Interactions of gamma rays with undoped and Mn-doped sodium phosphate glasses

Ultraviolet and visible spectroscopic measurements were used to investigate prepared undoped and Mn-doped sodium phosphate glasses before and after successive gamma irradiation. The effects of both glass composition and MnO₂ content on the generation of radiation-induced defects were investigated. Undoped sodium phosphate glass shows strong UV absorption, which is attributed to the presence of trace iron impurities present in the raw materials. Mn-doped glasses reveal an additional visible broad band centered at about 500 nm due to Mn³⁺, which has recently been related to the ⁵E_g →⁵T_2g transition. The radiation-induced bands are correlated with the generation of liberated electron–hole pairs during the process of gamma irradiation and the possibility of photochemical reactions especially with trace iron impurities and manganese ions. The intensity and the position of the induced bands are observed to depend on the type and composition of glass, concentration of the dopant and also on the irradiation dose. Manganese ions when present in relatively higher content have been found to show a shielding behavior towards the effects of progressive gamma irradiation causing a retardation of the growth of the induced defects. Infrared and Raman spectra of the undoped and Mn-doped glasses were measured to investigate the structural phosphate groups present and the effect of MnO₂ on the network structure. An ESR investigation was carried out to confirm the state of manganese ions in the prepared sodium phosphate glasses.     

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.     

Gamma ray interactions with MoO3-doped lead phosphate glasses

The UV–Visible, Fourier transform infrared (FTIR) and Raman and electron spin resonance (ESR) spectra of undoped lead phosphate and MoO₃-doped glassy samples have been investigated. The UV–VIS absorption spectra were re-measured after successive gamma irradiation. Before irradiation, undoped sample exhibited strong ultraviolet absorption, which was attributed to co-absorption due to trace iron impurities (mainly Fe³⁺ ions) and lead Pb²⁺ ions. With the introduction of MoO₃ in progressive amounts, extra visible bands were recorded at about 400–440, 540, 750 and 870?nm. These bands are most likely correlated with the presence of Mo³⁺, Mo⁴⁺ and Mo⁵⁺ ions in the host glass. In the undoped specimen, gamma irradiation produced UV absorption bands that increased slightly with irradiation but no visible bands were recorded. Samples containing high MoO₃ content showed some resistance to irradiation with no bands in the visible region being observed. FTIR absorption spectra of the undoped and MoO₃-doped samples revealed the formation of metaphosphate and pyrophosphate structural units. Highly MoO₃-doped samples exhibited additional bands due to molybdate groups. Raman and ESR spectra were in agreement with UV–VIS and IR data, indicating the presence of molybdenum ions in lead phosphate glass, as Mo³⁺, Mo⁴⁺ and Mo⁶⁺ with different ratios. However, such glassy systems favor the trivalent species.     

Bismuth silicate glass as host media for some selected rare-earth ions and effects of gamma irradiation

Ultraviolet, visible and infrared spectral measurements were used to investigate prepared undoped and rare-earth doped (2.5%) bismuth silicate glasses (80% Bi₂O₃–20%SiO₂) before and after being subjected to gamma irradiation (8?Mrad). The base bismuth silicate glass reveals strong extended UV–near visible absorption bands which are attributed to the presence of trace iron impurities in the raw materials together with absorption due to sharing of Bi³⁺ ions. The RE-doped samples show the same strong UV–near visible bands as the undoped glasses beside extra narrow characteristic bands mostly in the visible and near-infrared regions due to the respective studied rare-earth ions. The base undoped and all RE-doped samples except CeO₂ sample reveal quite resistance to the effect of gamma irradiation due to heavy atomic mass Bi³⁺ ions present in high content (80%) and the rare-earth ions are known to be weakly affected due to the known 5s, 5p shielding. The exceptional effect of CeO₂-doped sample is related to the ability of Ce³⁺ ions to change its oxidation state through photochemical reaction by irradiation or exchange with Fe³⁺ present as trace iron impurities. The FT infrared spectra of the prepared glasses reveal characteristic absorption bands which are related to the silicate groups together with the sharing of vibrational modes due to Bi–O groups. The IR spectra are slightly affected by gamma irradiation indicating the stability of the structural network groups consisting of SiO₄ and BiO₆ units.     

