Effect of some doping elements on the ionic conduction of mixed alkali-alumino-borosilicate glasses

Summary Some borosilicate glasses containing an equimolar ratio of different alkali types (K⁺ and Na⁺ ions) doped with 0.1 mole% R (R=Mn, Tb, Y, or Gd) were prepared. The results of d.c. electrical conductivity show that the absolute values of resistivities and the corresponding activation energies for the doped glasses are lower than those for glasses without doped ions. This behaviour is explained on the basis of the formation of elastic dipoles in such glasses and of the change of their fields owing to the existence of the doping ions. By thermal treatment of these glasses, it is found that the activation energies for the doped glasses are different from those obtained for glassess prepared without doping ions. This peculiarity is explained on the basis of the phase separation process in such glasses.     

Tb~(3+)激活的重金属氧化物闪烁玻璃的发光性能研究

采用高温熔融法制备了不同Ln2O3(Ln=Lu,Y,Gd)情况下Tb3+激活的重金属氧化物闪烁玻璃样品。测试了不同Ln2O3玻璃样品的密度,差热特性,透过、发射和激发光谱。着重研究了玻璃成分中不同稀土氧化物对闪烁玻璃的密度及发光性能的影响规律及机理。结果表明:在含Ln2O3闪烁玻璃中,含Lu2O3硅硼酸盐玻璃的密度最高,接近6g/cm3,发光强度性能最差。含Gd2O3硅硼酸盐玻璃的密度接近含Lu2O3硅硼酸盐玻璃的密度,其发光强度最大。其原因是Gd3+离子能把能量以共振能量传递的形式给Tb3+离子,提高Tb3+离子的发光强度。但当Gd3+离子浓度增大到一定程度时,能量传递的效率却明显减弱。含Gd3+离子的闪烁玻璃密度较高,发光强度大,是一种很有前景的闪烁材料。     

Effect of rare earth (Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3 and Er2O3 ) on the acoustic properties of glass belonging to bismuth-borate system

Bismuth-borate glasses doped with some rare earth ions were studied with respect to the density, molar volume and the elastic moduli, Poisson’s ratio, Debye temperature, microhardness, softening temperature, acoustic impedance, diffusion constant and latent heat of melting. Ultrasonic velocities were measured by the pulse echo overlap technique at a frequency of 10 MHz and at room temperature. From these velocities and density values, various elastic moduli were calculated. The correlation of elastic stiffness, the cross link density, and the fractal bond connectivity of these glasses are discussed. The derived experimental values of shear modulus, bulk modulus, Young’s modulus, and Poisson’s ratio for our glasses are compared with the theoretically calculated values in terms of the bond compression model and Makishima-Mackenize theory.     

Sb3+对Tb3+激活硅酸盐玻璃发光性能的影响

利用高温熔融法分别制备了Sb3 ,Tb3 单掺和共掺的硅酸盐发光玻璃,并分析了它们的光谱性质。根据对Sb3 和Tb3 掺杂硅酸盐玻璃的激发光谱、发射光谱和发光衰减时间等特性的分析,研究了澄清剂Sb2O3的加入对Tb3 激活硅酸盐玻璃发光性能的影响。结果表明,在紫外光激发下,Tb3 激活硅酸盐玻璃中存在Sb3 离子至Tb3 离子的能量传递,但能量传递效率较低,能量传递表现为Sb3 离子的3P1能级与Tb3 离子的5D3能级之间的能量无辐射共振转移。同时Sb3 离子的加入将在Sb3 离子和Tb3 离子的激发重叠区域(200～350nm)对Tb3 离子的激发产生不小的负面影响,尚不足以通过Sb3 离子至Tb3 离子的能量传递得以弥补。因此在使用Sb2O3作为Tb3 激活硅酸盐发光玻璃的澄清剂时,应当注意权衡Sb3 离子对Tb3 离子发光性能的影响。     

