Influence of cobalt oxide on the structure,optical transitions and ligand field parameters of lithium phosphate glasses

The influences of cobalt oxide (CoO) additions on the structure, optical transitions, ligand field parameters and stability of lithium phosphate glasses have been investigated. A series of glass systems (LiPhCo-glasses) was successfully prepared through the melt quenching approach. The amorphous nature was confirmed from X-ray diffraction measurements. The density and molar volume followed the typical opposite behavior, where the latter showed a decreasing behavior with CoO additions. Furthermore, it was found that the LiPhCo-glasses gradually changed their color from colorless (Co-free sample) into bluish glasses with CoO additions, thereby evidencing the presence of Co²⁺ ions. This is consistent with the absorption band identified in the optical absorption spectra at ~562–572 nm, which is related to ⁴A₂(⁴F) →⁴T₁(⁴P) electronic transitions of Co²⁺ (3d⁷ electronic configuration) in tetrahedral symmetry. Additional absorption band is detected at ~1412–1448 nm, which is correlated to ⁴A₂(⁴F) →⁴T₁(⁴F) transitions of Co²⁺ ions in tetrahedral symmetry. These two absorption bands were employed to study the ligand field splitting ($10D{q}_{\mathrm{t}}$)and Racah parameter (B), which sheds the light into the bonding character between Co ions and its ligands. The analysis showed that $10D{q}_t$ (B) is increased (reduced) indicating more covalency and less stability within the glass matrix with Co additions.     

Towards highly transparent tungsten zinc sodium borate glasses for radiation shielding purposes

The impact of tungsten oxide (WO₃) additions on the structure, some physical and radiation shielding parameters of sodium zinc borate glasses have been scrutinized. These glasses were properly produced by the melt quenching method. The amorphous state was affirmed by X-ray diffraction (XRD) data. The internal structure within the short-range order of the glassy network was studied by the method of infrared spectroscopy (IR). The results of IR showed that the BO₄ units are transformed to BO₃ accompanied by the formation of nonbridging oxygens with further WO₃ doping. This transformation of BO₄ to BO₃ and nonbridging oxygens is employed to explain the increase in the molar volume values with changing WO₃/ZnO amount. Further, the optical transmittance was measured within the visible range to assure the transparency of the prepared glasses. The transmittance results confirm the absence of W⁵⁺, W⁴⁺, W³⁺ states; based on the absence of their absorption bands. Also, the transmittance results indicate that the only oxidation state in the present glasses is hexavalent tungsten (W⁶⁺). Additionally, the parameters of radiation protection of the manufactured glasses were investigated. It was found that, the addition of WO₃ improves not only the radiation protection parameters (such as the linear attenuation coefficient) but also the transparency of the prepared glasses. Finally, we concluded that, the addition of WO₃ to the glass samples leads to transparent glasses with an improved shielding ability at low energies but effects slightly at high energies. Due to the high transparency and the increased values of the linear attenuation coefficient of the prepared glasses, they are considered promising glasses in the field of nuclear radiation protection, especially at low energies.     

Effect of mixed rare-earth ions on the structural and optical properties of some borate glasses

In order to study some effects of mixed ions of rare-earth (Sm and/or Dy) on the properties of a glass system, the formula 80% B₂O₃+ 18% Na₂O + (2-x)% Sm₂O₃ + (x) % Dy₂O₃; x = 0, 0.4, 1.6 and 2 mol. % has been prepared via the well-known melt quenching method. The presence of some structural groups such as BO₃, BO₄, as well as N₄ factor have been scrutinized via FTIR spectra. Absorbance of the prepared solid glass system has been performed by a spectrophotometer in wavelengths between 190 and 1100 nm. Using traditional techniques and standard formulas, the density (ρ_emp and ρ_exp), bond density (n_B), molar volume (V_m), Fermi energy (E_F), refractive index (n), optical bandgap (E_g) have been determined, then the impact of mixed rare-earth oxides (Dy and/or Sm) on the structural and optical properties have been scrutinized. The density, optical bandgap, IR intensity and the refractive index of glass samples shows nonlinear trend, which can be ascribed to the mixed effect of rare-earth cations. However Sm and Dy have been doped with the same percent in the glass system separated and mixed, the effect of Sm ions is obvious than Dy ions.     

