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.     

γ辐照后硼硅酸盐玻璃的吸收光谱研究

玻璃固化体是用来固化放射性废物的硅酸盐。作为放射性废物处理的第一道工程屏障,它的耐辐照性能尤其引人注目。本工作使用硼硅酸盐玻璃模拟玻璃固化体材料,用不同剂量的γ射线辐照硼硅酸盐玻璃模拟天然放射性对固化体的辐照损伤。通过测量和分析辐照后硼硅酸盐玻璃的吸收光谱,证实了辐照后在玻璃中产生了E'缺陷,非桥氧空位色心、过氧自由基以及过桥氧联接等缺陷。此外,还得出了不同微观结构随吸收剂量的演化关系。对于辐照后产生的缺陷,它们的浓度都随吸收剂量的增加而增大。同时,发现玻璃在辐照后其吸收光谱的带隙随着剂量的增加而逐渐变窄;而当吸收剂量大于等于105 Gy时,玻璃的带隙则达到饱和值。Vitrification is one kind of silicates which is used for immobilization of high-level waste (HLW). As the first engineered barrier of HLW disposition, its anti-irradiation characteristic is particularly noticeable. Vitrification is replaced by borosilicate glass to investigate radiation effect, and the irradiation damage generated by natural radioactivity in vitrification is simulated by different doses gamma rays on borosilicate glass. By measuring and analyzing the absorption spectrum of irradiated borosilicate glasses, it is confirmed that E'defect, non-bridging oxygen hole center, peroxy dangling bond and bridge oxygen link, etc. are induced in borosilicate glass after irradiation. Furthermore, the relations between the defects and absorbed doses are shown. For the concentrations of these defects induced by irradiation, all of them increase with absorbed dose. Meanwhile, absorption band gap in borosilicate glass after irradiation decreases with absorbed dose and the band gap becomes saturated when absorbed dose is equal to or greater than 105 Gy.     

FTIR structural investigation of gamma irradiated BaO–Na2O–B2O3–SiO2 glasses

Fourier transform infrared (FT-IR) spectra of xBaO–15Na₂O–(70−x)B₂O₃–15SiO₂ glass system with x=0, 5, 10, 15 and 20 (mol%) has been measured in the spectral range 400–4000 cm⁻¹ at room temperature in order to understand the characteristic frequencies of the chemical bonds and bonding mechanisms, which are susceptible to the structural and spectral changes. The effect of gamma irradiation in the dose range 0.1 kGy–60 kGy on the infrared absorption spectra of these glasses is also reported. The change in the glass structure due to the effect of composition is also discussed. It has been observed that irradiation of the glasses with the gamma rays increases the BO₃ groups and the non bridging oxygens which make the network loose.     

Solid-state NMR study of bioactive binary borosilicate glasses

A series of binary borosilicate glasses prepared by the sol-gel method are shown to be bioactive. Tetraethyl orthosilicate (TEOS) and trimethylborate (TMB) in acidic medium are used to prepare xB₂O₃·(1−x)SiO₂ glass systems for x=0.045-0.167. The formation of a layer of apatite-like mineral on the glass surface becomes apparent after soaking in simulated body fluid for 48 h. We have measured the ¹¹B-¹¹B homonuclear second moments of the borosilicate glasses and inferred that no macroscopic phase separation occurred in our glasses. The ¹¹B chemical shift data also show that the formation of clustered boroxol rings is negligible in our glass system. Although the bioactivity of our borosilicate glasses is less than that of CaO-SiO₂ sol-gel glasses, these simple binary systems could be taken as reference glass systems for the search of new bioactive borosilicate glasses.     

