Spectroscopic and Surface Crystallization Characterizations of Yttrium-Doped Phosphate Glasses

The composition, structure, and thermal behaviors of yttrium-containing phosphate glasses were studied in this work, and the glass-ceramics were prepared via the two-step crystallization method. The XRD and SEM-EDS results show the forming range of the phosphate glass system and the formation of YPO4 (xenotime) due to the addition of excessive Y2O3. The spectroscopic characterization of these glasses presented shifts of the infrared and Raman bands, demonstrating the depolymerization of the glass network and the formation of novel P–O–Y bonds, and the deconvoluted Raman spectra also exhibited the occurrence of the disproportionation reaction in the glass melting process. The content of non-bridging oxygen (NBOs) from the UV–vis spectra first increased and then decreased with increasing Y2O3. The thermal behaviors show that the Y2O3 reduced the crystallization peak temperature and the thermal stability of the glasses. The crystalline behaviors of the phosphate glass matrix were investigated at different crystallization times of 2–10 h, and a transformation of the crystallization mechanism from surface to volume crystallization was found. The yttrium phosphate glass-ceramics crystallized for 10 h exhibited transformation of the main crystalline phases with increasing Y2O3, and the grain-oriented crystalline surface became irregular.

Sintering Bi2O3–B2O3–ZnO ternary low temperature glass by hydration device to solidify iodine containing silver-coated silica gel

A new glass solidification process aims at radioactive iodine waste was explored in order to reduce the possible harm to environment. Samples with different iodine content in silver-coated silica gel were pretreated by hydration device at 300 °C and then sintered at relatively low temperatures (500, 550 and 600 °C). XRD results show that AgI is mainly chemically fixed in the glass network with some AgI particles being physically wrapped by the glass. Moreover, as the sintering temperature reached to 550 °C, B element crystallized. SEM-EDS results show that Ag and I elements are enriched, while the other elements are evenly distributed. AFM results showed that the sample surface becomes rougher as the iodine content increases in the silver coated silica gel. The FT-IR results show that the structure of the sintered sample is mainly composed of [BiO3], [BiO6] and [BO3]. This study provides a new sintering method by hydration device for the treatment of radioactive iodine waste.

Structural, Optical, Magnetic and Photon Attenuation of Novel Potassium Lead Borate Glasses Doped with MnO

Potassium lead borate glasses doped with MnO (40B2O3+40PbO+(20-x)K2O+xMnO: x= 0-5 mol%) have been prepared via standard melting quenching process. The impact of MnO on the structure, optical, magnetic and gamma-ray protection properties of pottisium lead borate glasses have been examined. The density was increased from 4.83±0.01 to 5.23±0.01 g/cm3 as MnO content increased. The obtained direct optical gap (Eg) values were 2.84, 2.59, 2.41, 2.19, 1.95, and 1.84 eV for the Mn-x (x=0, 1, 2, 3, 4, and 5) glass samples, respectively. FTIR spectra demonstrated that as the MnO concentration increases in the glass network the intensity and width of the IR bands were increased. The magnetic measurement revealed that the magnetic situation (Ms) was decreased while the magnetic coercivity (Hc) was increased with increasing MnO substitution ratio. The linear attenuation coefficient of the follows the order: µMn-0 < µMn-1 < µMn-2 < µMn-3 < µMn-4 < µMn-5. Half value layer (HVL) rises as µ decreases and vice versa. The range of the HVL is 0.002 – 3.378, 0.002 – 3.334, 0.002 – 3.291, 0.002 – 3.248, 0.002 – 3.176, and 0.002 – 3.106 cm for Mn-x (x=0, 1, 2, 3, 4, and5). The trend of Zeff variation is related to that of both linear and mass attenuation coefficients (µ and µm). The produced Mn-glasses can be employed in a variety of optical, magnetic and radiation protective applications.