UV-visible and infrared absorption spectra of Bi2O3 in lithium phosphate glasses and effect of gamma irradiation

Ultraviolet and visible absorption spectra of prepared undoped lithium phosphate glass and samples of the same nominal composition with additional Bi₂O₃ contents were measured before and after being subjected to gamma doses of 3 and 6 Mrad. The base undoped lithium phosphate glass exhibits strong charge transfer ultraviolet absorption bands, which are related to unavoidable presence of trace iron impurities within the raw materials for the preparation of this glass. Bi₂O₃-containing glasses show the extension of UV absorption beside the resolution of visible bands at 400, 450, and 700 nm with the increase of Bi₂O₃ content due the sharing of absorption of Bi³⁺ ions. Gamma irradiation of the base glass reveals extended induced bands; the UV bands are related to the conversion of some Fe²⁺ to Fe³⁺ through photochemical reactions during the irradiation process. The visible induced bands are related to the formation of positive hole centers from the host phosphate glass. Glasses containing Bi₂O₃ are observed to show some shielding behavior, which is attributed to the presence of heavy weight and large atomic number of Bi³⁺ ions. Infrared absorption spectral measurements of the base lithium phosphate glass show characteristic vibrational modes which are related to specific phosphate groups. The addition of Bi₂O₃ in measurable percent produces additional vibrational bands due to the introduction of Bi–O groups such as BiO₃ and BiO₆.     

Optical properties of vanadium-doped bismuth borate glasses before and after gamma-ray irradiation

UV–visible, infrared and Raman spectra, together with thermal properties, were measured for glasses from the system Bi₂O₃–B₂O₃–V₂O₅ before and after successive gamma irradiations. The UV–visible spectrum of the undoped glass before irradiation reveals five UV bands at 210, 275, 310, 350 nm, an intense band at 380 nm and a visible band at 420 nm due to the possible combined presence of trace iron impurities and Bi³⁺ ions. The V-doped glasses reveal six UV bands and two visible bands, probably arising from vanadium ions in three possible valencies, V³⁺, V⁴⁺ and V⁵⁺, beside that due to trace iron impurity beside Bi³⁺ ions. The spectra reveal an obvious resistance of the glasses to successive gamma irradiation. The Raman and infrared spectra show characteristic absorption bands, which indicate the sharing of Bi³⁺ ions as glass-forming (BiO₆) octahedral units together with the presence of various groups of the borate network.     

UV-visible and infrared absorption spectroscopic studies of gamma irradiated tungsten-doped lithium phosphate glasses

Ultraviolet-visible and infrared spectroscopic techniques were employed to investigate the undoped lithium phosphate glass and other samples of the same composition doped with varying WO₃ contents. The same spectroscopic properties were remeasured after subjecting the samples to 3 and 6 Mrad doses of gamma irradiation on the measured properties. Such combined analytical techniques are expected to give information about the state of tungsten ions in such lithium phosphate glass and justify the effect of gamma irradiation. The work aims to deduce the radiation-induced defects generated through successive gamma irradiation by optical measurements. Also, the study is expected to realize through IR spectroscopy, the main structural building groups and the influence of tungsten ions within the structural vibrational groups of the studied glasses.     

Effect of gamma ray irradiation on optical properties of Nd doped phosphate glass

The effect of gamma irradiation in the dose range of 5-500 kGy on the optical absorption and luminescence spectra of Nd doped phosphate glass is reported. The spectral absorption of this glass before and after gamma irradiation was measured in the spectral range 300-900 nm at room temperature using spectrophotometer and synchrotron beamline. Drastic increase in absorption was noted below 600 nm after gamma irradiation, which was dependent on the dose of irradiation. Additional absorption (AA) spectra of irradiated sample shows generation of two absorption bands below 600 nm, which finally became one very broad band peak with increased intensity at irradiation dose of 500 kGy. AA spectra also show the presence of negative peaks at the location of absorption peaks of Nd³⁺. Photoluminescence of Nd doped phosphate glass shows two strong bands which decreases to a very low intensity with a red shift after gamma irradiation. These results indicate that irradiation produces different kinds of defects in the glass material along with conversion of valence state of Nd³⁺ to Nd²⁺. This change was found irreversible at room temperature.     

Modeling,Structural, and Spectroscopic Studies of Cobalt-doped Lithium Phosphate Glasses and Effect of Gamma Irradiation

Undoped and cobalt oxide-doped lithium phosphate glasses were prepared by normal melt annealing technique. The structure and optical properties were investigated in order to understand the spectroscopic properties and state of cobalt in this host glass. The glass samples were characterized by combined UV-Visible and Fourier transform infrared absorption spectroscopic techniques. Ultraviolet and visible spectroscopy is used to determine the optical absorption spectra of the base undoped glass and that due to the cobalt ions in this host glass. Spectroscopic investigations were approved using the density functional theory calculations, which were employed to interpret both theoretical and experimental IR data of this glass system and to identify the main building structural groups present in these glasses. Experimental results indicate that divalent cobalt ions occupy more than one coordination state, namely, the octahedral and tetrahedral forms. The changes in the UV-Vis and infrared spectral data are discussed in relation to the change in the state of cobalt ions with glass composition or dopant concentration or structural evolution caused by the changes in glass constituents.     