Bismuth silicate glass containing heavy metal oxide as a promising radiation shielding material

Optical and FTIR spectroscopic measurements and electron paramagnetic resonance (EPR) properties have been utilized to investigate and characterize the given compositions of binary bismuth silicate glasses. In this work, it is aimed to study the possibility of using the prepared bismuth silicate glasses as a good shielding material for γ-rays in which adding bismuth oxide to silicate glasses causes distinguish increase in its density by an order of magnitude ranging from one to two more than mono divalent oxides. The good thermal stability and high density of the bismuth-based silicate glass encourage many studies to be undertaken to understand its radiation shielding efficiency. For this purpose a glass containing 20% bismuth oxide and 80% SiO₂ was prepared using the melting–annealing technique. In addition the effects of adding some alkali heavy metal oxides to this glass, such as PbO, BaO or SrO, were also studied. EPR measurements show that the prepared glasses have good stability when exposed to γ-irradiation. The changes in the FTIR spectra due to the presence of metal oxides were referred to the different housing positions and physical properties of the respective divalent Sr²⁺, Ba²⁺ and Pb²⁺ ions. Calculations of optical band gap energies were presented for some selected glasses from the UV data to support the probability of using these glasses as a gamma radiation shielding material. The results showed stability of both optical and magnetic spectra of the studied glasses toward gamma irradiation, which validates their irradiation shielding behavior and suitability as the radiation shielding candidate materials.     

Physical and Optical Properties of Calcium Zinc Borophosphate Glasses Doped with Manganese Ions

This article reports on the physical and optical properties, absorption, and luminescence spectra in the visible region, of calcium zinc borophosphate glasses doped with manganese ions. The manganese composition was varied up to 10 mol%. The aim of this work was to investigate the effect of the luminescence properties when the glasses were doped with different compositions of manganese ions. X-ray diffraction profiles confirmed their glassy nature. The optical absorption spectrum showed bands characteristic of manganese ions in octahedral symmetry. Both excitation and emission spectra were recorded for these glasses to understand their optical performances. The emission spectrum showed a single broad band (green region) in octahedral symmetry at 582 nm as a result of transition from the upper ⁴T_1g state to the ⁶A_1g ground state of manganese ions. As the concentration of manganese ions increased, the emission band increased from 582 nm (green-light emission) to 650 nm (red-light emission). Apart from the spectral analysis, different physical properties of these glasses were also analyzed. Based on the physical and optical properties, we found the samples to be more promising for their use as novel luminescent optical materials.     

Tm3+-Doped Oxyfluoride Silicate Glasses for TDFA

The fluorine doping along with heavy metal oxides was remarkably raised the lifetime and the quantum efficiency of 3H4 in silicate glasses. The fluorine doping changed the local structure around Tm3+ ions, then low energy vibrations related to fluorine are considered to largely reduce the multi-phonon relaxation rates in the oxyfluoride silicate glasses.     

氟化物、氟磷酸盐和磷酸盐玻璃中Er3+离子的发光研究

测定了氟化物、氟磷酸盐和磷酸盐玻璃中Er³⁺离子的吸收、荧光和激发光谱,解释了基质玻璃对Er³⁺离子发光的影响。进一步研究了在这三种基质玻璃中Er³⁺离子发光的浓度效应和温度效应,讨论了Er³⁺离子内和离子间的能量转移过程。 关键词：     

磷酸盐、锗酸盐和碲酸盐玻璃中Ce3+、Tb3+、Er3+和Tm3+离子的发光和敏化作用的研究——Ⅱ.辐射跃迁、无辐射跃迁和能量转移

对不同玻璃基质中的Tb3+、Er3+和Tm3+离子的辐射跃迁和无辐射跃迁速率进行了计算和测量,并讨论了基质玻璃对跃迁特性的影响。研究了Ce3+对Er3+、Tm3+,Tb3+的敏化作用,得出Ce3+对Er3+离子的敏化作用是弱的,而Ce3+对Tm3+和Tb3+是较强的,并对敏化机理进行了讨论。     

Identification of Multiply Charged Ions by Means of Detectors Based on Phosphate Glass

Physics of Atomic Nuclei - The detection and identification of heavy ions in phosphate glasses is based on an analysis of geometric parameters of tracks that manifest themselves upon the etching of...     

