带隙从3.1444eV降低到3.0256eV,Urbach能量从0.137eV逐渐减小到0.107eV。说明Sb₂O₃-K₂O-B₂O₃系统玻璃可以作为新型的非线性光学玻璃候选材料之一。     

P2O5对Na2O-Al2O3-SiO2系统玻璃结构和分相的影响

通过制备25Na2O-(25-x)Al2O3-50SiO2-xP2O5(x≤25mol％)系统玻璃,并且采用Raman和SEM,研究了高含量P2 O5对Na2 O-Al2 O3-SiO2系统玻璃结构和分相的影响.结果表明:随着P2 O5的不断加入,作为电价平衡体的Na+被逐渐释放,并且充当了网络改变体的角色,造成了硅酸盐网络结构聚合度降低,而磷酸盐网络结构聚合度增大.随着P2 O5的不断加入且Al/P<1时,该系统玻璃发生稳定分相,而且分相机理也由成核-生长转变为亚稳分解.     

光学玻璃进展（三）

碲酸盐玻璃的化学组成 以TeO2为主要组成的碲酸盐玻璃具有高折射率的特点.在光学方面的应用包括折射率2.0以上的高折射率玻璃和声光玻璃.50年以前,C.Stanworth研究了简单碲酸盐玻璃系统的性质,在二元BaO·5TeO2和PbO·5TeO2组成中获得折射率2.08和2.25的玻璃.TeO2本身不形成玻璃,加入其它氧化物以后,都能在很广的组成范围内形成玻璃.加入氧化物BaO、PbO、Bi2O3、Ta2O5、WO3等,可以提高折射率.图10总结了一些简单碲酸盐玻璃系统在nd-νd图中的位置.     

CsCl对GeS2-Sb2S3硫系玻璃光学及析晶特性的影响

通过熔融-淬冷法制备了(100-x)(0.9GeS2-0.1Sb2S3.)-xCsCl(x=5,10,15,20,以摩尔计)系列硫卤玻璃.测试了样品的折射率和吸收光谱.根据Tauc方程计算了间接允许光学带隙和直接允许光学带隙.通过差热分析对微晶玻璃析晶动力学进行了研究.利用析晶活化能(E)和频率因子(v),并结合动力学因素和热力学因素分析了玻璃的稳定性.结果表明:随着CsCl含鼍的增加,样品的线性折射率变小,短波截止波长蓝移,光学带隙逐渐增大,玻璃稳定性变差:85(0.9GeS2-0.1Sb2S3)15CsCl玻璃样品较适合制备透明的微晶玻璃,可用于研究硫系基质玻璃与微晶玻璃之间的三阶非线性效应.     

ZnO对Bi2 O3-B2 O3-ZnO低熔点玻璃结构与性能的影响

通过FTIR、Raman、27 Al NMR、XRD、DSC等测试方法,研究了ZnO含量对Bi2 O3-B2 O3-ZnO-SiO2-Al2 O3系统低熔点玻璃结构及热性能的影响.结果表明:当ZnO含量小于12wt％时,Zn2+与自由氧结合形成[ZnO4]四面体,增强网络结构,玻璃化转变温度增大,热膨胀系数减小;当ZnO含量大于12wt％时,锌氧多面体由四配位[ZnO4]转变为六配位[ZnO6],破坏网络结构,玻璃化转变温度减小,热膨胀系数增大;ZnO含量的提高和热处理温度的升高对玻璃析晶能力没有明显的促进作用.     

铋掺杂铝硅酸盐玻璃的超宽带近红外发光性质

采用高温熔融法制备了组分为50SiO_2-xAl_2O_3-(50-x)MgO-Bi_2O_3(x=5,10,15,20,摩尔比)的铋掺杂铝硅酸盐玻璃。研究了铋掺杂铝硅酸盐玻璃超宽带近红外发光性质,探讨了玻璃基质的光学碱度对铋离子宽带发光特性的影响。结果表明:在690nm和808nm的激发下,铋掺杂铝硅酸盐玻璃的红外荧光中心分别位于1106nm和1294nm;随光学碱度的增强,铋离子的红外发光强度减弱。并对铋离子超宽带发光的机理进行了探讨,认为其红外发光源于低价的Bi~+和Bi~(2+)。     

