Zirconia toughened fluorosilicate glass-ceramics for dental prosthetic restorations.

Background: Dental glass-ceramics have limited strength and are unsuitable for high-stress-bearing areas. Zirconia stands out as a popular choice for reinforcing dental glass-ceramics due to its biocompatibility and high fracture toughness. Objectives: The objective of the study is to investigate the effect of an increase in zirconia (25, 30, 35 and 50 wt%) on microstructure, chemical solubility, hardness, fracture toughness, and brittleness index of fluorosilicate glass systems for dental restorative applications. Material and methods: The fluorosilicate glass frit was obtained through the melt-quench technique. The glass frit was ball-milled with 25, 30, 35 and 50 wt % of 3 mol% yttria-stabilized zirconia (G-25Z, G-30Z, G-35Z, and G-50Z). The composites were sintered to 1000 °C for 48h at a heating rate of 5 °C/min. The glass frit was subject to differential scanning calorimetry. Phase analysis and microstructural characterization were carried out. The crystallite size of zirconia and glass-ceramics, micro-hardness, indentation fracture toughness, brittleness index, and chemical solubility were evaluated. Results: Phase analysis reveals tetragonal and monoclinic zirconia with minor peaks of forsterite, fluorphlogopite, norbergite, and spinel. Their microstructures reveal the characteristic house-of-cards arrangement of fluorophlogopite crystals with dispersed zirconia. The results of hardness and fracture toughness show a statistically significant improvement with an increase in zirconia content. The crystallite size of zirconia and fluorophlogopite crystals with aspect ratio, brittleness index, and chemical solubility declined as the zirconia content increased. Conclusions: Increase in zirconia content from 25 wt % to 50 wt % in heat-treated fluorosilicate glass systems reveals non-reactive zirconia with a stable glass matrix and limits the growth of fluorphlogopite crystals with a house-of-cards microstructure. This results in a range of properties suitable for dental restorations of enhanced hardness, and improved fracture toughness. Despite these improvements, the material maintains its machinability with reduced chemical solubility.

Exploring Optically Stable Reddish-Orange Fluorescent Magnetic Pigment (0.90)Y2O3:(0.10-x)Eu3+:(x)Bi3+ for Anti-counterfeiting Applications.

The (0.90)Y2O3:(0.10-x)Eu3+:(x)Bi3+ nanophosphors (0.00 ≤ x ≤ 0.06) are synthesised using chemical combustion citrate route and characterized via X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, UV- visible and photoluminescence spectroscopy. The scanning electron micrographs indicate that the grain size of the phosphors ranges between 40 to 50 nm. The photoluminescence (PL) spectra, acquired under the excitation wavelength of 365 nm of ultraviolet light, show emission peaks at wavelengths 580 nm, 586-598 nm, 610 nm, 629-661 nm and 686-695 nm corresponding to the 5D0 → 7FJ electronic transitions of the Eu3+ ion with J = 0, 1, 2, 3 and 4, respectively. The most intense PL spectra at 611 nm (5D0 → 7F2), showcasing reddish-orange emission, indicate a higher concentration of Eu3+ ions in asymmetric sites within the Y2O3 host matrix. The presence of the distinct electronic transitions of Eu3+ in PL spectra acclaims that Bi3+ ions transfer their energy efficiently to Eu3+ ions in the matrix. Physical and chemical tests are being conducted on nanophosphors with Bi3+ substitutional doping of x = 0.02 and x = 0.04, both demonstrating intense PL emission. Magnetisation measurements suggest the soft magnetic nature of the nanophosphors, attributing it to the presence of Eu3+ ions in the 7F2 state. The highest PL intensity is seen in the nanophosphor (x = 0.04) with substitutional doping of 6% of Eu3+ and 4% of Bi3+ in Y2O3. This nanophosphor also demonstrates excellent optical stability in the investigated conditions and exhibits soft magnetic behaviour, positioning it as a promising material for incorporation as a fluorescent magnetic pigment in security ink applications. These features serve to prevent counterfeiting of secured documents both optically and magnetically.

One material, many possibilities via enrichment of luminescence in La2Zr2O7:Tb3+ nanophosphors for forensic stimuli aided applications.

