Atomistic origin of brittle-to-ductile transition behavior of polycrystalline 3C–SiC in diamond cutting

The machinability of hard brittle polycrystalline ceramic has a strong correlation with internal microstructures and their accommodated deformation behavior. In the present work, we investigate the mechanisms governing the brittle-to-ductile transition behavior of polycrystalline 3C–SiC in diamond cutting by means of molecular dynamics simulations. Simulation results reveal the co-existence of dislocation slip and amorphization-dominated ductile deformation and cracking along grain boundaries-mediated brittle fracture, as well as the correlation of individual deformation modes with machining force variation and machined surface morphology. In addition, inter-granular fracture, grain boundary sliding and grain pull-up are also operating brittle deformation modes of polycrystalline 3C–SiC. The strong competition between above heterogeneous deformation modes determines the brittle-to-ductile transition behavior in grooving of polycrystalline 3C–SiC. Simulation results also demonstrate that grain size has a strong impact on the brittle-to-ductile transition and material deformation behavior of polycrystalline 3C–SiC under diamond cutting.     

Irradiation-induced microstructure damage in He-irradiated 3C-SiC at 1000℃

The effect of the high-temperature helium irradiation on microstructural evolution of 3C-SiC was investigated by the combination of Raman spectroscopy, conventional transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). 3C-SiC wafers were irradiated with 130 keV He⁺ ions at fluences of 2 × 10¹⁶ He⁺/cm², 4 × 10¹⁶ He⁺/cm² and 2 × 10¹⁷ He⁺/cm² at 1000℃. Helium bubbles, dislocation loops, and their interaction with the stacking faults were focused on and characterized by TEM. Helium bubbles preferentially nucleate and grow on stacking faults. Bubble links on the (100) plane in 3C-SiC are formed. In addition, stacking faults can effectively trap irradiation-induced lattice defects to enhance their recovery. The type of irradiation-induced lattice defects and elemental distribution are also investigated. The research results are valuable for the 3C-SiC used in the advanced nuclear energy systems.     

Piezoelectric porous α-quartz membrane by aqueous gel-casting with enhanced antifouling and mechanical properties

Porous α-quartz ceramics with improved mechanical strength were fabricated by using silica sol as a bonding agent in an aqueous gel-casting process. α-quartz dispersion was prepared with a solid load of 75 wt% and a viscosity of 1.66 Pa·s. α-Al₂O₃ particles were added to promote dispersion of the bonding agent. The optimum amounts of amorphous silica and α-Al₂O₃ were 10 % and 8 % of the mass of α-quartz powder, respectively. The thermal treatment of α-quartz green bodies was optimized for mechanical and permeation properties. Electrical fields up to 1 kV/mm were applied to the green bodies to accomplish α-quartz grains orientation and hence piezoelectric response. This caused an increase of piezo-acoustic response by 58 % at an excitation frequency of 200 kHz. In-situ mitigation of fouling was obtained by applying an alternating voltage of 60 V, during TiO₂ suspension filtration, which resulted in an increase of the stationary flux by 23 %.     

Toward revealing atomic deformation mechanics in lithium disilicate and β-quartz containing glass-ceramics

The mechanics of glass-ceramics subjected to sharp contact or other loading conditions remain elusive, even after being commercialized in many industrial applications. We present work herein to reveal atomic details of such deformations that are otherwise extremely difficult to probe experimentally for a lithium disilicate (LS2) and β-quartz containing glass-ceramics via molecular dynamics simulations. Specifically, the materials are comprised of LS2 and β-quartz nanocrystals in a residual glass matrix. Regardless of the deformation mechanism, whether it be nanoindentation or crack propagation for samples with pre-existing flaws, we observe that the LS2 nanocrystal itself undergoes substantial deformation, either by activating dislocations, forming an amorphization zone, or by initiating microcracks at glass-crystal interfaces or weak crystallographic planes. In contrast, the β-quartz nanocrystal is not easily deformed and remains almost intact with minimal plastic deformation, thereby forcing shear flow and crack propagation pathways to predominately occur in the residual glass and/or at interfaces. The dramatic difference between the crystalline phases also manifests itself in the deformation mode of interfaces under pure shear loading, in which shear bands preferably occur at the LS2-glass interfaces, while cavities form at the β-quartz-glass interfaces. These observations significantly advance our understanding of glass-ceramics and pave ways to exploit the understanding for more applications.     

Metal–insulator transition in boron-ion implanted type IIa diamond

Electrical conductivity measurements for selected boron-ion dopant concentrations have been made on type IIa diamond specimens in the temperature range 1.5–30 K. Samples have been implanted using the CIRA (cold implantation–rapid annealing) process, in which small implantation increments were used followed by high-temperature annealing to achieve a significant reduction in the levels of implantation-induced radiation damage and to obtain maximum boron activation. Further post anneals at temperatures up to 1700°C were carried out. Using this procedure, we have recorded, for the first time, metallic conductivity behaviour in implanted surface layers in single-crystal diamond specimens with boron concentrations measured by secondary-ion mass spectrometry to be of the order of n=10²¹ cm⁻³. The occurrence of a metal–insulator transition in this system is discussed.     