Optical properties of ternary zinc magnesium phosphate glasses

Ternary phosphate glasses of the system (ZnO)₃₀(MgO)_x(P₂O₅)_70−x with x ranging from 5 to 20 mol% were prepared by melt quenching technique. The optical absorption spectra of these glasses were measured at room temperature in the wavelength range between 190 and 1100 nm while the refractive index at wavelength 632.8 nm. The optical absorption indicates that the electronic transition is indirect and associated with phonon-assisted transition. From the absorption spectra, the optical energy band gap (E_opt) and Urbach energy (E_U) values for all the glass samples were calculated from their ultraviolet edges. The values of E_opt is found to increase from 3.36 to 3.44 eV and values of E_U decrease from 0.47 to 0.29 eV with the increase of MgO content. Variation in these optical parameters, density and molar volume is discussed and correlated with the structural changes within the glassy matrix.     

The role of PbO/Bi2O3 insertion on the shielding characteristics of novel borate glasses

Impacts of lead and bismuth oxides insertion on a novel glass system of P₂O₅, B₂O₃, Li₂O, Al₂O₃ according the formula 25B₂O₃–25P₂O₅–10Li₂O–5Al₂O₃–5ZnO-xPbO+ (30-x)Bi₂O₃, x = 5,10, 15, 20, 25 mol%. The mass attenuation coefficient (μ_m = μ/ρ) simulated between 0.015 and 15 MeV using MCNP and calculated theoretically using Phy-X/PSD program. Based on the simulated μ_m, other significant parameters such as linear attenuation coefficient (LAC), half and tenth value layer (HVL, TVL), mean free path (MFP), and effective atomic number (Z_eff) were calculated for fabricated glasses. The G-P fitting methods were used to calculate the exposure and energy absorption buildup factors (EBF and EABF) for fabricated glasses. Furthermore, fast neutron removal cross sections (Σ_R) were calculated theoretically for fabricated glasses. The prepared glasses were effective shielding material which can reduce fast neutrons as well as gamma rays.     

PbWO4 formation during controlled crystallization of lead borate glasses

Lead borate glasses were prepared and then heat treated in order to obtain transparent glass-ceramics. Controlled crystallization of precursor lead borate glass at appropriate annealing temperature and time led to formation of the PbWO₄ crystallites. The observed broad blue emission band is related to the PbWO₄ crystallites. The influence of PbX₂ content (X=F, Cl, Br), PbF₂ concentration and lanthanide doping (Eu, Dy) on the excitation and emission spectra of lead borate glass-ceramics containing PbWO₄ phase was examined. The relationship between Pb–X bond and spectral line width of the blue emission can be successfully observed, when halogen X ions (X=F, Cl or Br) are also present in the distorted PbWO₄ crystallites.     

Fabrication and in vitro studies on bioactive borate glasses containing dopant chromium sulfate

This research aims to assess the bioactive properties of the modified borate glasses containing extremely low concentrations (≤5 mol.%) from chromium sulfate (Cr₂(SO₄)₃). The glasses in the system xCr₂(SO₄)₃.(60–x)B₂O₃.15CaO.15Na₂O.10P₂O₅, where x = 0, 1, 2, and 5 mol.% were prepared by the melt quenching technique. All glass samples have been treated thermally at 600 °C for 6 h. Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), and X-ray Diffraction (XRD) measurements were carried out to differentiate between the structural changes before and after soaking in the simulated body fluid (SBF) at about 37 °C for 1, 2, and 3 weeks. Glass-ceramic samples have showed sharper peaks that are identified using X-ray diffraction data. These crystalline phases are indexed to crystalline calcium borate (Ca₂B₂O₃) and calcium phosphate (Ca₃(PO₄)₂). In vitro tests, FTIR spectra revealed two small bands in the 560-610 cm⁻¹ range which might be assigned to the formation of a hydroxyapatite layer (HA). The formation of HA was also confirmed by XRD results, particularly after immersion in SBF for 21 days. The study suggests that the presently studied glasses containing Cr₂(SO₄)₃ can possess good bioactivity which might be considered to be suitable for some bio and medical applications.     