Magnetic properties of MnO nanocrystals dispersed in a silica matrix

Magnetic nanocrystalline MnO particles have been synthesized in a silica glass matrix by the sol-gel method at calcination temperatures up to 1000 °C. EPR spectra of 0.1 mol% MnO doped silica gel and glasses studied in the temperature range 10-290 K show with the exception of those samples calcined at 900 and 1000 °C 6-line characteristic Mn(II) hyperfine (HF) lines. Additionally five spin-forbidden doublets have been observed at 100 K and below. Small spreads in spin Hamiltonian parameters (D and E) imply that the ligand field environments of Mn(II) ions embedded in the silica glass are nearly uniform. Monotonous decrease in HF linewidth in going from 120 °C gel to 800 °C calcined glass has been interpreted as the continuous decrease in population of isolated Mn²⁺ ions in silica glass matrix resulting in the decrease of magnetic dipolar interactions leading to the observed decrease in HF linewidth. XRD and TEM of sample calcined at 1000 °C shows the presence of nanocrystals of MnO having orthorhombic crystalline phase and sizes about 10 nm. The thermal behavior of magnetization (zero-field-cooled and field-cooled) and magnetic hysteresis of MnO nanocrystals in the 5-300 K temperature interval have demonstrated that the MnO nanocrystals display superparamagnetic-ferromagnetic transition at low temperatures. X-band EPR linewidth data plotted versus inverse of temperature (1/T) for samples calcined at 900 and 1000 °C (EPR recorded in the vicinity of 0.35 T applied field) depict similar transitions.     

Investigation of gamma radiation induced changes in local structure of borosilicate glass by TDPAC and EXAFS

Gamma radiation induced changes in local structure around the probe atom (Hafnium) were investigated in sodium barium borosilicate (NBS) glass, used for immobilization of high level liquid waste generated from the reprocessing plant at Trombay, Mumbai. The (NBS) glass was doped with ¹⁸¹Hf as a probe for time differential perturbed angular correlation (TDPAC) spectroscopy studies, while for studies using extended X-ray absorption fine structure (EXAFS) spectroscopy, the same was doped with 0.5 and 2 % (mole %) hafnium oxide. The irradiated as well as un-irradiated glass samples were studied by TDPAC and EXAFS techniques to obtain information about the changes (if any) around the probe atom due to gamma irradiation. TDPAC spectra of unirradiated and irradiated glasses were similar and reminescent of amorphous materials, indicating negligible effect of gamma radiation on the microstructure around Hafnium probe atom, though the quaqdrupole interaction frequency (ω _Q) and asymmetry parameter (η) did show a marginal decrease in the irradiated glass compared to that in the unirradiated glass. EXAFS measurements showed a slight decrease in the Hf-O bond distance upon gamma irradiation of Hf doped NBS glass indicating densification of the glass matrix, while the cordination number around hafnium remains unchanged.     

Substrate effect on excimer laser assisted crystal growth in phosphor Ca0.997Pr0.002TiO3 polycrystalline thin films

Ca_0.997Pr_0.002TiO₃ thin films that show strong red luminescence were successfully prepared by means of an excimer laser assisted metal organic deposition process with a KrF laser at a fluence of 100 mJ/cm² at 100 °C. The CPTO films grew on the silica, borosilicate, and indium-tin-oxide coated glasses. The crystallinity of the Ca_0.997Pr_0.002TiO₃ films depended on the substrates; the borosilicate and indium-tin-oxide coated glasses with a large optical absorption of a KrF laser (λ = 248 nm) were effective for the crystallization for the Ca_0.997Pr_0.002TiO₃. In addition, a high thermal conductivity of the indium-tin-oxide coated glass substrate could also improve the crystallinity due to an enhancement of thermal propagation to the film. Oxygen annealing at 500 °C for 6 h successfully eliminated the oxygen vacancy produced by the laser irradiation, and also remarkably improved the PL emission intensity. Thus, we have shown that substrate properties such as an optical absorbance and a thermal conductivity were quite important factors for the crystal growth and the PL emission for the Ca_0.997Pr_0.002TiO₃ in the excimer laser assisted metal organic deposition process.     

UV-vis spectroscopic Investigation on γ-irradiated alkali aluminoborate glasses

This research paper reports about the change in optical spectra of alkali aluminoborate glasses under high dose of gamma irradiation. Effect of irradiation on visible spectra finds remarkable applications in optoelectronic materials.Glasses with a host matrix composed of M₂O (where M=Na, K)_, Al₂O_3, B2O3 were prepared by conventional melt quench technique. Gamma irradiation was performed at a dose-rate of 573 Gy/h to a total dose of 50 kGy. Samples were characterised before and immediately after irradiation by UV-vis transmission spectra in the range of 200-800 nm. The induced absorption coefficient and loss of transmission due to irradiation were attributed to the nature of alkali metals as well as the host matrix.     