Optical properties of bismuth tellurite based glass

A series of binary tellurite based glasses (Bi(2)O(3))(x) (TeO(2))(100-) (x) was prepared by melt quenching method. The density, molar volume and refractive index increase when bismuth ions Bi(3+) increase, this is due to the increased polarization of the ions Bi(3+) and the enhanced formation of non-bridging oxygen (NBO). The Fourier transform infrared spectroscopy (FTIR) results show the bonding of the glass sample and the optical band gap, E(opt) decreases while the refractive index increases when the ion Bi(3+) content increases.     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

SrO、La2O3、ZrO2对无铅水晶玻璃折射率,密度和耐碱性能的影响

熔融法制备不同氧化物含量的SiO2-B2O3 -R2O系无铅水晶玻璃,并表征了玻璃的密度、折射率和耐碱性能.结果表明:随着氧化锶含量的增加,玻璃密度、折射率和耐碱性能都随之增加;适量氧化镧(w(La2O3)≤22%)的加入可以提高玻璃的折射率、密度和耐碱性能,过量则反之;适量氧化锆的加入(w(ZrO2)≤28%)能够显著提高玻璃耐碱性能并提高玻璃折射率和密度,过多则促使玻璃析晶失透.     

掺Bi的MgO-CaO-Al_2O_3-SiO_2玻璃的吸收和近红外发光特性

研究了4种不同Bi_2O_3掺杂量(0.5%,1%,2%和3%,摩尔分数)的23MgO-11CaO-15Al_2O_3-51SiO_2(摩尔比)玻璃的发光特性。测量了吸收光谱、荧光光谱和荧光寿命。通过电子顺磁共振图谱观察了玻璃受γ辐射前后结构的变化,探讨了玻璃颜色变化和近红外发光的机理。结果表明:在500nm激发下,随着Bi_2O_3掺杂量从1%到3%的逐渐增加,发光波长发生红移,荧光半高宽从312nm增加到352 nm;最优的Bi_2O_3掺杂量为1%,玻璃的受激发射截面和荧光寿命的乘积为3.10×10~(-24)cm~2·s;γ辐射后发光强度的增加和玻璃颜色加深的现象说明Bi掺杂玻璃的近红外发光中心可能是低价态的Bi离子或者Bi团簇。     

Optical properties,thermal stability,and forming region of high refractive index La2O3–TiO2–Nb2O5 glasses

The high refractive index La₂O₃–TiO₂–Nb₂O₅ glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO_3/2–(70?x)TiO₂–xNbO_5/2 (0 ≤ x ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.     

氧化铋对浮法玻璃的结构与性能的影响

浮法玻璃的熔化是在非常高的温度下进行的且需要大量的能量。玻璃的熔化和澄清占总能耗的60%左右。氧化铋是一种非常有效的助熔剂,本文研究了氧化铋对浮法玻璃结构与性能的影响。研究表明：在浮法玻璃组成中引入氧化铋,没有改变玻璃的基本结构,Al2O3是以[AlO4]单元,Bi2O3是以[BiO6]为主要单元存在于玻璃的结构之中。随着Bi2O3含量的增加,玻璃抗折强度有所降低,玻璃的密度有所增加。     

Bi2O3-ZnO-B2O3低熔点封接玻璃的烧结特性

利用X射线衍射、扫描电子显微镜对Bi2O3-ZnO-B2O3系统低熔点玻璃的烧结性能、结晶特性以及烧结后玻璃试样的结构进行了研究.结果表明:随着B2O3含量的增加,玻璃的转变温度与软化温度都随之提高,影响了玻璃的烧结.Bi2O3-ZnO-B2O3系统低熔点玻璃粉末的烧结有黏性液相参与,使得玻璃试样的致密化更加有效,效率更高.当B2O3含量为5.24%(以质量计)时,玻璃的析晶倾向增大,试样中析出了Bi2482O39晶相.当温度继续升高时,试样的烧结收缩出现了"滞缓",有大量的液相出现,且在表面张力的作用F出现了流散.     

Thermal and optical properties of La2O3–Ga2O3– (Nb2O5 or Ta2O5) ternary glasses

La₂O₃–Ga₂O₃–M₂O₅ (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb₂O₅ and Ta₂O₅ drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga₂O₃ with Nb₂O₅, and the decrease in the Abbe number was significantly suppressed when Ta₂O₅ was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La₂O₃–Ga₂O₃–Ta₂O₅ glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.