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.

Slow crack growth and reliability of dental ceramics

Objective. To determine the slow crack growth (SCG) and Weibull parameters of five dental ceramics: a vitreous porcelain (V), a leucite-based porcelain (D), a leucite-based glass-ceramic (E1), a lithium disilicate glass-ceramic (E2) and a glass-infiltrated alumina composite (IC). Methods. Eighty disks (empty set 12mm x 1.1mm thick) of each material were constructed according to manufacturers` recommendations and polished. The stress corrosion susceptibility coefficient (n) was obtained by dynamic fatigue test, and specimens were tested in biaxial flexure at five stress rates immersed in artificial saliva at 37 degrees C. Weibull parameters were calculated for the 30 specimens tested at 1MPa/s in artificial saliva at 37 degrees C. The 80 specimens were distributed as follows: 10 for each stress rate (10(-2), 10(-1), 10(1), 10(2) MPa/s), 10 for inert strength (10(2) MPa/s, silicon oil) and 30 for 10(0) MPa/s. Fractographic analysis was also performed to investigate the fracture origin. Results. E2 showed the lowest slow crack growth susceptibility coefficient (17.2), followed by D (20.4) and V (26.3). E1 and IC presented the highest n values (30.1 and 31.1, respectively). Porcelain V presented the lowest Weibull modulus (5.2). All other materials showed similar Weibull modulus values, ranging from 9.4 to 11.7. Fractographic analysis indicated that for porcelain D, glass-ceramics E1 and E2, and composite IC crack deflection was the main toughening mechanism. Significance. This study provides a detailed microstructural and slow crack growth characterization of widely used dental ceramics. This is important from a clinical standpoint to assist the clinician in choosing the best ceramic material for each situation as well as predicting its clinical longevity. It also can be helpful in developing new materials for dental prostheses. (c) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of processing induced particle alignment on the fracture toughness and fracture behavior of multiphase dental ceramics

Objective. To investigate the processing induced particle alignment on fracture behavior of four multiphase dental ceramics (one porcelain, two glass-ceramics and a glass-infiltrated-alumina composite). Methods. Disks (empty set12mm x 1.1 mm-thick) and bars (3 mm x 4 mm x 20 mm) of each material were processed according to manufacturer instructions, machined and polished. Fracture toughness (K(IC)) was determined by the indentation strength method using 3-point bending and biaxial flexure fixtures for the fracture of bars and disks, respectively. Microstructural and fractographic analyses were performed with scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Results. The isotropic microstructure of the porcelain and the leucite-based glass-ceramic resulted in similar fracture toughness values regardless of the specimen geometry. On the other hand, materials containing second-phase particles with high aspect ratio (lithium disilicate glass-ceramic and glass-infiltrated-alumina composite) showed lower fracture toughness for disk specimens compared to bars. For the lithium disilicate glass-ceramic disks, it was demonstrated that the occurrence of particle alignment during the heat-pressing procedure resulted in an unfavorable pattern that created weak microstructural paths during the biaxial test. For the glass-infiltrated-alumina composite, the microstructural analysis showed that the large alumina platelets tended to align their large surfaces perpendicularly to the direction of particle deposition during slip casting of green preforms. Significance. The fracture toughness of dental ceramics with anisotropic microstructure should be determined by means of biaxial testing, since it results in lower values. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of temperature and heating rate on the sintering of leucite-based dental porcelains

The aim of this work was to determine the effect of temperature and heating rate on the densification of four leucite-based dental porcelains: two low-fusion (Dentsply Ceramco and Ivoclar) and two high-fusion commercial porcelains (Dentsply Ceramco). Porcelain powders were characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), particle size distribution, helium picnometry, and by scanning electron microscopy. Test specimens were sintered from 600 to 1050 degrees C, with heating rates of 55 degrees C/min and 10 degrees C/min. The bulk density of the specimens was measured by the Archimedes method in water, and microstructures of fracture surfaces were analyzed by scanning electron microscopy (SEM). The results showed that densification of specimens increased with the increase in temperature. The increase in the heating rate had no effect on the densification of the porcelains studied. Both high-fusion materials and one of the low-fusing porcelains reached the maximum densification at a temperature that was 50 degrees C lower than that recommended by the manufactures. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

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.