Engineering a single material with multidirectional applications is crucial for improving productivity, low cost, flexibility, least power consumption, etc. To achieve these requirements, novel design structures and high-performance materials are in urgent need. Lanthanide-doped nanophosphors have the greatest strengths and ability in order to tune their applications in various dimensions. However, applications of nanophosphor in latent fingerprints visualization, anti-counterfeiting, and luminescent gels/films are still in their infancy. This study demonstrated a simple strategy to enhance the luminescence of Tb3+ (1-11 mol %) doped La2Zr2O7 nanophosphors by conjugating various fluxes via a simple solution combustion route. The photoluminescence emission spectra reveal intense peaks at ~ 491, 546, 587, and 622 nm, which arises from 5D4 → 7FJ (J = 6, 5, 4, 3) transitions of Tb3+ ions, respectively. The highest emission intensity was achieved in the NH4Cl flux assisted nanophosphor as compared to NaBr and NH4F assisted samples. The colorimetric images of fingerprints visualized using the optimized nanophosphor on forensic related surfaces exhibit level -III ridge details, including sweat pores, the width of the ridges, bifurcation angle, and the successive distance between sweat pores, etc. These results are decisive parameters that clearly support the statement "no two persons have ever been found to have the same fingerprints". The anti-counterfeiting security ink was formulated using optimized nanophosphor and various patterns were designed by simple screen printing and dip pen technologies. The encoded information was decrypted only under ultraviolet 254 nm light. All the designed patterns are exhibit not just what it looks/feel like and how better it works. As a synergetic contribution of enhanced luminescence of the prepared nanophosphor, the green-emissive films were fabricated, which display excellent flexibility, uniformity, and transparency in the normal and ultraviolet 254 nm light illumination. The aforementioned results revealed that the prepared NH4Cl flux-assisted La2Zr2O7: Tb3+(7 mol %) NPs are considered to be the best candidate for multi-dimensional applications.

Aggregation induced emission based active conjugated imidazole luminogens for visualization of latent fingerprints and multiple anticounterfeiting applications.

Aggregation-induced emission based organic heterocyclic luminogens bearing conjugated electronic structures showed much attention due to its excellent fluorescence in aggregation state. In this communication, a novel conjugated blue light emitting imidazole molecule is synthesized by one pot multicomponent reaction route is reported for the first time. The prepared molecule exhibits a strong fluorescence in aggregation state with exceptional properties, such as high purity, inexpensive, eco-friendly, large scale production, high photostability, etc. By considering these advantages, a new fluorescence based platform has been setup for in-situ visualization of latent fingerprints and its preservation by spray method followed by Poly(vinyl alcohol) masking. A clear and well defined fluorescence fingerprint images are noticed on variety of surfaces by revealing level 1-3 ridge features upon ultraviolet 365 nm light exposure. The dual nature of binding specificity as well as excellent fluorescence properties permits the visualization of latent fingerprints for longer durations (up to 365 days) with superior contrast, high sensitivity, efficiency, selectivity and minimal background hindrance. We further fabricated unclonable invisible security ink for various printing modes on valuable goods for protection against forging. The developed labels are displaying uniform distribution of ink and exceptional stability under various atmospheric environments. The development of long preservative information using aggregation-induced emission based luminogen opens up a new avenue in advanced forensic and data security applications.

Surface functionalized inorganic phosphor by grafting organic antenna for long term preservation of latent fingerprints and data-security applications.

Creative advancements are enormously sought for the advanced forensic and data security in modern era. Herein, fabrication of Bovine Serum Albumin (BSA) functionalized Gd2O3:Eu3+ (5 mol %) nanopowders dispersed in a poly(vinyl alcohol) (PVA) matrix for long term preservation and visualization of latent fingerprints, as well as printing. Efficient intramolecular energy transfers from coordinated ligand to the doped Eu3+ ions, called the antenna effect was precisely organized by grafting organic molecule, resultant to an enhanced photoluminescence emission. On this basis, the masking of PVA/Gd2O3:Eu3+ (5 mol %)@BSA solution on a latent fingerprints results a flexible transparent film; a highly stable fingerprint images with well-defined ridge characteristics was developed on the film, which enabling personal individualization. Interestingly, the followed latent fingerprints development technique was non-destructive and stored long duration up to 1 year on filtrating and non-filtrating surfaces. The same mechanism was also validated by utilized for application of PVA/Gd2O3:Eu3+ (5 mol %)@BSA nanocomposites in dip pen and intaglio printing. Hence, the prepared nanocomposites signify an competent method towards long preservative fingerprints as well as great performance for data security operations. This work endorses a prospective paradigm for luminescence enhancement and its applications in advanced forensic science.

Novel EGCG assisted ultrasound synthesis of self-assembled Ca2SiO4:Eu(3+) hierarchical superstructures: Photometric characteristics and LED applications.