Electron paramagnetic resonance and the thermoluminescence emission mechanism of the 280 °C peak in natural andalusite crystal

Samples of natural andalusite (Al₂SiO₅) crystal have been investigated in terms of thermoluminescence (TL) and electron paramagnetic resonance (EPR) measurements. The TL glow curves of samples previously annealed at 600 °C for 30 min and subsequently gamma-irradiated gave rise to four glow peaks at 150, 210, 280 and 350 °C. The EPR spectra of natural samples heat-treated at 600 °C for 30 min show signals at g=5.94 and 2.014 that do not change after gamma irradiation and thermal treatments. However, it was observed that the appearance of a paramagnetic center at g=1.882 for the samples annealed at 600 °C for 30 min followed gamma irradiation. This line was attributed to Ti³⁺ centers. The EPR signals observed at g=5.94 and 2.014 are due to Fe³⁺. Correlations between EPR and TL results of these crystals show that the EPR line at g=1.882 and the TL peak at 280 °C can be attributed to the same defect center.     

Electrical studies on bulk Se96Sn4 semiconducting glass before and after gamma irradiation

Bulk Se₉₆Sn₄ chalcogenide glass was prepared by melt quenching technique and irradiated by different doses of 4, 8, 12, 24 and 33 kGy using ⁶⁰Co gamma emitter. I-V characteristics were obtained for this glass, before and after gamma irradiation, in the temperature range 200-300 K. Ohmic behavior was observed at low electric fields (≤1×10⁴ V/m), while at higher fields, a deviation from ohmic towards non-ohmic behavior was observed. The plots of ln(I/V) vs. V were found to be straight lines and the slopes of these lines decrease linearly with temperature indicating the presence of SCLC. In the temperature range of measurements, the dependence of DC conductivity on temperature at low electric field shows two types of conduction channels, one in high temperature range 270-300 K and the other at low temperature range 200-270 K. Analysis of the experimental data shows that the conductivity at room temperature decreases with increase in irradiation dose. This is attributed to rupturing of SnSe_4/2 structural units, upon irradiation, and rebuilt of Se atoms between Se chains. This redistribution of bonds, induced by gamma irradiation, is responsible for the corresponding increase in the activation energy. The obtained values of the activation energy indicate that the conduction occurs due to thermally assisted charge carriers movement in the band tail of localized states. However, in the low temperature range, results obtained from Mott’s variable range hopping (VRH) model reveal that the density of localized states has its maximum value at a gamma dose of 12 kGy, while the disorder parameter T_o, hopping distance R_hop and hopping energy W have their minimum value at this particular dose.     

Xe离子束辐照硼硅酸盐玻璃和石英玻璃效应对比研究

玻璃固化体作为放射性废物地质处置的第一道安全屏障,它的耐辐照性能研究至关重要.玻璃固化体主要网络结构硅氧四面体与石英玻璃的硅氧四面体是一致的,所以这里用石英玻璃代替玻璃固化体作为研究对象.本文采用Xe离子在相同条件下辐照石英玻璃和硼硅酸盐玻璃.利用纳米压痕技术和椭圆偏振仪表征了辐照前后样品的硬度、模量以及折射率的变化情况.结果表明:硼硅酸盐玻璃和石英玻璃的硬度均随着辐照剂量的增大而减小,硼硅酸盐玻璃的模量随着辐照剂量的增大而减小;石英玻璃的模量随着辐照剂量的增大而增大.模量的变化可能和密度的变化有关,这点与折射率的结果相符.     

Response of commercial window glass to gamma doses

This work reports experimental results of an effort undertaken to identify and characterize the radiation-induced defects created during gamma (γ)-irradiation of commercial glass on the basis of optical absorption measurements performed before and after irradiation. It is assumed that the induced absorption band formed after γ-irradiation of soda-lime-silica (SLS) glasses are created by some hole-type color centers related with non-bridging oxygen ions (NBO⁻) located in different surroundings.Results have been discussed taking into consideration the presence of iron as impurity in the glass structure. It is well known that the absorption bands of Fe³⁺ in the visible range is at 420-440 nm, in this study the band at 430 nm was followed. Also, the optical gap variations (ΔE_opt) induced by γ-irradiation were investigated.Moreover, the study illustrated that the optical absorption sensitivity and the mechanism of fading either at room or elevated temperature has been discussed in relation to successive irradiation doses, dose rate and thickness. The results are discussed on the basis of the annihilation mechanisms of induced irradiation defects.     

