EPR in glass ceramics
Abstract The development of novel materials requires a profound understanding of the relationship between a material's performance and its structural properties. Electron paramagnetic resonance (EPR) is a well-established technique for a direct detection and identification of paramagnetic defects in solids. This chapter provides an overview of the applicability of continuous wave EPR spectroscopy in the studies of glass ceramics focusing on transition metal (Mn2 +, Cu2 +, Cr3 +) and rare earth (Gd3 +, Eu2 +, Er3 +, Yb3 +) ion local structure analysis. EPR spectra features of the above-mentioned paramagnetic probes in glasses and glass ceramics are compared and discussed in detail. The chapt…
Effect of Mn doping on the low-temperature synthesis of tricalcium phosphate (TCP) polymorphs
Abstract Effect of Mn doping on the low-temperature synthesis of tricalcium phosphate (TCP) polymorphs was demonstrated in α- and β-TCP polymorphs prepared by wet precipitation method under identical conditions and annealed at 700 °C. Calcium phosphates with Mn doping level in the range from 1 to 5 mol% were studied and the formation of desired polymorph was controlled by varying Mn content in as-prepared precipitates. It was found that increasing Mn content resulted in the formation of β-TCP, while α-TCP was obtained with low Mn doping level, whereas a mixture of two polymorphs was obtained for intermediate Mn concentrations. Moreover, doping with Mn ions allowed the synthesis of β-TCP at …
Defect formation in photochromic Ca2SnO4: Al3+
Abstract Photoluminescence, photochromism and defect formation were analysed in Ca2SnO4 doped with 0–20% Al3+. Bright cyan luminescence attributed to Sn2+ was detected in all samples. Introduction of Al3+ in Ca2SnO4 led to an enhancement of Sn2+ emission by up to 70% in comparison with an undoped sample. After exposure to UV irradiation, two absorbance bands centered at 520 nm and 710 nm and three paramagnetic defects were observed in Al3+-doped Ca2SnO4 samples. The paramagnetic centers were identified as a hole type and two different Sn3+ centers. Electron paramagnetic resonance (EPR) data suggested that one of the Sn3+ centers is located in a close proximity of Al3+. Analysis of the stabi…
Oxidation State and Local Structure of Chromium Ions in LaOCl
This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335. Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017- TeamingPhase2 under grant agreement No. 739508, project CAMART2.
Electron paramagnetic resonance and photoluminescence investigation of europium local structure in oxyfluoride glass ceramics containing SrF2 nanocrystals
Different compositions of europium doped aluminosilicate oxyfluoride glass ceramics prepared in air atmosphere have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy methods. X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements show presence of homogenously distributed SrF2 nanocrystals after the heat treatment of the precursor glass. Efficient Eu3+ incorporation in the high symmetry environment of glass ceramics is observed from the photoluminescence spectra. EPR spectra indicate Eu3+ → Eu2+ reduction upon precipitation of crystalline phases in the glass matrix. For composition abundant with Eu2+ in the glassy state such behaviour is …
EPR Study of Gd3+local structure in ScF3crystal with negative thermal expansion coefficient
Zero field splitting (ZFS) of Gd3+ impurity in ScF3 is studied by electron paramagnetic resonance at 77 and 295 K. ZFS parameter b4 values obtained from angular dependence simulations show that regardless of negative thermal expansion in ScF3 temperature dependence of |b4| is similar to other cubic fluoroperovskites. Our analysis of ZFS parameters indicates that the local structure of Gd3+ centres expands positively with temperature.
Upconversion luminescence in transparent oxyfluoride glass ceramics containing hexagonal NaErF4
The authors wish to express gratitude to K. Smits for TEM measurements. This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335. GK wishes to expresses gratitude to Arnis Riekstins "MikroTik" donation. Donations are administered by the University of Latvia Foundation. © 2019. This work is licensed under a CC BY-NC-ND 4.0 license.
