Thermal stability of crystalline phases in MnO-doped zinc borosilicate glasses
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Thermal stability of crystalline phases in MnO‑doped zinc borosilicate glasses G. J. Vander Stouw1 · S. K. Sundaram1 Received: 2 April 2020 / Accepted: 22 June 2020 © Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract We have studied a relatively overlooked subset of the MnO-doped zinc borosilicate glass system with a goal of investigating the effects of MnO-doping on the thermal stability of crystalline phase formation in the system. A glass system of general composition 55ZnO–20B2O3–25SiO2 with added MnO dopant, which replaces Zn modifier locations with Mn, ratios of 0, 0.005, 0.01, and 0.015 MnO:ZnO were prepared, via batch melting at 1550 °C for 1.5 h. The glasses were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS). Thermal analysis, followed by detailed XRD and Rietveld structural refinement, revealed the formation of zinc borate ( Zn4O(BO2)6), willemite ( Zn2SiO4), and manganese zinc silicate ((ZnMn)SiO4) crystallites after heat-treatment at 875 °C for 4 h and zinc borate crystallites influenced by the borate anomaly in samples heated to ≈ 955 °C at a ramp rate of 10 °C/min and held for 4 h. Microstructure and elemental maps confirmed that the zinc borate had become an integral part of both glass and crystalline phases in the resulting glass–ceramic samples. MnO-content influenced the formation of the boron-containing glass phase via the borate anomaly. Keywords Manganese dopant · High zinc content zinc borosilicate glass · Thermal analysis · Phase analysis
1 Introduction Zinc borosilicate glasses are known for their thermal shock resistance, high elastic moduli, chemical durability, low level of optical absorbance, and the piezoelectric properties of ZnO [1, 2]. In recent years, there has been an increased interest and reporting of the fluorescent behavior of zinc borosilicate glasses through the formation of zincite, a rarer mineral form of ZnO, and willemite (Zn2SiO4) crystalline phases as ultraviolet (UV) emission centers [3–5]. These glasses need to be crystallized via heat-treatment, or other methods, and converted into a glass–ceramics to generate these phases, bringing the added benefits of strength, heat resistance, low production cost, and higher thermal shock * G. J. Vander Stouw [email protected] S. K. Sundaram [email protected] 1
Ultrafast Materials Science and Engineering Laboratory (U‑Lab), Kazuo Inamori School of Engineering, The New York State College of Ceramics, Alfred University, Alfred, NY, USA
resistance at the cost of some optical clarity [4]. These glass–ceramics have recently been investigated for use in optical devices such as high energy detectors [3–5]. In our study, we chose the ternary ZnO–B2O3–SiO2 system as a base system to study the effects of controlled postprocessing thermal applications on the thermal stability of these glasses. In the chosen system, S iO2 and B 2O3 act as network formers.
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