Synthesis,physical, optical,structural and radiation shielding characterization of borate glasses: A focus on the role of SrO/Al2O3 substitution

In a bid to expand the amount of information available on glass systems and their potential applications for radiation shielding design, glass samples with the compositions (30-x)SrO-xAl₂O₃–68B₂O₃–2V₂O₅(x = 5, 7.5, 10, 12.5&15 mol %) coded as SABV0 - 4 were prepared by the melt-quenching technique and analyzed for their optical, structural, physical, and radiation shielding features. The glassy (amorphous) nature of the SABV glass samples was affirmed by broad peaks of X-ray diffraction spectra. Calculated values of density and molar volume shown opposite behavior and the variation of these values were discussed as structural modifications in the glass matrix. From recorded optical absorption spectra optical band gap energy (Eg)-indirect transition, Urbach energy and optical basicity were estimated. FTIR spectra were recorded for all the samples in the range 400 cm^?1 to 4000 cm^?1. The FTIR absorbance spectra unveiled the SABV network structure mainly incorporating of BO₃ and BO₄ units. Raman spectroscopy is achieved to detect the structural changes and at higher wavenumber, B–O stretching modes in [BO₃] observed with one or two NBO's. The results of ESR spectra of glasses have indicated the highly covalent environment of vanadium ions. Analysis of the photon shielding parameters of the glasses which were obtained primarily from FLUKA Monte Carlo simulations and XCOM computations revealed photon energy and glass chemical composition dependence. The mass attenuation coefficient and effective atomic number ranged from 0.2668 to 0.3385 cm²g^-1 and 12.98–15.93 accordingly as the weight fraction of Sr increased from 16.06 to 26.72% in the glasses. Generally, photon shielding ability of the SABV glasses follows the trend: SABV0 > SABV1 > SABV2 > SABV3 > SABV4. The thermal neutron total cross section follows the same trend with values fluctuating between 71.9553 and 80.6268 cm^?1. However, SABV1 showed superior fast neutron moderating capacity among the glasses. The present SABV glasses showed outstanding photon shielding ability compared to common shields. The prepared glasses are thus suitable candidates for radiation protection applications.     

Influence of La2O3 on the structural,mechanical and optical features of cobalt doped heavy metal borate glasses

The impact of rare-earth oxide (La₂O₃) on the structural, mechanical and optical properties of cobalt-doped heavy metal borate glassy system is studied. XRD assured the amorphous nature of the prepared samples. The density and average boron-boron separation were found to increase with La₂O₃ content, thereby enforcing the compactness of the glass network. FT-IR analysis revealed the growth of NBO's ratio due to the gradual conversion of the tetrahedral (BO₄) to trigonal (BO₃) units with the development of a certain boroxol group (B₃O₆) fraction. A noticeable enhancement of the elasticity properties, such as the elastic, bulk, and Young's moduli, as well as the microhardness, was confirmed by measuring the ultrasound velocities within prepared samples. The absorption and photoluminescence emission spectra showed a progressive enhancement of Co³⁺/Co²⁺ ions in the tetrahedral and/or octahedral positions with La₂O₃ content. The ligand field strength and Racah parameters were estimated, in which the ionicity nature between Co²⁺ ions and the nearby ligands is inferred from the nephelauxetic effect. Absorption edge analysis, here performed through Tauc's model, showed a decrease in the band gap and a rise in Urbach energy; the values of each, together with the metallization parameter, reflect the semiconducting character of the prepared samples. The dispersion of the refractive index was determined using the Wemple-DiDomenico single oscillator model and compared to the optical gap energy. Additionally, the nonlinear optical coefficients, here determined within the lower energy spectral range using a third-order nonlinear susceptibility, exhibited progressively increasing value, suggesting a possible integration of the current system in potential nonlinear optical applications. Furthermore, the absorption and photoluminescence spectral tunability here offered through La₂O₃ additives qualifies the current glasses as optically active materials for many possible applications in multifunctional optical devices operating in visible and near-infrared spectral regimes.     