Electron paramagnetic resonance and magnetic circular dichroism of Gd3+ ions in oxyfluoride glass–ceramics containing CaF2 nanocrystals
Abstract Magnetic resonance investigations of the Gd3 + centre structure in the oxyfluoride glass and glass–ceramics (GCs) have been carried out. The electron paramagnetic resonance (EPR) measurements showed the presence of low symmetry Gd3 + centres in the glass sample. The cubic Gd3 + centre appeared in the glass–ceramics after heat treatment of the samples at temperatures above 650 °C. The magnetic circular dichroism (MCD) measurements of both glass and glass–ceramics showed wide absorption band around 310 nm. In the GC samples MCD–EPR of the cubic Gd3 + centre has been detected.
Recombination luminescence of X-ray induced paramagnetic defects in BaY2F8
This research is funded by the Latvian Council of Science , project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1–0335 . The crystal growth research was funded by the CNPq (Brazil), project NO 421581/2016–6 .
Eu3+ ion distribution in oxyfluoride glass nanocomposites
The authors are grateful to Dr. Andris Fedotovs for photography of the samples. This research is funded by the Latvian Council of Science, project “Novel transparent nanocomposite oxyfluoride materials for optical applications”, project No. LZP-2018/1-0335.
EPR and optical spectroscopy of neutron-irradiated Gd3Ga5O12 single crystals
Abstract In this paper, we have performed comparative analysis of EPR, optical absorption (OA) and luminescence spectra for a series of Gd3Ga5O12 (GGG) single crystals irradiated with fast neutrons with fluencies varied from 1016 to 1020n/cm2. In a crystal irradiated with the maximum neutron fluence, the EPR spectra demonstrated the formation of several paramagnetic defects. In particular, EPR spectrum shows a strong resonance at (effective) g ≈ 1.4 with practically isotropic behavior in the crystal rotation around the [1 1 1] direction (magnetic field being perpendicular to [1 1 1]) and several weaker lines in the g ≈ 1.1–2.6 region, which show more pronounced angular dependences. While th…
Radiation-Induced Stable Radicals in Calcium Phosphates: Results of Multifrequency EPR, EDNMR, ESEEM, and ENDOR Studies
This article presents the results of a study of radiation-induced defects in various synthetic calcium phosphate (CP) powder materials (hydroxyapatite—HA and octacalcium phosphate—OCP) by electron paramagnetic resonance (EPR) spectroscopy at the X, Q, and W-bands (9, 34, 95 GHz for the microwave frequencies, respectively). Currently, CP materials are widely used in orthopedics and dentistry owing to their high biocompatibility and physico-chemical similarity with human hard tissue. It is shown that in addition to the classical EPR techniques, other experimental approaches such as ELDOR-detected NMR (EDNMR), electron spin echo envelope modulation (ESEEM), and electronnuclear double resonance…
Synthesis, structural and luminescent properties of Mn-doped calcium pyrophosphate (Ca2P2O7) polymorphs
The study was partially funded by the Swedish Research Council FORMAS project “Utilization of solid inorganic waste from the aquaculture industry as wood reinforcement material for flame retardancy” (grant no. 2018-01198). Vilnius University is highly acknowledged for financial support from the Science Promotion Foundation (MSF-JM-5/2021). This project has also received funding from European Social Fund (project No 09.3.3-LMT-K-712-19-0069) under grant agreement with the Research Council of Lithuania (LMTLT). The authors acknowledge the Center of Spectroscopic Characterization of Materials and Electronic/Molecular Processes ("SPECTROVERSUM" www.spectroversum.ff.vu.lt ) at the Lithuanian Nat…
Spectroscopic studies of Cr3+ ions in natural single crystal of magnesium aluminate spinel MgAl2O4
Abstract The natural spinel crystal MgAl2O4 containing the Cr3+ ions was studied experimentally and theoretically in this paper. The absorption and emission spectra at room and low temperatures were recorded. The experimental spectroscopic results were aided with the crystal field calculations, which returned the energy level schemes of the Cr3+ ions at the Al sites with the local D3d symmetry. Effects of the trigonal crystal field were clearly seen in the calculated results, which were compared with the experimental spectra to yield a good agreement between both data sets.