A rapid combustion process for the preparation of MgSrAl10O17:Eu phosphor and related luminescence and defect investigations

Blue-emitting europium-ion-doped MgSrAl₁₀O₁₇ phosphor, prepared using the combustion method, is described. An efficient phosphor can be prepared by this method in a muffle furnace maintained at 500 °C in a very short time of few minutes. The phosphor is characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and BET surface area measurements. Photoluminescence (PL) spectra revealed that europium ions were present in divalent oxidation state. The thermoluminescence (TL) glow curve shows two peaks at around 178 and at 354 °C. The defect centres formed in the phosphor are studied using electron spin resonance (ESR). The ESR spectrum indicates the presence of Fe³⁺ ions in the non-irradiated system. Irradiated MgSrAl₁₀O₁₇:Eu exhibits lines due to radiation-sensitive Fe³⁺ ion and a defect centre. The centre is characterized by an isotropic g-value of 2.0012 and is assigned to a F⁺ centre. The radiation-sensitive Fe³⁺ ion appears to correlate with the main TL peak at 178 °C. During irradiation an electron is released from Fe²⁺ and is trapped at an anion vacancy to form F⁺ centre. During heating, an electron is liberated from the defect centre and recombines with Fe³⁺ emitting light.     

Luminescence and EPR studies of YBO3:U

Yttrium borate doped with uranium was prepared by mixing and heating yttrium oxide obtained through oxalate precipitation route, boric acid and requisite amount of nuclear-grade uranium oxide at high temperature. Photoluminescence (PL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on gamma-irradiated doped/undoped yttrium borate samples in the temperature range 300-600 K. TSL studies showed the presence of two glow peaks at 414 and 471 K. PL studies along with lifetime decay investigation suggested uranium goes in the matrix as UO₂²⁺. EPR studies showed the presence of O₂⁻radical ion along with electron trapped in defect centres, which might have been produced for charge compensation. Apart from this, CO₂⁻ radical was also observed in the system having its origin from residual oxalate ion. Temperature dependence EPR studies of the observed radical confirmed the involvement of the CO₂⁻ and dioxide radical ion in the observed glow peaks. By correlating the TSL, PL and ESR data, probable mechanism is proposed for the observed TSL glow in the system.     

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.     

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 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.     

Visible luminescence of Al2O3 nanoparticles embedded in silica glass host matrix

This paper deals with the sol-gel elaboration and defects photoluminescence (PL) examination of Al₂O₃ nanocrystallites (size ∼30 nm) confined in glass based on silica aerogel. Aluminium oxide aerogels were synthesized using esterification reaction for hydrolysis of the precursor and supercritical conditions of ethyl alcohol for drying. The obtained nanopowder was incorporated in SiO₂ host matrix. After heating under natural atmosphere at 1150 °C for 2 h, the composite Al₂O₃/SiO₂ (AS) exhibited a strong PL bands at 400-600 and 700-900 nm in 78-300 K temperature range. PL excitation (PLE) measurements show different origins of the emission. It was suggested that OH-related radiative centres and non-bridging oxygen hole centres (NBOHCs) were responsible for the bands at 400-600 and 700-900 nm, respectively.     

Change of conduction mechanism with gamma dose of irradiated borosilicate glasses containing copper ions

The d.c. electrical resistivity of sodium borosilicate glasses containing copper ions has been measured at the temperature range 300–623 K before and after gamma irradiation. The results obtained indicate that conduction may proceed ionically for the unirradiated glasses, with an activation energy in the range 23–24.2 Kcal/mol. Relatively low gamma doses (3.6–25 Mrads) induce two regions, separated at a critical temperature (T_c), of different activation energies. An activation energy E₁, 3.4 Kcal/mol, in the temperature range from 300–370 K, and E₂ 16.8–20.9 Kcal/mol, in the range of higher temperatures. The mechanism suggested is that the ionic conduction is replaced by an electronic one up to about 370 K then seems to be replaced at higher temperature region by ionic-like mechanism which can be expressed by exciton-like process. High gamma doses (28.33 M rads) cause the glasses to have activation energy ranges between 19.9–22.7 Kcal/mol, which may substantiate the predominance of the proposed ionic-like mechanism.The transition region around T_c seems to be divided into three regions, precritical, critical and post-critical.     

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.