Spectroscopic investigation of synergetic bioactivity behavior of some ternary borate glasses containing fluoride anions

Ternary borate glasses containing LiF, ZnF₂, NaF or CaF₂ were prepared by full replacement of silica by borate in patented Hench′s bioglass. Prepared samples were examined for their corrosion behavior with the expected final formation of fluoroapatite after immersion in SBF (simulated body fluid). Characterization of the glasses was carried by FTIR (Fourier transform infrared) absorption spectra before and after immersion. DAT (deconvolution analysis technique) was used to identify the formation of fluoroxyapatite from FTIR data after immersion in SBF. X-ray diffraction analyses were done for all samples to identify the crystalline phases that were formed after immersion in SBF and also to determine the degree of crystallinity for each sample. Also, scanning electron microscopic (SEM) investigations were carried out to examine the morphological changes of the surfaces upon immersion and the effects of different individual fluoride additives. The solubility testing for glassy samples was performed and the changes in the pH of the leaching solution were measured and evaluated.     

Boron-containing bioactive glasses in bone and soft tissue engineering

Boron is considered to influence the performance of several metabolic enzymes and boron deficiency is associated with impaired growth and abnormal bone development. As such, boron is a beneficial bioactive element for animals and humans. It is also well known that boron stimulates wound healing and improves bone health. The addition of boron in different proportions to bioactive glasses has significant effects on glass structure, glass processing parameters, biodegradability, biocompatibility, bioactivity and cytotoxicity. Different compositions of bioactive glasses (BGs) containing boron, including boron-doped, borosilicate and borate glasses, are being investigated for bone and soft tissue engineering under the premise that these BGs are suitable carriers of boron, indicating controlled release of B species in the biological environment. This paper reviews up to date research and applications of borate, borosilicate, and boron doped silicate and phosphate BGs focussing on their physical, structural, degradation and biological properties for hard and soft tissue regeneration.     

Impact of bismuth oxide on the structure,optical features and ligand field parameters of borosilicate glasses doped with nickel oxide

Understanding the impact of bismuth cations on the optical properties of borosilicate glass is significant for manipulating borate glass applications. In this paper, the influence of bismuth cations on both structural and optical properties of borosilicate glass doped with NiO was investigated. Different glass samples, containing different amounts of Bi₂O₃ and a constant amount of NiO, were prepared and studied. Infrared (IR) analysis was carried out to study the internal structure within the investigated glass samples. Optical absorption studies were performed to investigate the impact of Bi₂O₃ content on optical properties of the BiBaNiB-glasses. Astonishingly, with Bi₂O₃ addition, an absorption band at 380 nm has appeared. Moreover, this band is overlapped with the Urbach edge; which regularly produced an artificial edge-like feature at ~450 nm. A detailed deconvolution protocol has been implemented for an appropriate understanding of these spectra and unraveling the hidden Urbach edge. Optical band gap energy, linear and nonlinear refractive index for each BiBaNiB sample were calculated. Furthermore, the metallization criterion was calculated to examine the metallic or insulating nature of the BiBaNiB-glasses. The values of the nonlinear third-order susceptibility and nonlinear refractive index were increased with Bi₂O₃ doping. The BiBaNiB-glasses exhibited outstanding stability and optical band gap than the pristine glass sample, which makes it possible for practical applications.     

Synthesis,FTIR, and mechanical as well as radiation shielding characteristics in Nd2O3-doped bismuth lithium borate glasses

A melt quenching method was applied to fabricate a series of bismuth lithium borate glasses with a chemical composition of 65(B₂O₅) + 20(Bi₂O₃) + (15 ? x)(Li₂O) + x(Nd₂O₃), where x = 0, 1, 2, 3, and 4 mol%. The structural changes in the fabricate glasses were studied via the Fourier transform infrared spectroscopy (FT-IR). The FT-IR spectra of the manufactured glasses indicated the transformation of the structural unit BO₄. The mechanical properties of the produced glasses were evaluated via the ultrasonic measurement (longitudinal and shear velocities) and the Makishima–Mackenzie modulus calculations. Furthermore, the role of Nd₂O₃ in improving mechanical properties was studied theoretically and experimentally and results showed that ultrasonic velocities and elastic moduli decreased with increasing the Nd₂O₃ content. The Young's modulus decreased from 68.47 to 50.61 GPa as the Nd₂O₃ content increased from 0 to 4 mol%, respectively. The gamma ray shielding properties of the studied glass samples were evaluated using the Monte Carlo simulations between 0.223 and 2.506 MeV. The simulated data showed that the fabricated glass without Nd₂O₃ has the highest linear attenuation coefficient, which varied between 0.210 and 0.212 cm^?1 for photons with energies ranging from 0.2234 to 2.506 MeV.     