This paper reports for the first time ultrasound, EGCG assisted synthesis of pure and Eu(3+) (1-5mol%) activated Ca2SiO4 nanophosphors having self-assembled superstructures with high purity. The shape, size and morphology of the product were tuned by controlling influential parameters. It was found that morphology was highly dependent on EGCG concentration, sonication time, pH and sonication power. The probable formation mechanism for various hierarchical superstructures was proposed. The PL studies of Ca2SiO4:Eu(3+) phosphors can be effectively excited by the near ultraviolet (UV) (396nm) light and exhibited strong red emission around 613nm, which was attributed to the Eu(3+) ((5)D0→(7)F2) transition. The concentration quenching phenomenon was explained based on energy transfer between defect and Eu(3+) ions, electron-phonon coupling and Eu(3+)-Eu(3+) interaction. The Judd-Ofelt intensity parameters and radiative properties were estimated by using PL emission spectra. The photometric studies indicate that the obtained phosphors could be a promising red component for possible applications in the field of white light emitting diodes.

Effective fingerprint recognition technique using doped yttrium aluminate nano phosphor material.

First time the yttrium aluminate nanoparticles are used to improve the fingerprint quality. Eco-friendly green combustion process is used to synthesize YAlO3:Sm(3+) (0.5-11mol%) nanophosphor using green tea leaf extract as non-toxic and eco-friendly fuel. Powder X-ray diffraction study confirms the orthorhombic phase. The average sizes of the crystallites were found to be in the range 20-35nm. The emission peaks centered at 564, 601 and 647nm is attributed to 4f-4f (4)G5/2→(6)HJ=5/2,7/2,9/2 forbidden transitions of Sm(3+) ions. Judd-Ofelt theory is applied to experimental data for providing qualitative support by determining J-O intensity parameters. The Commission International De I-Eclairage chromaticity co-ordinates are very close to National Television System Committee standard value of white emission (x=0.296, y=0.237). Further, correlated color temperature is found to be ∼11,900K. A simple, fast, highly sensitive and low-cost method for the detection and enhancement of fingermarks in a broad range of surfaces is developed and constitutes an alternative to traditional luminescent powders.

Shape tailored green synthesis of CeO2:Ho³âº nanopowders, its structural, photoluminescence and gamma radiation sensing properties.

CeO2:Ho(3+) (1-9 mol%) nanopowders have been prepared by efficient and environmental friendly green combustion method using Aloe vera gel as fuel for the first time. The final products are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), fourier transform infrared (FTIR). Bell, urchin, core shell and flower like morphologies are observed with different concentrations of the A. vera gel. It is apparent that by adjusting the concentration of the gel, considerable changes in the formation of CeO2:Ho(3+) nano structures can be achieved. Photoluminescence (PL) studies show green (543, 548 nm) and red (645, 732 nm) emissions upon excited at 400 nm wavelength. The emission peaks at ∼526, 548, 655 and 732 nm are associated with the transitions of (5)F3→(5)I8, (5)S2→(5)I8, (5)F5→(5)I8 and (5)S2→(5)I7, respectively. Three TL glow peaks are observed at 118, 267 and 204°C for all the γ irradiated samples which specify the surface and deeper traps. Linear TL response in the range 0.1-2kGy shows that phosphor is fairly useful as γ radiation dosimeter. Kinetic parameters associated with the glow peaks are estimated using Chen's half width method. The CIE coordinate values show that phosphor is quite useful for the possible applications in WLEDs as orange red phosphor.

A single phase, red emissive Mg2SiO4:Sm3+ nanophosphor prepared via rapid propellant combustion route.

Mg2SiO4:Sm3+ (1-11 mol%) nanoparticles were prepared by a rapid low temperature solution combustion route. The powder X-ray diffraction (PXRD) patterns exhibit orthorhombic structure with α-phase. The average crystallite size estimated using Scherer's method, W-H plot and strain-size plots were found to be in the range 25-50 nm and the same was confirmed by Transmission Electron Microscopy (TEM). Scanning electron microscopy (SEM) pictures show porous structure and crystallites were agglomerated. The effect of Sm3+ cations on luminescence of Mg2SiO4 was well studied. Interestingly the samples could be effectively excited with 315 nm and emitted light in the red region, which was suitable for the demands of high efficiency WLEDs. The emission spectra consists of four main peaks which can be assigned to the intra 4-f orbital transitions of Sm3+ ions 4G5/2→6H5/2 (576 nm), 4G5/2→6H7/2 (611 nm), 4G5/2→6H9/2 (656 nm) and 4G5/2→6H11/2 (713 nm). The optimal luminescence intensity was obtained for 5 mol% Sm3+ ions. The CIE (Commission International de I'Eclairage) chromaticity co-ordinates were calculated from emission spectra, the values (0.588, 0.386) were close to the NTSC (National Television Standard Committee) standard value of red emission. Coordinated color temperature (CCT) was found to be 1756 K. Therefore optimized Mg2SiO4:Sm3+ (5 mol%) phosphor was quite useful for solid state lighting.

