Raman and infrared investigations of glass and glass-ceramics with composition 2Na2O·1CaO·3SiO2

Precursor glass and glass-ceramics with molar composition 2Na2O·1CaO·3SiO2 are studied by infrared, conventional, and microprobe Raman techniques. The Gaussian deconvoluted Raman spectrum of the glass presents bands at 625 and 660 cm-1, attributed to bending vibrations of Si-O-Si bonds, and at 860, 920, 975, and 1030 cm-1, attributed to symmetric stretching vibrations of SiO4 tetrahedra with 4, 3, 2, and 1 nonbridging oxygens, respectively. The Raman microprobe spectrum of a highly crystallized sample presents two narrow and intense bands at about 590 and 980 cm-1, associated with vibrations of SiO4 tetrahedra with two nonbridging oxygens, in agreement with the predicted chain-like structure of crystalline metasilicates. Scanning electron microscopy shows that the crystals distributed in partially crystallized samples have a spherical shape, built up by radially oriented needle-like single crystals. The Raman microprobe spectra of these spherulites show that they still contain residual amorphous material. A comparison of Raman and infrared spectra of amorphous and highly crystallized samples is presented.

Determination of relative in vivo osteoconductivity of modified potassium fluorrichterite glass-ceramics compared with 45S5 bioglass

Potassium fluorrichterite (KNaCaMg5Si8O22F2) glass-ceramics were modified by either increasing the concentration of calcium (GC5) or by the addition of P2O5 (GP2). Rods (2 x 4 mm) of stoichiometric fluorrichterite (GST), modified compositions (GC5 and GP2) and 45S5 bioglass, which was used as the reference material, were prepared using a conventional lost-wax technique. Osteoconductivity was investigated by implantation into healing defects in the midshaft of rabbit femora. Specimens were harvested at 4 and 12 weeks following implantation and tissue response was investigated using computed microtomography (mu CT) and histological analyses. The results showed greatest bone to implant contact in the 45S5 bioglass reference material at 4 and 12 weeks following implantation, however, GST, GC5 and GP2 all showed direct bone tissue contact with evidence of new bone formation and cell proliferation along the implant surface into the medullary space. There was no evidence of bone necrosis or fibrous tissue encapsulation around the test specimens. Of the modified potassium fluorrichterite compositions, GP2 showed the greatest promise as a bone substitute material due to its osteoconductive potential and superior mechanical properties.

Development of glass-ceramics from combination of industrial wastes together with boron mining waste

The utilization of borate mineral wastes with glass-ceramic technology was first time studied and primarily not investigated combinations of wastes were incorporated into the research. These wastes consist of; soda lime silica glass, meat bone and meal ash and fly ash. In order to investigate possible and relevant application areas in ceramics, kaolin clay, an essential raw material for ceramic industry was also employed in some studied compositions. As a result, three different glass-ceramic articles obtained by using powder sintering method via individual sintering processes. Light weight micro porous glass-ceramic from borate mining waste, meat bone and meal ash and kaolin clay was developed. In some compositions in related study, soda lime silica glass waste was used as an additive providing lightweight structure with a density below 0.45 g/cm3 and a crushing strength of 1.8±0.1 MPa. In another study within the research, compositions respecting the B2O3–P2O5–SiO2 glass-ceramic ternary system were prepared from; borate wastes, meat bone and meal ash and soda lime silica glass waste and sintered up to 950ºC. Low porous, highly crystallized glass-ceramic structures with density ranging between 1.8 ± 0,7 to 2.0 ± 0,3 g/cm3 and tensile strength ranging between 8,0 ± 2 to 15,0 ± 0,5 MPa were achieved. Lastly, diopside - wollastonite (SiO2-Al2O3-CaO )glass-ceramics from borate wastes, fly ash and soda lime silica glass waste were successfully obtained with controlled rapid sintering between 950 and 1050ºC. The wollastonite and diopside crystal sizes were improved by adopting varied combinations of formulations and heating rates. The properties of the obtained materials show; the articles with a uniform pore structure could be useful for thermal and acoustic insulations and can be embedded in lightweight concrete where low porous glass-ceramics can be employed as building blocks or additive in cement and ceramic industries.