Crystalline phase detection in glass ceramics by EPR spectroscopy
The advances of EPR spectroscopy for the detection of activators as well as determining their local structure in the crystalline phase of glass ceramics is considered. The feasibility of d-element (Mn2+, Cu2+) and f-element (Gd3+, Eu2+) ion probes for the investigation of glass ceramics is discussed. In the case of Mn2+, the information is obtained from the EPR spectrum superhyperfine structure, for Gd3+ and Eu2+ probes – from the EPR spectrum fine structure, whereas for Cu2+ ions the changes in the EPR spectrum shape could be useful. The examples of EPR spectra of the above-mentioned probes in oxyfluoride glass ceramics are illustrated. ----/ / /---- This is the preprint version of the fol…
Local structure of gadolinium in oxyfluoride glass matrices containing SrF2 and BaF2 crystallites
Abstract Gd3 + doped aluminosilicate oxyfluoride glasses and glass-ceramics containing SrF2 and BaF2 crystallites have been studied by differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) and electron paramagnetic resonance (EPR) spectroscopy techniques. A pronounced EPR fine structure emerges after the heat treatment of the glass matrix. EPR spectra simulations indicate the formation of cubic, tetragonal and trigonal Gd3 + centres in the studied compositions.
Black carbon-doped TiO2 films: Synthesis, characterization and photocatalysis
This research is funded by the European Social Fund according to the activity ‘Improvement of researchers’ qualification by implementing world-class R&D projects’ of Measure No. 09.3.3-LMT- K-712, project „Investigation of the application of TiO2 and ZnO for the visible light assisted photocatalytical disinfection of the biologically contaminated water“ (09.3.3-LMT-K-712-01-0175). The authors express gratitude for the S. Tuckute, M. Urbonavicius, G. Laukaitis and K. Bockute for their valuable input in current work. © 2019. This work is licensed under a CC BY-NC-ND 4.0 license.
Investigation of lanthanum substitution effects in yttrium aluminium garnet: importance of solid state NMR and EPR methods
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UV and X-ray excited red persistent luminescence in Mn2+ doped MgGeO3 material synthesized in air and reducing atmosphere
Abstract Materials with long persistent luminescence (PersL) have caused widespread interest among scientists and industry for decades. Currently, there is widely available information on the long persistent luminescence materials with emission in the blue and green spectral range, while the number of publications on the afterglow in the red and near-infrared spectral range is considerably lower. In the course of this work MgGeO3 material doped with 0.1 mol% Mn2+ was produced using solid-state reaction synthesis in ambient and reducing atmospheres. The material exhibits a broad luminescence band with a peak around 680 nm, excited by either X-rays or UV. After cessation of irradiation, the a…
Synthesis and luminescent properties of Mn-doped alpha-tricalcium phosphate
This project has received funding from European Social Fund (project No 09.3.3-LMT-K-712-19-0069) under grant agreement with the Research Council of Lithuania (LMTLT). Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART². The World Federation of Scientists is highly acknowledged for the National Scholarship to AZ. © 2021. This work is licensed under a CC BY-NC-ND 4.0 license.
Low-temperature studies of Cr 3+ ions in natural and neutron-irradiated g-Al spinel
This study was supported by a grant from Latvian Council of Science (agreement No. LZP-2018/1-0214).
Changes in Surface Free Energy and Surface Conductivity of Carbon Nanotube/Polyimide Nanocomposite Films Induced by UV Irradiation.