Optical characterization of the phosphate glasses containing pair transition ions

The paper deals with optical and electronic properties of the aluminophosphate glasses containing Fe–Mn and Fe–Cr ion pairs in different concentration. The influence of the mixed alkali ions over the electronic properties has been investigated. The optical behavior (optical transmission) of the glass samples has been studied by UV-VIS spectroscopy and the refractive index dependency on wavelength has been discussed. The transmission spectra show features specific for the doping transition ions (TM), revealing different oxidation states of iron (Fe²⁺/Fe³⁺), manganese (Mn²⁺/Mn³⁺) and chromium (Cr³⁺/Cr⁶⁺) in the vitreous network. Mössbauer spectroscopy offers information regarding the TM oxidation states, redox processes and the iron coordination symmetry in the vitreous network. In the case of Fe–Mn doped glasses, the percentage of Fe²⁺ is about 40% and a doubled iron content leads to an increasing of Fe²⁺ percentage up to 53%. The replacing of lithium ions by natrium ions (mixed alkali effect) provides an increasing of the Fe²⁺ percentage up to 56%. The occurrence of the tetrahedral or octahedral symmetry of Fe²⁺ ions bonded by O^2? ions depends on the transition ion nature and Li⁺/Na⁺ ratio. Infrared absorption spectra of the pair transition ions-doped aluminophosphate glasses reveal optical phonons specific for the phosphate glass matrix.     

Visible upconversion emissions in Pr3+-doped TeO2–ZnO glass

The Pr³⁺-doped tellurite zinc oxide (TZO) glasses by conventional melt and quenching technique have been prepared. The absorption spectra of samples doped with different concentrations of triply ionized praseodymium ions have been analyzed. Several upconversion emission bands of the Pr³⁺ ions doped in tellurite zinc oxide glasses under 980?nm excitation have been observed. The possible excitation mechanisms responsible for upconversion emissions spanning from blue to near infrared region have been discussed in detail.     

Luminescence properties of silver zinc phosphate glasses following different irradiations

We report on exposing a photosensitive zinc phosphate glass containing silver to different radiation (electron, gamma, optical). Laser irradiations using nanosecond ultraviolet (UV) and femtosecond infrared (IR) laser are compared with gamma and electron exposure. All irradiated glasses exhibit absorption maxima around 320 nm and 380 nm and emission in the visible spectral range. Following exposure, silver clusters are formed. The optical response of such species is investigated using absorption and fluorescence spectroscopic techniques. The mechanism of formation of these clusters is discussed.     

Effect of gamma irradiation on X‐ray absorption and photoelectron spectroscopy of Nd‐doped phosphate glass

X‐ray absorption near‐edge structure (XANES) and X‐ray photoelectron spectroscopy (XPS) of Nd‐doped phosphate glasses have been studied before and after gamma irradiation. The intensity and the location of the white line peak of the L₃‐edge XANES of Nd are found to be dependent on the ratio O/Nd in the glass matrix. Gamma irradiation changes the elemental concentration of atoms in the glass matrix, which affects the peak intensity of the white line due to changes in the covalence of the chemical bonds with Nd atoms in the glass (structural changes). Sharpening of the Nd 3d_5/2 peak profile in XPS spectra indicates a deficiency of oxygen in the glasses after gamma irradiation, which is supported by energy‐dispersive X‐ray spectroscopy measurements. The ratio of non‐bridging oxygen to total oxygen in the glass after gamma radiation has been found to be correlated to the concentration of defects in the glass samples, which are responsible for its radiation resistance as well as for its coloration.     

Optical Properties of Gamma Irradiated Soda-Lime Silicate Glasses Exchanged with Copper

The effect of copper ion exchange upon the optical absorption and room temperature gamma colouration of soda lime silicate glasses has been investigated. After ion exchange performed at 720 K, copper ions substitute mainly the alkali ions and do modify the optical absorption spectra of the specimens. It has been shown that gamma irradiation does not induce the formation of colloidal copper. Moreover, the colouration process itself is independent of the presence of copper ions. The generated colour centres are rather related to the presence of sodium and potassium ions. The optical bleaching by the UV light occurs in two stages. First disappear centres related to the Na-type defects and next those related to the K-type defects.     