Titanate-based paraelectric glass-ceramics for applications in GHz electronics

Das Gebiet der drahtlosen Kommunikationsanwendungen befindet sich in einem permanenten Entwicklungsprozess (Mobilfunkstandards: GSM/UMTS/LTE/5G, glo-bale Navigationssatellitensysteme (GNSS): GPS, GLONASS, Galileo, Beidou) zu immer höheren Datenraten und zunehmender Miniaturisierung, woraus ein hoher Bedarf für neue, optimierte Hochfrequenzmaterialien resultiert. Diese Entwicklung zeigt sich besonders in den letzten Jahren in der zunehmenden Entwicklung und Anzahl von Smartphones, welche verschiedene Technologien mit unterschiedlichen Arbeitsfrequenzen innerhalb eines Geräts kombinieren (data: 1G-4G, GPS, WLAN, Bluetooth). Die für zukünftige Technologien (z.B. 5G) benötigte Performance-steigerung kann durch die Verwendung von auf MIMO basierenden Antennensystemen realisiert werden (multiple-input & multiple-output, gesteuerte Kombination von mehreren Antennen) für welche auf dielectric Loading basierende Technologien als eine der vielversprechendsten Implementierungslösungen angesehen werden. rnDas Ziel dieser Arbeit war die Entwicklung einer geeigneten paraelektrischen Glaskeramik ($varepsilon_{r}$ > 20, $Qf$ > 5000 GHz, |$tau_f$| < 20 ppm/K; im GHz Frequenzbe-reich) im $mathrm{La_{2}O_{3}}$-$mathrm{TiO_{2}}$-$mathrm{SiO_{2}}$-$mathrm{B_{2}O_{3}}$-System für auf dielectric Loading basierende Mobilfunkkommunikationstechnologien als Alternative zu existierenden kommerziell genutzten Sinterkeramiken. Der Fokus lag hierbei auf der Frage, wie die makroskopi-schen dielektrischen Eigenschaften der Glaskeramik mit ihrer Mikrostruktur korreliert bzw. modifiziert werden können. Es konnte gezeigt werden, dass die dielektrischen Materialanforderungen durch das untersuchte System erfüllt werden und dass auf Glaskeramik basierende Dielektrika weitere vorteilhafte nichtelektro-nische Eigenschaften gegenüber gesinterten Keramiken besitzen, womit dielektrische Glaskeramiken durchaus als geeignete Alternative angesehen werden können. rnEin stabiles Grünglas mit minimalen Glasbildneranteil wurde entwickelt und die chemische Zusammensetzung bezüglich Entglasung und Redoxinstabilitäten optimiert. Geeignete Dotierungen für dielektrisch verlustarme $mathrm{TiO_{2}}$-haltige Glaskeramiken wurden identifiziert.rnDer Einfluss der Schmelzbedingungen auf die Keimbildung wurde untersucht und der Keramisierungsprozess auf einen maximalen Anteil der gewünschten Kristallphasen optimiert um optimale dielektrische Eigenschaften zu erhalten. Die mikroskopische Struktur der Glaskeramiken wurde analysiert und ihr Einfluss auf die makroskopischen dielektrischen Eigenschaften bestimmt. Die Hochfrequenzverlustmechanismen wurden untersucht und Antennen-Prototypenserien wurden analysiert um die Eignung von auf Glaskeramik basierenden Dielektrika für die Verwendung in dielectric Loading Anwendungen zu zeigen.

Light curing through glass ceramics: effect of curing mode on micromechanical properties of dual-curing resin cements