Structural and magnetic properties of CaO-P2O5-SiO2-Fe2O3 glass-ceramics for hyperthermia

Calcium–silica–phosphate glasses containing iron were partially crystallised to obtain a glass-ceramic system, applicable in hyperthermia treatments. The increasing iron content determines a higher glass transition temperature and the disposal of iron ions in small clusters. The magnetisation values for vitroceramic samples suggest that the main contribution to magnetisation is due to iron ions from magnetite.     

Eu~(3+)作探针研究铋铕共掺硼硅酸盐玻璃光学特性

利用高温烧结法制备了铕/铋铕共掺硼硅酸盐玻璃系列样品,测量了样品的激发光谱、发射光谱和声子边带谱,利用Eu3+离子作为探针进一步研究了敏化剂Bi3+的掺入对Eu3+发光的影响.结果表明:本文制作的玻璃样品的电子-声子耦合系数比以往报道过的硼铅等玻璃材料的值都要小,但在硼硅酸盐玻璃中掺入Bi3+会使Eu3+的无辐射跃迁概率增加;Bi3+对Eu3+有敏化作用,Bi3+的掺入使材料的共价性增强,对称性降低,这又使得Eu3+的发光整体变强.所以,在硼硅酸盐玻璃体系中,Eu3+发光的增强不仅仅是由于Bi3+对Eu3+的能量传递,而是以上各因素综合作用的结果.     

Li~+对Tb~(3+)掺杂硅酸盐玻璃闪烁性能的影响

利用高温熔融法制备了Li+掺杂Tb3+激活硅酸盐闪烁玻璃。通过Li+掺杂Tb3+激活硅酸盐玻璃的紫外可见透射光谱、发射光谱和发光衰减时间谱,研究了Li+的加入对Tb3+掺杂硅酸盐玻璃发光性能的影响。结果表明:适量Li+的加入可有效增强Tb3+激活硅酸盐玻璃的发光强度,且相比于不掺杂Li+的Tb3+掺杂硅酸盐玻璃而言,当掺入质量分数为2.0%的Li+时,Tb3+在玻璃中的最佳掺杂质量分数由12.8%提高至15.3%。其原因是Li+掺杂增加了玻璃体系中非桥氧的数量,从而有利于改善Tb3+在玻璃体中的均匀性,降低Tb3+间因非辐射跃迁而引起的能量损失,以及提高Tb3+的最佳掺杂质量分数。但当掺入Li+的质量分数超过2.0%时,会对Tb3+激活硅酸盐玻璃的闪烁光强产生负面影响,这是因为过多的非桥氧阻碍了X射线激发能达到Tb3+离子的能量传递。     

Eu2+掺杂P2O5-BaO-Na2O-K2O与Na2O-TeO2-ZnO系统玻璃的制备与光谱性质

用高温熔融法,把Eu₂O₃掺入到P₂O₅-BaO-Na₂O-K₂O与Na₂O-TeO₂-ZnO系统玻璃中。测定了玻璃的荧光光谱与激发光谱。结果表明,Eu离子在P₂O₅-BaO-Na₂O-K₂O玻璃中呈现出Eu³⁺态。然而在Na₂O-TeO₂-ZnO系统玻璃中,尽管在空气气氛下,大部分的Eu离子在玻璃中以二价的状态存在。从玻璃的结构及化学组分解释了产生Eu²⁺的原因。在磷酸盐玻璃配料中加入适量的硅粉(Si)作还原剂,能有效地把玻璃中的极大部分Eu³⁺还原成Eu²⁺,获得含Eu²⁺的优质透明磷酸盐玻璃。     