Bio-inspired synthesis of Y2O3: Eu(3+) red nanophosphor for eco-friendly photocatalysis.

We report the synthesis of Y2O3: Eu(3+) (1-11 mol%) nanoparticles (NPs) with different morphologies via eco-friendly, inexpensive and simple low temperature solution combustion method using Aloe Vera gel as fuel. The formation of different morphologies of Y2O3: Eu(3+) NPs were characterized by PXRD, SEM, TEM, HRTEM, UV-Visible and PL techniques. The PXRD data and Rietveld analysis confirms the formation of single phase Y2O3 with cubic crystal structure. The influence of Eu(3+) ion concentration on the morphology, UV-Visible absorption, PL emission and photocatalytic activity of Y2O3: Eu(3+) nanostructures were investigated. Y2O3: Eu(3+) NPs exhibit intense red emission with CIE chromaticity coordinates (0.50, 0.47) and correlated color temperature values at different excitation ranges from 1868 to 2600 K. The control of Eu(3+) ion on Y2O3 matrix influences the photocatalytic decolorization of methylene blue (MB) as a model compound was evaluated under UVA light. Enhanced photocatalytic activity of conical shaped Y2O3: Eu(3+) (1 mol%) was attributed to dopant concentration, crystallite size, textural properties and capability of reducing the electron-hole pair recombination. The trend of inhibitory effect in the presence of different radical scavengers followed the order SO4(2-)>Cl(-)>C2H5OH>HCO3(-)>CO3(2-). These findings show great promise of Y2O3: Eu(3+) NPs as a red phosphor in warm white LEDs as well as eco-friendly heterogeneous photocatalysis.

Zn2TiO4:Eu(3+) nanophosphor: self explosive route and its near UV excited photoluminescence properties for WLEDs.

A simple and low-cost solution combustion method was used to prepare Eu(3+) (1-11mol%) doped Zn2TiO4 nanophosphors at 500°C using zinc nitrates as precursors and oxalyl di-hydrazide (ODH) as fuel. The final product was calcined at 1100°C for 3h and then characterized by powder X-ray diffraction (PXRD), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-visible absorption (UV-Vis). The PXRD patterns of the sample calcined at 1100°C show pure cubic phase. The crystallite size was estimated using Scherrer's method and found to be in the range 20-25nm and the same was confirmed by TEM studies. Effects of Eu(3+) (1-11mol%) cations on the luminescence properties of Zn2TiO4 nanoparticles were studied. The samples exhibit intense red emission upon 395nm near ultra violet (NUV) excitation. The characteristic emission peaks recorded at ∼578, 592, 613 and 654nm may be attributed to the 4f-4f intra shell transitions ((5)D0→(7)Fj=0,1,2,3) of Eu(3+) cations. The CIE chromaticity co-ordinates and CCT were calculated from emission spectra and the values (x, y) were very close to NTSC standard values for red emission and CCT was close to Plankian locus. Therefore, the present phosphor may be highly useful for display applications.

Synthesis, EPR and luminescent properties of YAlO3:Fe3+ (0.1-0.9mol%) nanopowders.

A simple and inexpensive combustion method was used to prepare Fe(3+) doped YAlO3 perovskite within few minutes at low temperature (400±10°C). This might be useful in lowering the cost of the material. The final products were well characterized by various spectroscopic techniques such as PXRD, SEM, TEM, FTIR and UV-Visible. The average crystallite size was estimated from the broadening of the PXRD peaks and found to be in the range 45-90nm, the results were in good agreement with the W-H plots and TEM. The crystallites show dumbbell shape, agglomerated particles with different size. The TL glow curves of 1-5kGy γ-irradiated YAlO3:Fe(3+) (0.1mol%) nanopowder warmed at a heating rate of 3°Cs(-1) records a single glow peak at ∼260°C. The kinetic parameters namely activation energy (E), order of kinetics (b) and frequency factor (s) were determined at different gamma doses using the Chens glow peak shape method and the results were discussed in detail. The photoluminescence spectra for Fe(3+) (0.1-0.9mol%) doped YAlO3 records the lower energy band at 720nm ((4)T1 (4G)→(6)A1 (6S)) and the intermediate band located at 620nm ((4)T2 ((4)G)→(6)A1 (6S)) with the excitation of 378nm. The higher energy band located at 514nm was associated to (4)E+(4)A1 ((4)G)→(6)A1 (6S) transition. The resonance signals at g values 7.6, 4.97, 4.10, 2.94, 2.33 and 1.98 were observed in EPR spectra of Fe(3+) (0.1-0.9mol%) doped YAlO3 recorded at room temperature. The g values indicate that the iron ions were in trivalent state and distorted octahedral site symmetry was observed.