OBJECTIVES The aim of this study was to investigate micromechanical properties of five dual-curing resin cements after different curing modes including light curing through glass ceramic materials. MATERIALS AND METHODS Vickers hardness (VH) and indentation modulus (Y HU) of Panavia F2.0, RelyX Unicem 2 Automix, SpeedCEM, BisCem, and BeautiCem SA were measured after 1 week of storage (37 °C, 100 % humidity). The resin cements were tested following self-curing or light curing with the second-generation light-emitting diode (LED) curing unit Elipar FreeLight 2 in Standard Mode (1,545 mW/cm(2)) or with the third-generation LED curing unit VALO in High Power Mode (1,869 mW/cm(2)) or in XtraPower Mode (3,505 mW/cm(2)). Light curing was performed directly or through glass ceramic discs of 1.5 or 3 mm thickness of IPS Empress CAD or IPS e.max CAD. VH and Y HU were analysed with Kruskal-Wallis tests followed by pairwise Wilcoxon rank sum tests (α = 0.05). RESULTS RelyX Unicem 2 Automix resulted in the highest VH and Y HU followed by BeautiCem SA, BisCem, SpeedCEM, and finally Panavia F2.0. Self-curing of RelyX Unicem 2 Automix and SpeedCEM lowered VH and Y HU compared to light curing whereas self-curing of Panavia F2.0, BisCem, and BeautiCem SA led to similar or significantly higher VH and Y HU compared to light curing. Generally, direct light curing resulted in similar or lower VH and Y HU compared to light curing through 1.5-mm-thick ceramic discs. Light curing through 3-mm-thick discs of IPS e.max CAD generally reduced VH and Y HU for all resin cements except SpeedCEM, which was the least affected by light curing through ceramic discs. CONCLUSIONS The resin cements responded heterogeneously to changes in curing mode. The applied irradiances and light curing times adequately cured the resin cements even through 1.5-mm-thick ceramic discs. CLINICAL RELEVANCE When light curing resin cements through thick glass ceramic restorations, clinicians should consider to prolong the light curing times even with LED curing units providing high irradiances.

Light curing through glass ceramics with a second- and a third-generation LED curing unit: effect of curing mode on the degree of conversion of dual-curing resin cements

Objectives The aim of this study was to measure the degree of conversion (DC) of five dual-curing resin cements after different curing modes with a second- and a third-generation light-emitting diode (LED) curing unit. Additionally, irradiance of both light curing units was measured at increasing distances and through discs of two glass ceramics for computer-aided design/manufacturing (CAD/CAM). Materials and methods Irradiance and spectra of the Elipar FreeLight 2 (Standard Mode (SM)) and of the VALO light curing unit (High Power Mode (HPM) and Xtra Power Mode (XPM)) were measured with a MARC radiometer. Irradiance was measured at increasing distances (control) and through discs (1.5 to 6 mm thickness) of IPS Empress CAD and IPS e.max CAD. DC of Panavia F2.0, RelyX Unicem 2 Automix, SpeedCEM, BisCem, and BeautiCem SA was measured with an attenuated total reflectance–Fourier transform infrared spectrometer when self-cured (negative control) or light cured in SM for 40 s, HPM for 32 s, or XPM for 18 s. Light curing was performed directly (positive control) or through discs of either 1.5- or 3-mm thickness of IPS Empress CAD or IPS e.max CAD. DC was analysed with Kruskal–Wallis tests followed by pairwise Wilcoxon rank sum tests (α = 0.05). Results Maximum irradiances were 1,545 mW/cm2 (SM), 2,179 mW/cm2 (HPM), and 4,156 mW/cm2 (XPM), and all irradiances decreased by >80 % through discs of 1.5 mm, ≥95 % through 3 mm, and up to >99 % through 6 mm. Generally, self-curing resulted in the lowest DC. For some cements, direct light curing did not result in higher DC compared to when light cured through ceramic discs. For other cements, light curing through ceramic discs of 3 mm generally reduced DC. Conclusions Light curing was favourable for dual-curing cements. Some cements were more susceptible to variations in curing mode than others. Clinical relevance When light curing a given cement, the higher irradiances of the third-generation LED curing unit resulted in similar DC compared to the second-generation one, though at shorter light curing times.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Interaction of fluorescence of resin cements with glass ceramics

Poster presented at the 24th Annual Meeting of the Portuguese Dental Association, Lisbon, 12-14 November 2015.

Flexural Strength of Glass-Infiltrated Zirconia/Alumina-Based Ceramics and Feldspathic Veneering Porcelains