硫系玻璃的N^＋离子注入及表面改性研究

首次对Ａｓ－Ｇｅ－Ｓｅ三元系统和Ａｓ－Ｇｅ－Ｓｅ－Ｔｅ四元系统的硫系玻璃试样进行了Ｎ＋离子注入试验。结果表明，玻璃试样的显微硬度随Ｎ＋离子注入剂量的增加而提高，并且在注入剂量达到２．５×１０１６附近的数值时为最大。ＸＰＳ谱结果显示，在Ａｒ＋离子轰击６分钟后的试样表面出现Ｎ１ｓ的结合能峰，此外各元素的结合能峰也在Ｎ＋离子注入后发生了位移，并随Ａｒ＋离子轰击时间向高能方向移动。     

Fluorescence yield in rare-earth-doped sol-gel silicate glasses

We have used trivalent terbium to investigate the mechanism behind fluorescence enhancement by Al³⁺ co-doping. Our results indicate that rare-earth (RE) ions cluster together in aluminum-rich regions of the glass, and behave as if they were dispersed uniformly throughout these regions when the ratio of Al to RE is ∼10 or greater. We also studied the effects of adding chemical drying agents to the precursor solution for the synthesis of sol-gel-derived silicate glasses. Such glasses can be treated at significantly higher annealing temperatures without degradation of optical quality, and have the density of melt glass. Fluorescence yield from doped RE ions improves markedly with the addition of the drying agents, and the denser glasses are not subject to rehydration.     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.     

Electric conductivity and relaxation in ZnF2–AlF3–PbF2–LiF glasses

The electric conductivity of ZnF₂–AlF₃–PbF₂–LiF glasses has been studied in the frequency range 10 Hz–2 MHz and in the temperature range from 300 K to just below the glass transition temperature. The conductivity decreases with the increase in the LiF content in the composition, which results from the trapping of F⁻ ions by Li⁺ ions. Small values of the stretching exponent β are observed for the present glasses. The value of the decoupling index decreases with an increase in LiF content, consistent with the composition dependence of the conductivity.     

Laser spectroscopy of rare earth ions in lead borate glasses and transparent glass-ceramics

Rare earth doped lead borate glasses and transparent glass-ceramics have been studied using optical spectroscopy. Based on the absorption, emission and its decay and the Judd-Ofelt calculations, several radiative and laser parameters for Ln ³⁺ (Ln = Pr, Nd, Eu, Dy, Er, Tm) were evaluated. The large values of luminescence lifetime, quantum efficiency of excited state and room temperature peak stimulated emission cross-section suggest efficient laser transitions of Ln ³⁺ ions in lead borate glasses. The obtained results indicate that lead borate glasses and glass-ceramics containing Ln ³⁺ ions are promising host matrices for solid-state laser applications.     

Effect of neutron-irradiation on optical properties of SiO2-Na2O-MgO-Al2O3 glasses

Silica based glasses are used as nuclear shielding materials. The effect of radiation on these glasses varies as per the constituents used in these glasses. Glasses of different composition of SiO₂-Na₂OMgO-Al₂O₃ were made by melt casting techniques. These glasses were irradiated with neutrons of different fluences. Optical absorption measurements of neutron-irradiated silica based glasses were performed at room temperature (RT) to detect and characterize the induced radiation damage in these materials. The absorption band found for neutron-irradiated glasses are induced by hole type color centers related to non-bridging oxygen ions (NBO) located in different surroundings of glass matrix. Decrease in the transmittance indicates the formation of color-center defects. Values for band gap energy and the width of the energy tail above the mobility gap have been measured before and after irradiation. The band gap energy has been found to decrease with increasing fluence while the Urbach energy shows an increase. The effects of the composition of the glasses on these parameters have been discussed in detail in this paper.