Changes in surface energy and electrical conductivity of polyimide (PI)-based nanocomposite films filled with carbon nanotubes (CNTs) induced by UV exposure are gaining considerable interest in microelectronic, aeronautical, and aerospace applications. However, the underlying mechanism of PI photochemistry and oxidation reactions induced by UV irradiation upon the surface in the presence of CNTs is still not clear. Here, we probed the interplay between CNTs and PIs under UV exposure in the surface properties of CNT/PI nanocomposite films. Changes in contact angles and surface electrical conductivity at the surface of CNT/PI nanocomposite films after UV exposure were measured. The unpaired e…
Chapter 8: EPR in glass ceramics
The development of novel materials requires a profound understanding of the relationship between a material's performance and its structural properties. Electron paramagnetic resonance (EPR) is a well-established technique for a direct detection and identification of paramagnetic defects in solids. This chapter provides an overview of the applicability of continuous wave EPR spectroscopy in the studies of glass ceramics focusing on transition metal (Mn2 +, Cu2 +, Cr3 +) and rare earth (Gd3 +, Eu2 +, Er3 +, Yb3 +) ion local structure analysis. EPR spectra features of the above-mentioned paramagnetic probes in glasses and glass ceramics are compared and discussed in detail. The chapter also s…
Enhancement of persistent luminescence in Ca2SnO4: Sm3+
Abstract Reddish-orange persistent luminescent Ca2SnO4: 0.1% Sm3+ co-doped with 0–10% Gd3+ was prepared using solid state synthesis. The phase formation and morphology was analyzed using X-ray diffraction and scanning electron microscopy. Incorporation of Sm3+ and Gd3+ in Ca2SnO4 lattice was investigated using site-selective spectroscopy and electron paramagnetic resonance. In all samples reddish-orange persistent luminescence and photochromic effect was observed after excitation with UV as well as X-rays. The thermostimulated luminescence curves indicated that the introduction of Gd3+ increases the number of shallow traps of charges which enhance the intensity of persistent luminescence. I…
Photoluminescence and Electron Spin Resonance of Silicon Dioxide Crystal with Rutile Structure (Stishovite)
This work was supported by ERANET MYND. Also, financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2017/2 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged. The authors express our gratitude to R.I. Mashkovtsev for help in ESR signal interpretation. The authors are appreciative to T.I. Dyuzheva, L.M. Lityagina, N.A. Bendeliani for stishovite single crystals and to K. Hubner and H.-J. Fitting for stishovite powder of Barringer Meteor Crater.
EPR characterization of erbium in glasses and glass ceramics
Electron paramagnetic resonance (EPR) is a well-established spectroscopic technique for electronic structure characterization of rare-earth ion impurities in crystalline and amorphous hosts. EPR spectra of erbium-doped glass matrices and nanocomposites can provide information about local structure variations induced by changes in chemical composition or crystallization processes. Characterization possibilities of Er3+ ions in glasses and glass ceramics including direct EPR measurements, indirect investigations via secondary paramagnetic probes, and optically detected magnetic resonance techniques are considered in this article. ----/ / /---- This is the pre-print of the following article: A…
Multisite formation in gadolinium doped SrF2 nanoparticles
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Fe and Zn co-substituted beta-tricalcium phosphate (β-TCP): Synthesis, structural, magnetic, mechanical and biological properties
This work was supported by the European Social Fund under the No. 09.3.3- LMT-K-712 “Development of Competences of Scientists, other Researchers and Students through Practical Research Activities” measure. AK would like to express sincere gratitude for Fellowship administrated by The Japan Society for the Promotion of Science (JSPS). Fellow’s ID No.: L12546. Authors are grateful to R. Vargalis (Vilnius University) for taking SEM images. © 2020. This work is licensed under a CC BY-NC-ND license.
Shortwave Ultraviolet Persistent Luminescence of Sr2MgSi2O7: Pr3+
Currently, extensive research activities are devoted to developing persistent phosphors which extend beyond the visible range. In some emerging applications, long-lasting emission of high-energy photons is required; however, suitable materials for the shortwave ultraviolet (UV–C) band are extremely limited. This study reports a novel Sr2MgSi2O7 phosphor doped with Pr3+ ions, which exhibits UV–C persistent luminescence with maximum intensity at 243 nm. The solubility of Pr3+ in the matrix is analysed by X-ray diffraction (XRD) and optimal activator concentration is determined. Optical and structural properties are characterised by photoluminescence (PL), thermally stimulated lumi…
The influence of Fe3+ doping on thermally induced crystallization and phase evolution of amorphous calcium phosphate
The present study investigates thermally induced crystallization and phase evolution of amorphous calcium phosphate (ACP) partially substituted with Fe3+ ions (M/P = 1.5 : 1). It was demonstrated that the presence of Fe3+ ions radically changes the crystallization behavior of ACP and completely prevents the formation of α-tricalcium phosphate (α-TCP, Ca3(PO4)2), which is the first crystalline phase obtained from non-substituted ACP upon thermal treatment. Surprisingly, calcium deficient hydroxyapatite (CDHA) was obtained instead of α-TCP. Such unusual crystallization behavior was observed with a doping level as low as 0.1 mol% with respect to Ca ions. Moreover, it was shown that the presenc…
Luminescence of phosphorus doped silica glass
This work is supported by Material Science program IMIS2 of Latvia.