Quantification of gas-accessible microporosity in metal-organic framework glasses

Metal-organic framework (MOF) glasses are a new class of microporous glass materials with immense potential for applications ranging from gas separation to optics and solid electrolytes. Due to the inherent difficulty to determine the atomistic structure of amorphous glasses, the intrinsic structural porosity of MOF glasses is only poorly understood. In this work, the porosity features of a series of prototypical MOF glass formers from the family of zeolitic imidazolate frameworks (ZIFs) and their corresponding glasses is investigated comprehensively. CO2 gas sorption at 195 K allows to follow the evolution of microporosity when transforming from the crystalline to the glassy state of these materials. Based on these data, the pore volume and the real density of the ZIF glasses is quantified for the first time. Additional hydrocarbon sorption data (n-butane, propane and propylene) together with X-ray total scattering experiments prove that the porosity features (in particular the pore size and the pore limiting diameter) of the ZIF glasses depend on the types of organic linkers present in the glass network. This allows formulating first design principles for a targeted tuning of the intrinsic microporosity of MOF glasses. Importantly, these principles are counterintuitive and contrary to established porosity design concepts for crystalline MOFs but show similarities to strategies previously developed for porous polymers.

NMR Spectral Characteristics of Ultrahigh Pressure High Temperature Impact Glasses of the Giant Kara Crater (Pay-Khoy, Russia)

In this study, we carried out the analysis of the impact melt vein glasses from the Kara impact crater (Russia) in comparison to low-pressure impact melt glasses (tektites) of the Zhamanshin crater (Kazakhstan). 27Al, 23Na, and 29Si MAS NMR spectra of the samples of these glasses were analyzed. The samples of the natural glass contained inclusions of crystalline phases, paramagnetic elements that greatly complicate and distort the NMR signals from the glass phase itself. Taking into account the Mossbauer distribution of Fe in these glasses, the analysis of the spectra of MAS NMR of glass network-former (Si, Al) and potential network-modifiers (Na) of nuclei leads to the conclusion that the Kara impact melt vein glasses are characterized by complete polymerization of (Si,Al)O4 tetrahedral structural units. The NMR features of the glasses are consistent with the vein hypothesis of their formation under conditions of high pressures and temperatures resulting in their fluidity, relatively slow solidification with partial melt differentiation, polymerization, and precipitation of mineral phases as the impact melt cools. The 70 Ma stability of the Kara impact vein glass can be explained by the stabilization of the glass network with primary fine-dispersed pyroxene and coesite precipitates and by the high polymerization level of the impact glass.

The chemistry of melting oxynitride phosphate glasses

Oxide glasses are the most commonly studied non-crystalline materials in Science and Technology, though compositions where part of the oxygen is replaced by other anions, e.g. fluoride, sulfide or nitride, have given rise to a good number of works and several key applications, from optics to ionic conductors. Oxynitride silicate or phosphate glasses stand out among all others because of their higher chemical and mechanical stability and their research continues particularly focused onto the development of solid electrolytes. In phosphate glasses, the easiest way of introducing nitrogen is by the remelting of the parent glass under a flow of ammonia, a method that allows the homogeneous nitridation of the bulk glass and which is governed by diffusion through the liquid-gas reaction between NH3 and the PO4 chemical groupings. After nitridation, two new structural units appear, the PO3N and PO2N2 ones, where nitrogen atoms can be bonded to either two or three neighboring phosphorus, thus increasing the bonding density of the glass network and resulting in a quantitative improvement of their properties. This short review will gather all important aspects of the synthesis of oxynitride phosphate glasses with emphasis on the influence of chemical composition and structure.