MgO:Eu3+ red nanophosphor: low temperature synthesis and photoluminescence properties.

Nanoparticles of Eu(3+) doped (0-9 mol%) MgO were prepared using low temperature (400°C) solution combustion technique with metal nitrate as precursor and glycine as fuel. The powder X-ray diffraction (PXRD) patterns of the as-formed products show single cubic phase and no further calcination was required. The crystallite size was obtained using Scherer's formula and was found to be 5-6 nm. The effect of Eu(3+) ions on luminescence characteristics of MgO was studied and the results were discussed in detail. These phosphors exhibit bright red emission upon 395 nm excitation. The characteristic photoluminescence (PL) emission peaks at ∼580, 596, 616, 653, 696 and 706 nm ((5)D0→(7)Fj=0, 1, 2, 3, 4) were recorded due to Eu(3+) ions. The electronic transition corresponding to (5)D0→(7)F2 of Eu(3+) ions (616 nm) was stronger than the magnetic dipole transition corresponding to (5)D0→(7)F1 of Eu(3+) ions (596 nm). The international commission on illumination (CIE) chromaticity co-ordinates were calculated from emission spectra, the values (x, y) were very close to national television system committee (NTSC) standard value of red emission. Therefore the present phosphor was highly useful for display applications.

Investigation of structural and luminescence properties of Ho(3+) doped YAlO3 nanophosphors synthesized through solution combustion route.

YAlO3:Ho(3+) (1-5mol%) nanophosphors have been prepared by solution combustion route using oxalyl dihydrazide (ODH) as a fuel. The final product was well characterized by powder X-ray diffraction (PXRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), UV-Vis, etc. PXRD patterns confirm the formation of highly crystalline orthorhombic phase structure. SEM and TEM studies show the particles are dumbbell shape, highly agglomerated and nano-size (∼30nm). The direct energy band gap (Eg) values estimated from Tauc's relation were found to be in the range 5.76-5.99eV. Photoluminescence (PL) studies show green (540 and 548nm) and red (645 and 742nm) emissions upon excited at 452nm wavelength. The emission peaks at ∼742 and 645nm was associated with the transitions of (5)F4→(5)I7 and (5)F5→(5)I8 respectively. The higher energy bands located at 540 and 548nm were associated with (5)F4, (5)S2→(5)I8 transitions. Thermoluminescence (TL) studies of γ-irradiated YAlO3:Ho(3+) (1-5mol%) show two glow peaks at 223 and 325°C recorded at a heating rate of 2.5°Cs(-1). The 223°C glow peak follow linear behavior up to 1kGy and after that, it showed sub-linearity. Up to 1kGy, the phosphor is quite useful in radiation dosimetry. The kinetic parameters (E, b and s) were estimated from glow peak shape method. The CIE coordinate values lies within the green region. Therefore, the present phosphors may have potential application in WLEDs as green phosphor.

YAlO3:Cr3+ nanophosphor: synthesis, photoluminescence, EPR, dosimetric studies.

YAlO(3):Cr(3+) (0.1 mol%) nanophosphor has been synthesized by low temperature solution combustion method. The X-ray diffraction studies reveal an orthorhombic structure. Transmission electron microscopy reveals that the particles are spherical in shape with nano-size ~40-65 nm. Electron paramagnetic resonance (EPR) spectrum shows a resonance signal with effective g value at g=1.978 which can be attributed to the exchange coupled Cr(3+) ion pairs in weakly distorted sites. The photoluminescence spectrum shows an intense doublet at 677 nm and 694 nm (R lines) assigned to spin-forbidden (2)E(g)→(4)A(2)(g) transition of Cr(3+) ions. EPR and PL studies reveal that the Cr(3+) ions occupy Al(3+) sites in YAlO(3). The interesting feature reported in this work concerns the linearity with gamma dose in the wide range (0.1-6 kGy). Prominent TL glow peaks at 226 °C and 346 °C were observed for both γ and UV-rays respectively. It is observed that the peaks at 226 °C and 346 °C eventually show a linear response up to 5 kGy which makes them a candidate for high dose dosimetry of ionizing radiation. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped and Cr doped samples were determined using Chens glow peak shape method and the results are discussed in detail.