Influence of acid-etching and ceramic primers on the repair of a glass ceramic

The objective of this study was to evaluate the influence of different primers on the microtensile bond strength (μT BS) between a feldspathic ceramic and two composites. Forty blocks (6.0 × 6.0 × 5.0 mm 3) were prepared from Vita Mark II . After polishing, they were randomly divided into 10 groups according to the surface treatment: Group 1, hydrofluoric acid 10% (HF) + silane; Group 2, CoJet + silane; Group 3, HF + Metal/Zirconia Primer; Group 4, HF + Clearfil Primer; Group 5, HF + Alloy Primer; Group 6, HF + V-Primer; Group 7, Metal/Zirconia Primer; Group 8, Clearfil Primer; Group 9, Alloy Primer; Group 10, V-Primer. After each surface treatment, an adhesive was applied and one of two composite resins was incrementally built up. The sticks obtained from each block (bonded area: 1.0 mm2 ± 0.2 mm) were stored in distilled water at 37°C for 30 days and submitted to thermocycling (7,000 cycles; 5°C/55°C ± 1°C). The μT BS test was carried out using a universal testing machine (1.0 mm/min). Data were analyzed using ANOVA and a Tukey test (α = 0.05). The surface treatments significantly affected the results (P < 0.05); no difference was observed between the composites (P > 0.05). The bond strength means (MPa) were as follows: Group 1a = 29.6; Group 1b = 33.7; Group 2a = 28.9; Group 2b = 27.1; Group 3a = 13.8; Group 3b = 14.9; Group 4a = 18.6; Group 4b = 19.4; Group 5a = 15.3; Group 5b = 16.5; Group 6a = 11; Group 6b = 18; Groups 7a to 10b = 0. While the use of primers alone was not sufficient for adequate bond strengths to feldspathic ceramic, HF etching followed by any silane delivered higher bond strength.

Mechanical and tribological properties of a sintered glass-ceramic compared to granite and porcelainized stoneware

Mechanical and tribological properties of a partially crystallized sintered glass-ceramic were compared to two commercial floor tiles: black granite and porcelainized stoneware. Mechanical properties, hardness and elastic modulus were evaluated by instrumented indentation. Friction coefficient and wear characterization were evaluated using a reciprocating ball-on-flat tribometer in two controlled environments: air with relative humidity of 53% and under running water at 23 degrees C. The sintered glass-ceramic and porcelainized stoneware presented similar mechanical and tribological properties. Regarding the mechanical and tribological properties, the results suggest that this glass-ceramic is suitable to be used as industrial tile. (C) 2011 Elsevier B.V. All rights reserved.

Surface characterization of 6H-SiC (0001) substrates in indentation and abrasive machining

Surface characterization of 6H-SiC (0001) substrates in indentation and abrasive machining was carried out to investigate microfracture, residual damage, and surface roughness associated with material removal and surface generation. Brittle versus plastic deformation was studied using Vickers indention and nano-indentation. To characterize the abrasive machining response, the 6H-SiC (0001) substrates were ground using diamond wheels with grit sizes of 25, 15 and 7 mum, and then polished with diamond suspensions of 3 and 0.05 mum. It is found that in indentation, there was a scale effect for brittle versus plastic deformation in 6H-SiC substrates. Also, in grinding, the scales of fracture and surface roughness of the substrates decreased with a decrease in diamond grit size. However, in polishing, a reduction in grit size of diamond suspensions gave no significant improvement in surface roughness. Furthermore, the results showed that fracture-free 6H-SiC (0001) surfaces were generated in polishing with the existence of the residual crystal defects, which were associated with the origin of defects in single crystal growth. (C) 2003 Elsevier Ltd. All rights reserved.