Preparation and optical spectroscopy of phosphate glasses containing divalent europium ions

P2O5.BaO.Na2O.K2O glasses doped with various content of Eu2O3 were prepared using high temperature melting method, and the Eu2+ ions in the phosphate glasses were obtained with the aid of the reductive action of silicon powder. The fabricating conditions, fluorescence, excitation spectra of the glasses were then studied. The glasses containing europium show a broad emission band at 450 nm and sharp bands from 580 to 650 nm, and the co-existence of Eu2+ and Eu3+ is identified. Also, a good glass with a dominant proportion and large quantity of Eu2+ ions can be obtained by the reductive action of silicon powder and proper processing.     

Absorption phenomena in multicomponent phosphate glasses with Mn

The absorption and ESR spectra of multicomponent alumino-phosphate glasses doped with manganese (0·2–20 mol %) has been measured and compared with the absorption spectra of manganous and manganic ions in model solutions. The unirradiated glasses show in ultraviolet region increasing absorption below 200 nm with the shoulder at 235 nm and the absorption bands due to manganous oxygen complexes in octahedral symmetry. They are similar to the absorption bands of Mn²⁺ in concentrated H₃PO₄ acid. In irradiated glasses the bands at 200, 235, 275 (only if Mn is present) and a broad band at 540 nm appear. After the annealing at 450 C all radiation-induced bands disappear and the bands at 235 nm is more pronounced. The Mn³⁺ in H₃PO₄ solution exhibit the absorption spectrum with a weak band at 530 nm and a very intense band at 270 nm. It is therefore proposed that both the 540 and 275 nm bands in irradiated glasses can be assigned to octahedral oxygen complexes of Mn³⁺, i.e. to hole centres. The band at 200 nm which is practically independent of the modifiers (Be, Mg, Ca, Sr and Ba) is, therefore, associated with electron centres (electrons trapped in non-bridging oxygen vacancies). It is suggested that the band at 235 nm in irradiated and annealed glasses is associated with irreversible structural changes.The authors wish to express their appreciation to H.Dvoáková for preparing the solutions and E.Linhartová for careful measurements.     

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.     

掺铜磷酸盐和氟磷酸盐玻璃的光谱研究

本文对掺铜Ca-Al磷酸盐玻璃和、Na-Mg-Ca-Sr-Ba-Al氟磷酸盐玻璃分别作了吸收光谱、ESR谱、激发光谱、荧光光谱和荧光寿命测定。实验结果表明,玻璃中的Cu2+在近红外有一吸收带,属于畸变0h格位中2Eg→2T2g的跃迁。Cu+在紫外区有一吸收带,属于3d10→3d94s1跃迁。用紫外激发,玻璃中Cu+在可见区有一较宽的发光带。磷酸盐玻璃中,荧光峰值位于458nm。氟磷酸盐玻璃中,荧光峰值位于420nm。前者荧光寿命为26μs,后者为60μs。     

Surface plasmons for fluorescence enhancement in Sm-doped borate glasses

Heat treatment of Sm-activated lithium and sodium borate glasses which are additionally doped with silver oxide leads to a reduction of the doped silver ions and to the formation of metallic silver nanoparticles indicated by a broad plasmon-related absorption band in the visible spectral range. The influence of the plasmon resonance field enhancement on the Sm³⁺ fluorescence excitation bands is too small to lead to enhanced fluorescence emission intensities.     

Ion transport studies in zinc/cadmium halide doped silver phosphate glasses

A number of samples of silver phosphate glasses Ag₂O−P₂O₅−Zn/CdX₂ (X=Cl, Br or I) with 1, 5, 10 and 20 mol-% zinc or cadmium halides have been prepared. Control samples of undoped silver phosphate glasses were also prepared. These glasses were characterized by elemental analysis, X-ray diffraction, IR spectra, differential scanning calorimetry, transference number measurements and electrical conductivity studies. These glasses were found to be essentially ionic conductors. The undoped silver phosphate glass (Ag₂O−P₂O₅) has a low σ value in comparison to the doped ones. The conductivity (σ) in the doped glasses increases substantially with increasing concentration of dopant salts Zn/or CdX₂ and as the anions of the dopants are changed from Cl⁻ to I⁻. It is found that the σ values of the ZnX₂ doped glasses are slightly greater than those of the CdX₂ doped ones, and the silver phosphate glasses doped with (20 mol-%) Zn/CdI₂ yielded maximum conductivity. The results have been discussed and explained on the basis of changes in the structure of the glass matrix by the addition of dopant ions of different sizes, IR spectra and thermal studies.