An in situ and ex situ study of the microstructural evolution of a novel lithium silicate glass-ceramic during crystallization firing.

OBJECTIVE: To elucidate the compositional and microstructural developments of a novel lithium silicate glass-ceramic during its crystallization cycle. METHODS: Blocks of a lithium silicate glass-ceramic (Obsidian®, Glidewell Laboratories) were cut into 1mm thick plates and polished to 1µm finish. Some of them were crystallized prior to polishing. Firstly, ex situ compositional and microstructural characterizations of both the pre- and post-crystallized samples were performed by wavelength dispersive X-ray fluorescence, field-emission scanning electron microscopy, and X-ray diffractometry. Secondly, the pre-crystallized samples were subjected to in situ compositional and microstructural characterizations under non-isothermal heating by simultaneous thermogravimetry/differential scanning calorimetry, X-ray thermo-diffractometry, and field-emission scanning electron thermo-microscopy. RESULTS: The microstructure of pre-crystallized Obsidian® consists of an abundant population of perlitic-like/dendritic lithium silicate (Li2SiO3) nanocrystals in a glass matrix. Upon heating, the residual glassy matrix does not crystallize into any form of SiO2; elemental oxides do not precipitate unless over-heated above 820°C; and the Li2SiO3 nanocrystals do not react with the glassy matrix to form typical lithium disilicate (Li2Si2O5) crystals. Nonetheless, the Li2SiO3 nanocrystals grow and spheroidize through the solution-reprecipitation process in the softened glass, and new lithium orthophosphate (Li3PO4) nanocrystals precipitate from the glass matrix. SIGNIFICANCE: The identification of compositional and microstructural developments of Obsidian® indicates that, by controlling the firing conditions, it is possible to tailor its microstructure, which in turn could affect its mechanical and optical properties, and ultimately its clinical performance.

Reinforcing 13-93 bioglass scaffolds fabricated by robocasting and pressureless spark plasma sintering with graphene oxide.

13-93 bioglass (BG) scaffolds reinforced with graphene oxide (GO) were fabricated by robocasting (direct-ink-writing) technique. Composite scaffolds with 0-4 vol% content of GO platelets were printed, and then consolidated by pressureless spark plasma sintering at 650 °C. It was found that, despite hampering densification of the bioglass, the addition of GO platelets up to a certain content enhanced the mechanical performance of the 13-93 bioglass scaffolds in terms of strength and, especially, toughness. Best performance was obtained for 2 vol.% GO, which increased strain energy density (toughness) of the scaffolds by ∼894%, and their compressive strength by ∼26%. At higher contents, agglomeration of the nanoplatelets and increased porosity significantly reduced the mechanical enhancement obtained. Implications of the results on the fabrication of novel bioglass scaffolds that may find use in load-bearing bone tissue engineering applications are discussed.

Microstructural development during heat treatment of a commercially available dental-grade lithium disilicate glass-ceramic.

OBJECTIVE: To elucidate the microstructural evolution of a commercial dental-grade lithium disilicate glass-ceramic using a wide battery of in-situ and ex-situ characterization techniques. METHODS: In-situ X-ray thermo-diffractometry experiments were conducted on a commercially available dental-grade lithium disilicate glass-ceramic under both non-isothermal and isothermal heat treatments in air. These analyses were complemented by experiments of ex-situ X-ray diffractometry, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, differential scanning calorimetry, and field-emission scanning electron thermo-microscopy. RESULTS: It was found that the non-fired blue block consists of ∼40 vol % crystals embedded in a glass matrix. The crystals are mainly lithium metasilicate (Li2SiO3) along with small amounts of lithium orthophosphate (Li3PO4) and lithium disilicate (Li2Si2O5). Upon heating, the glassy matrix in the as-received block first crystallizes partially as SiO2 (i.e., cristobalite) at ∼660 °C. Then, the SiO2 crystals react with the original Li2SiO3 crystals at ∼735 °C, forming the desired Li2Si2O5 crystals by a solid-state reaction in equimolar concentration (SiO2 + Li2SiO3 → Li2Si2O5). Precipitation of added colourant Ce ions in the form of CeO2 appears at ∼775 °C. These events result in a glass-ceramic material with the aesthetic quality and mechanical integrity required for dental restorations. It also has a microstructure consisting essentially of elongated Li2Si2O5 grains in a glassy matrix plus small cubic CeO2 grains at the outermost part of the surface. SIGNIFICANCE: It was found that by judiciously controlling the heat treatment parameters, it is possible to tailor the microstructure of the resulting glass-ceramics and thus optimizing their performance and lifespan as dental restorations.

Expression of CHRFAM7A and CHRNA7 in neuronal cells and postmortem brain of HIV-infected patients: considerations for HIV-associated neurocognitive disorder.