Study of the influence of MoO3 concentration on the chemical structure, physical properties, and radiation absorption prowess of alumino lead borate glasses

The present study established a glass system with composition of 55B2O3 -30Pb3O4-(15 - x) Al2O3- xMoO3, where x: (0≤x≤5 mol %) by melt quenching conventional method. The structure of the synthesized samples was examined by XRD and FT-IR techniques. It is found that the molybdenum acts as a modifier and enhances the change between BO3 and BO4 structural units. Increasing MoO3 in the sample improved the glass network compactness and enhanced the coherence of the glass network and the structure stiffening. Some physical parameters were studied with increasing MoO3 content in the samples such as Ri, ri, rp, dB-B average coordination number, number of bonds, field strength of (Mo+3), the floppy modes, the cross-linking density and effective coordination number and found to be enhanced. Increasing MoO3 dopingconcentration from 0 – 5 mol % produced corresponding increase in fast neutron effective removal cross section ΣR from 0.07127 – 0.10825 cm-1, total cross section for thermal neutrons σT from 68.35875 – 105.7526 cm-1, and an increment in the cold neutron scattering cross section. Furthermore, the influence of MoO3 doping in the glasses is such that the stopping powers (Sp) and ranges RCSDA /Rp of electrons, proton, alpha particles, and carbon ion follows the trend: (Sp)BPAM-G1 > (Sp)BPAM-G2 > (Sp)BPAM-G3 >(Sp)BPAM-G4 > (Sp)BPAM-G5, and(RCSDA /Rp)BPAM-G1 > (RCSDA /Rp)BPAM-G2 > (RCSDA /Rp)BPAM-G3 > (RCSDA /Rp)BPAM-G4 > ((RCSDA /Rp)BPAM-G5 respectively. On the other hand, the doping produced no noticeable differences in the equivalent atomic number and the exposure buildup factor of the glasses.

Investigations on Structural and Optical Properties of Various Modifier Oxides (MO = ZnO, CdO, BaO, and PbO) Containing Bismuth Borate Lithium Glasses

Bismuth based quaternary glasses with compositions BiBLM: 50Bi2O3–20B2O3–15Li2O–15MO (where MO = ZnO, CdO, BaO, and PbO) were processed by conventional melt quenching. The effectiveness of various modifier oxides on the optical and structural properties of the developed glasses was studied systematically by XRD, DSC, FTIR, Raman, and optical absorption (OA) measurements. The synthesized glass specimens were characterized by XRD and the patterns demonstrated an amorphous nature. The physical characteristics such as molar mass, density, and OPD values were found to increase with an increase in the molar mass of the modifier oxides, while there was a decrement in oxygen molar volume, thus resulting in decrement of complete molar volume of the prepared glasses. From DSC analysis, incorrigible reduction and enhancement of Tg and thermal stability among various modifier oxides in the glass network was noticed. Optical absorption data for glass specimens have confirmed the decrease in both direct and indirect optical band gap values among various modifier oxides incorporation. These investigations support the obtained Urbach energy (UE) and metallization criteria of synthesized glasses. The ionic characteristic for the glass specimens were confirmed by the values of electronic polarizability and electronegativity. The Raman and FT-IR spectra of the glass specimens displayed the existence of BiO3, BiO6, ZnO4, CdO4, BaO4, BO3, PbO4, and BO4 structural units within the glass matrix. These structural results can support the applications of as-developed glasses in the area of photonics.

Different low-cost materials to prevent the alteration induced by formic acid on unstable glasses

The most frequent cause of glass degradation is environmental moisture, which is adsorbed on its surface forming a hydration layer that induces the rupture of the glass network. This pathology is accelerated by the accumulation of volatile organic compounds (VOCs), like formic acid. Although there is extensive knowledge about their impact, concentrations inside display cases are difficult to reduce efficiently. This study presents the assessment of different materials to reduce the concentration of formic acid to mitigate the degradation produced in unstable glasses. With this objective, copper threads, steel wool, silica gel, and activated carbon were chosen as low-cost materials with good adsorption or reactivity to the VOCs, exposing them in desiccators to an environment of 100% RH and 10 ppm of formic acid. Given that silica gel obtained the best results, its optimization as a sorbent material was evaluated by maintaining, regenerating, or renewing it when exposed next to the same glass. The tests carried out concluded that the hygroscopic capacity of the glasses exposed with silica gel decreased and, therefore, a lower degradation is observed on its surface. In addition, regenerating and renewing weekly the silica gel improved the results.