Comparative investigation of physical,X-ray and neutron radiation shielding properties for B2O3-MnO2-CdO borate glasses

B₂O₃-MnO₂-CdO ternary oxide glasses with amorphous properties were synthesised using the melt-quenching method. Structural and physical property analyses showed that the amount of non-bridging oxygen and the system stiffness increases, and the oxide network filling is more tightly packed as cadmium oxide (CdO) gradually replaces manganese Oxide (MnO₂) in the glass. The radiation-shielding performance of the B₂O₃-MnO₂-CdO glasses was evaluated using the shielding parameters calculated by the MCNPX simulation and the Phy-X program. Glasses with 40% and 50% CdO loading exhibited an average specific lead equivalent (PbE) of 0.241 and 0.294 mmPb/mm in the medical X-ray diagnostic area at 0.03–0.08 MeV; thus, they could fully meet the specific PbE requirements for application as "protection devices against diagnostic medical X-radiation". Furthermore, their photon attenuation capability is superior to that of various commercial shielding glasses in fast-neutron nuclear applications at 1°–10³ MeV. In addition, compared to the borate glass systems studied in the literature, B₂O₃-MnO₂-CdO glasses have fast neutron removal cross-sections of 0.125 cm⁻¹ at a smaller density of 3.9043–4.8135 g/cm³, making them potentially excellent fast neutron absorbers.     

Kinetics of fluid–solid reaction with an insoluble product: zinc borate by the reaction of boric acid and zinc oxide

Mixing parameters influencing the final particle size and conversion of zinc oxide were studied for the formation of zinc borate. Formation of zinc borate was via a fluid–solid reaction. The process was kinetically controlled above the minimum speed for particle suspension, N_s. The reaction kinetics was developed and the rate constant was estimated. Copyright © 2004 Society of Chemical Industry     

Role of annealing temperature on structural and optical properties of zinc oxy-nitride films synthesized by powder vapor transport technique

Zinc oxy-nitride (ZnON) is an emerging semiconductor having tunable energy bandgap (Eg) and refractive index (n). Herein, the effect of annealing temperature on ZnON films synthesized on glass substrates at different (50, 100 and 150 sccm) nitrogen gas flow rates (NGFR) by simple powder vapor transport (PVT) technique is studied. All the synthesized ZnON films are annealed at 300 °C for 60 min. The unannealed and annealed ZnON (Un-&-An-ZnON) films are characterized by XRD, SEM, Raman and UV spectroscopies. XRD analysis confirms the formation of polycrystalline ZnN films and no diffraction plane related to oxide phase. The crystallinity of Un-ZnN films is increased after annealing, however, it is maximum for 100 sccm NGFR. Raman analysis indicates the presence of vibrational modes related to ZnN and ZnO phases, thereby confirming the formation of ZnON films. After annealing, the surface morphologies of Un-ZnON films is transformed from nano-sheets/nano-blocks to rounded nanoparticles. The change in structural and morphological features of ZnON films, associated with annealing temperature causes to create stresses and defects and hence Eg and n. The values of n (1.85–1.87) and Eg (2.6–2.7 eV) of Un-ZnON films are increased to (1.98–2.62) and (3.16–3.25 eV), after annealing, respectively. These inexpensive but high quality ZnON films can be used for semiconducting and optoelectronic devices.     

The role of cadmium oxides in the enhancement of radiation shielding capacities for alkali borate glasses