Despite the recent advances in antiretroviral therapy, human immunodeficiency virus type 1 (HIV-1) remains a global health threat. HIV-1 affects the central nervous system by releasing viral proteins that trigger neuronal death and neuroinflammation, and promotes alterations known as HIV-associated neurocognitive disorders (HAND). This disorder is not fully understood, and no specific treatments are available. Recently, we demonstrated that the HIV-1 envelope protein gp120IIIB induces a functional upregulation of the α7-nicotinic acetylcholine receptor (α7) in neuronal cells. Furthermore, this upregulation promotes cell death that can be abrogated with receptor antagonists, suggesting that α7 may play an important role in the development of HAND. The partial duplication of the gene coding for the α7, known as CHRFAM7A, negatively regulates α7 expression but its role in HIV infection has not been studied. Hence, we studied both CHRNA7 and CHRFAM7A regulation patterns in various gp120IIIB in vitro conditions. In addition, we measured CHRNA7 and CHRFAM7A expression levels in postmortem brain samples from patients suffering from different stages of HAND. Our results demonstrate the induction of CHRNA7 expression accompanied by a significant downregulation of CHRFAM7A in neuronal cells when exposed to pathophysiological concentrations of gp120IIIB. Our results suggest a dysregulation of CHRFAM7A and CHRNA7 expressions in the basal ganglia from postmortem brain samples of HIV+ subjects and expand the current knowledge about the consequences of HIV infection in the brain.

A line-broadening analysis model for the microstructural characterization of nanocrystalline materials from asymmetric x-ray diffraction peaks.

Nanograin sizes and crystal lattice microstrains in nanocrystalline materials are typically evaluated from the broadening of their x-ray diffraction (XRD) peaks under the assumption of symmetrical diffraction profiles. Since this assumption is not entirely satisfactory, we formulate a line-broadening analysis model of a single peak that considers explicitly the XRD peak asymmetry. The model is a generalization of the variance method in which the shape of the XRD peaks is idealized through asymmetrical split pseudo-Voigt functions. The model is validated on two nanocrystalline powders.

A family of hydrogels based on ureido-linked aminopolyol-derived amphiphiles and bolaamphiphiles: synthesis, gelation under thermal and sonochemical stimuli, and mesomorphic characterization.

This article describes the systematic preparation of a novel family of carbohydrate amphiphiles and bolaamphiphiles in which hydrophilic and hydrophobic units are connected via a ureido or bis(ureido) moiety. The sugar core is derived from aminopolyols such as D-glucamine (1), N-methyl-D-glucamine (2), or the sugar-like species tris(hydroxymethyl)aminomethane (3). The O-unprotected derivatives behave as self-organizing nonionic surfactants with good water gelation ability, which can be induced under thermal or ultrasound-driven stimuli. In addition, some derivatives of 1 and 2, and rarely 3 also formed lyotropic liquid crystals with lamellar or hexagonal structures that exhibit low-temperature transitions.

Influence of preparation conditions in the textural and chemical properties of activated carbons from a novel biomass precursor: the coffee endocarp.

In this work a novel biomass precursor for the production of activated carbons (AC) was studied. The lignocellulosic material used as precursor is the coffee bean endocarp, which constitutes an industrial residue from the Portuguese coffee industry. Activation by carbon dioxide and potassium hydroxide produces activated carbons with small external areas and pore volumes up to 0.22 and 0.43cm3g(-1), respectively, for CO2 and KOH activation. All the AC's produced are very basic in nature with point of zero charge higher than 8. SEM/EDX studies indicate the presence of K, O, Ca and Si. By FTIR it was possible to identify the formation on the AC's surface of several functional groups, namely phenol, alcohol, quinone, lactone, pyrone and ether as well as SiH groups. The tailoring of the porous and chemical structure of the activated carbons produced is possible by selecting the appropriate production conditions.

Stability of lithium hydride in argon and air.

The oxidation behaviors of LiH under a high purity argon atmosphere, an argon atmosphere with some O2 and H2O impurities, and ambient air at both room and high temperatures, are investigated using a variety of analytical instruments including X-ray diffractometry, thermogravimetry, mass spectrometry, scanning electron microscopy, and specific surface area analysis. The oxidation behaviors of the ball-milled LiH under different atmospheres are also studied and compared with those without ball milling. It is shown that no oxidation of LiH occurs under a high-purity argon atmosphere. However, oxidation of LiH takes place when the argon atmosphere contains some H2O and O2 impurities. At temperatures higher than approximately 55 degrees C, oxidation of LiH proceeds via the reaction of LiH + 1/4 O2 = 1/2 Li2O + 1/2 H2, whereas at room temperature oxidation of LiH is likely caused by the simultaneous reactions of LiH + H2O = LiOH + H2 and LiH + 1/2 O2 = LiOH. The oxidation behavior of LiH in ambient air with a 27% relative humidity can be well described by the Johnson-Mehl-Avrami equation. Furthermore, the ball-milled LiH oxidizes faster than the unmilled one, which is due to the finer particle size and larger surface area of the ball-milled powder.