Purpose: To compare the flexural strength of two glass-infiltrated high-strength ceramics and two veneering glass-ceramics.Materials and Methods: Four ceramic materials were tested: two glass-infiltrated high-strength ceramics used as framework in metal-free restorations [In-Ceram Zirconia IZ (Gr1) and In-Ceram Alumina IA (Gr2)], and two glass-ceramics used as veneering material in metal-free restorations [Vita VM7 (Gr3) and Vitadur-alpha (Gr4)]. Bar specimens (25 x 5 x 2 mm(3)) made from core ceramics, alumina, and zirconia/alumina composites were prepared and applied to a silicone mold, which rested on a base from a gypsum die material. The IZ and IA specimens were partially sintered in an In-Ceram furnace according to the firing cycle of each material, and then were infiltrated with a low-viscosity glass to yield bar specimens of high density and strength. The Vita VM7 and Vitadur-alpha specimens were made from veneering materials, by vibration of slurry porcelain powder and condensation into a two-part brass Teflon matrix (25 x 5 x 2 mm(3)). Excess water was removed with absorbent paper. The veneering ceramic specimens were then removed from the matrix and were fired as recommended by the manufacturer. Another ceramic application and sintering were performed to compensate the contraction of the feldspar ceramic. The bar specimens were then tested in a three-point bending test.Results: The core materials (Gr1: 436.1 +/- 54.8; Gr2: 419.4 +/- 83.8) presented significantly higher flexural strength (MPa) than the veneer ceramics (Gr3: 63.5 +/- 9.9; Gr4: 57.8 +/- 12.7).Conclusion: In-Ceram Alumina and Zirconia were similar statistically and more resistant than VM7 and Vitadur-alpha.

Structural, dielectric and optical properties of lithium borate-bismuth tungstate glass-ceramicsc

Glasses in the system (1 - x)Li2B4O7-xBi(2)WO(6) (0.1 less than or equal to x less than or equal to 0.35) were prepared by splat quenching technique. Powder X-ray diffraction (XRD) and differential thermal analysis (DTA) were employed to characterize the as-quenched glasses. High-resolution transmission electron microscopy (HR TEM) revealed the presence of fine, nearly spherical crystallites of Bi2WO6 varying from 1.5 to 20 nm in size, depending on x in the as-quenched glasses. The glasses (corresponding to x = 0.3) heat-treated at 723 K for 6 h gave rise to a clear crystalline phase of Bi2WO6 embedded in the Li2B4O7 glass matrix, as observed by X-ray studies. The dielectric constants of the as-quenched glasses as well as the glass-ceramics decreased with increase in frequency (40Hz-100 kHz) at 300 K, and the value obtained for the glass-ceramic (x = 0.2) is in agreement with the values predicted using Maxwell's model and the logarithmic mixture rule. The dielectric constants for both the as-quenched glass and the glass-ceramic increased with increase in temperature (300 - 873 K) and exhibited anomalies close to the onset of the crystallization temperature of the host glass matrix. The optical transmission properties:of these glass-ceramics were found to be compositional dependant. (C) 2000 Elsevier Science Ltd.

Early osseointegration of a strontium containing glass ceramic in a rabbit model

The most important property of a bone cement or a bone substitute in load bearing orthopaedic implants is good integration with host bone with reduced bone resorption and increased bone regeneration at the implant interface. Long term implantation of metal-based joint replacements often results in corrosion and particle release, initiating chronic inflammation leading onto osteoporosis of host bone. An alternative solution is the coating of metal implants with hydroxyapatite (HA) or bioglass or the use of bulk bioglass or HA-based composites. In the above perspective, the present study reports the in vivo biocompatibility and bone healing of the strontium (Sr)-stabilized bulk glass ceramics with the nominal composition of 4.5SiO(2)-3Al(2)O(3)-1.5P(2)O(5)-3SrO-2SrF(2) during short term implantation of up to 12 weeks in rabbit animal model. The progression of healing and bone regeneration was qualitatively and quantitatively assessed using fluorescence microscopy, histological analysis and micro-computed tomography. The overall assessment of the present study establishes that the investigated glass ceramic is biocompatible in vivo with regards to local effects after short term implantation in rabbit animal model. Excellent healing was observed, which is comparable to that seen in response to a commercially available implant of HA-based bioglass alone. (C) 2013 Elsevier Ltd. All rights reserved.

Ballistic impact of ceramics

The impact behaviour of a range of glass and ceramic materials has been studied using high-speed photography. A gas gun was used to project hardened spheres at plate specimens in the velocity range 30 to 1000m s-1. The target materials included soda-lime glass, boron carbide and various glass ceramics and aluminas. The performance of a particular ceramic was found to depend on a combination of parameters but of key importance was the relative hardness of the projectile and target materials. The fracture toughness, K(IC), had only a secondary effect.

Intense greeen upconversion luminescence in Er3+: Yb3+ codoped fluorophosphate glass ceramic containing SrTe5O11 nanocrystals

Er3+:Yb3+ codoped tellurite-fluorophosphate (TFP) glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540 nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte (FP) glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540 nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.