The radiation shielding capacity of 80B₂O₃–(20-x) Na₂O–x CdO (where x = 0, 2, 4, 6, 8, 10, 12 and 14 mol%) cadmium-doped sodium borate glasses was evaluated. The linear attenuation coefficient (LAC) of the studied glasses was simulated using the Monte Carlo simulation code (MCNP-5) for gamma photons with energy between 0.01 and 15 MeV. Other pivotal gamma ray shielding parameters such as mass attenuation coefficient (MAC), half value layer (HVL), effective atomic number (Z_eff), and buildup factors (EBF and EABF) for the selected cadmium-doped sodium borate glasses were examined. The achieved data showed that, BNC 8 glass with CdO contents of 14 mol % possesses the highest LAC and varied between 0.0650 and 83.636 cm^-1 and also it has thinner HVL than other BNC glasses and varied between 0.008 and 10.686 cm for gamma ray energy between 0.01 and 15 MeV. Moreover, the removal cross sections of fast neutrons (Σ_R) were also calculated theoretically for the selected cadmium-doped sodium borate glasses. The obtained data shows that the insertion of CdO appears to enhance gamma ray and neutron shielding capacity. BNC8 with CdO content (14 mol%) was found to possess the best shielding parameters among the studied cadmium-doped sodium borate glasses.     

Designing optical glasses by machine learning coupled with a genetic algorithm

Engineering new glass compositions have experienced a sturdy tendency to move forward from (educated) trial-and-error to data- and simulation-driven strategies. In this work, we developed a computer program that combines data-driven predictive models (in this case, neural networks) with a genetic algorithm to design glass compositions with desired combinations of properties. First, we induced predictive models for the glass transition temperature (T_g) using a dataset of 45,302 compositions with 39 different chemical elements, and for the refractive index (n_d) using a dataset of 41,225 compositions with 38 different chemical elements. Then, we searched for relevant glass compositions using a genetic algorithm informed by a design trend of glasses having high n_d (1.7 or more) and low T_g (500 °C or less). Two candidate compositions suggested by the combined algorithms were selected and produced in the laboratory. These compositions are significantly different from those in the datasets used to induce the predictive models, showing that the used method is indeed capable of exploration. Both glasses met the constraints of the work, which supports the proposed framework. Therefore, this new tool can be immediately used for accelerating the design of new glasses. These results are a stepping stone in the pathway of machine learning-guided design of novel glasses.     

Photoluminescence of dysprosium doped antimony-magnesium-strontium-oxyfluoroborate glasses

Dysprosium (Dy³⁺)-doped antimony-magnesium-strontium-oxyfluoroborate (B₂O₃ MgF₂ SrO Sb₂O₃ Dy₂O₃, BMFSrSbD), glasses were synthesized by traditional melt-quenching method. The synthesized samples have been analyzed by X-ray diffraction, optical absorption and fluorescence techniques for deriving various characteristic properties. Emission spectra of Dy³⁺: samples were exhibit three well resolved emission bands at around 482, 575 and 666?nm which originated from the ⁴F_9/2→⁶H_15/2,⁴F_9/2→⁶H_13/2 and ⁴F_9/2→⁶H_11/2 transitions upon excitation of wavelength at 452?nm. Decay curves of the ⁴F_9/2 level of Dy³⁺ ion were display mono-exponential at low Dy³⁺ concentration (0.1?mol%) and deviated to non-exponential behavior at high concentration of Dy³⁺ ions (≥?0.5?mol%). Lifetime of the ⁴F_9/2 level was decreased with increase of Dy³⁺ ions concentration. Chromaticity coordinates (x,y) of Dy³⁺:BMFSrSbD samples were evaluated and represented in CIE 1931 chromaticity diagram, appear in the whitish-yellow region. The results suggest that these glasses could be utilized as a potential candidate for the development of display devices and lasers at a wavelength of 575?nm.     

Influence of molybdenum oxide on structural,optical and physical properties of oxychloride glasses for nonlinear optical devices

The unconventional Heavy Metal Oxide Glasses (HMOG) are characterized by a low phonon energy, large infrared range transmission, high refractive index and nonlinear optical properties. Ternary glasses have been synthesized and studied in the Sb₂O₃– MoO₃-ZnCl₂ system. Further, the glass formation compositional limits are reported and some glass samples with the formula: (90-x)Sb₂O₃ -xMoO₃–10 ZnCl₂ (10 ≤ x ≤ 50, mole%) were elaborated. Thermal properties have been measured and indicating that the glass transition temperature decreases with increasing proportions of molybdenum oxide. The evolution of density, microhardness and elastic modulus has been studied as functions of parameter x and Raman spectra measurements have been shown the partial conversion of MoO₆ octahedral units into MoO₄ tetrahedral.