Stability of α-Sialons in Low Temperature Annealing

Phase and microstructural change due to post-sintering annealing of Nd, Dy, Y and Yb-α-sialon ceramics have been investigated for the composition of α-sialon-rare earth aluminum garnet (RAG) systems. For R= Dy, Y and Yb, only α-sialon was observed as the crystalline phase after sintering at 1750°C. After subsequent post-sintering annealing at 1450°C for 72 h, no phase transformation from α-to β-sialon was observed, although the crystallization of garnet phase at grain boundaries was detected. However, for R=Nd, α-,β-sialon and melilite phase (M’) were observed after sintering at 1750°C. The β-sialon and melilite phases increased with low-temperature heat treatment, implying that the transformation from α- to β-sialon occurred. It was concluded that the α-sialon phase stabilized by small ions like Y, Dy or Yb has high thermal stability and does not transform to β-sialon when there is no chemical reaction between α-sialon grains and the grain boundary phase.     

Enantioselective Pharmacokinetics of α-Lipoic Acid in Rats

α-Lipoic acid (LA) is widely used for nutritional supplements as a racemic mixture, even though the R enantiomer is biologically active. After oral administration of the racemic mixture (R-α-lipoic acid (RLA) and S-α-lipoic acid (SLA) mixed at the ratio of 50:50) to rats, RLA showed higher plasma concentration than SLA, and its area under the plasma concentration-time curve from time zero to the last (AUC) was significantly about 1.26 times higher than that of SLA. However, after intravenous administration of the racemic mixture, the pharmacokinetic profiles, initial concentration (C₀), AUC, and half-life (T_1/2) of the enantiomers were not significantly different. After oral and intraduodenal administration of the racemic mixture to pyrolus-ligated rats, the AUCs of RLA were significantly about 1.24 and 1.32 times higher than that of SLA, respectively. In addition, after intraportal administration the AUC of RLA was significantly 1.16 times higher than that of SLA. In conclusion, the enantioselective pharmacokinetics of LA in rats arose from the fraction absorbed multiplied by gastrointestinal availability (F_aF_g) and hepatic availability (F_h), and not from the total clearance.     

Flow regime transition for cocurrent gas–liquid flow in micro-channels

Experimental investigations of gas–liquid two-phase flow regimes in micro-channels were carried out in this work. Four distinctive flow patterns of slug flow, slug-annular flow, annular flow and parallel stratified flow were captured by a digital video recording (DVR) system and the transitions among different flow regimes were studied. The effect of fluid properties and wetting properties of the channel wall on the flow regime and flow pattern transition were studied as well. Novel empirical correlations for predicting flow pattern transitions during the steady gas–liquid flow in micro-channels have been developed with the fluid properties and the wetting properties of micro-channels incorporated, whereas the traditional flow criteria were based on gas and liquid superficial velocities only. The predictions of the present empirical models agree well with the experimental data.     

Observation of the semiconductor–metal transition behavior in monolayer graphene

We have observed that during temperature-dependent four-terminal resistance measurement of monolayer graphene, the resistance exhibits anomalous rising and falling behavior at different temperature regions. At lower temperature region (2–200 K) the resistance decreases gradually, but when the temperature rise further it turn to a sudden increase, and after 280 K it resumes gradual decrease. The rising and falling resistance behavior is characteristic of semiconductor or metal property. Consequently, the resistance transition follows a phase of semiconductor–metal–semiconductor. However, when a perpendicular magnetic field is applied, the resistance shows reverse transition behavior which follows a sequence of metal–semiconductor–metal. The novel transition property is attributed to the competition between the disorder of lattice defects as a short-range scattering in monolayer graphene and the Landau levels interaction. Magneto-transport measurement reveals that the excitonic gap induced by magnetic field in the monolayer graphene show an anomalous thermally activated property.     

Incorporation of α-tocopherol in marine lipid-based liposomes: in vitro and in vivo studies

Liposomes made from a natural marine lipid extract and containing a high polyunsaturated n−3 fatty lipid ratio were envisaged as oral route vectors and a potential α-tocopherol supplement. The behavior of vesicles obtained by simple filtration and of giant vesicles prepared by electroformation was investigated in gastrointestinal-like conditions. The influence of α-tocopherol incorporation into liposomes was studied on both physical and chemical membrane stability. Propanal, as an oxidation product of n−3 polyunsaturated fatty acids, was quantified by static headspace gas chromatography when α-tocopherol incorporation into liposome ratios ranged from 0.01 to 12 mol%. Best oxidative stability was obtained for liposomes that contained 5 mol% α-tocopherol. Compared to the other formulas, propanal formation was reduced, and time of the oxidation induction phase was longer. Moreover, α-tocopherol induced both liposome structural modifications, evidenced by turbidity, and phospholipid chemical hydrolysis, quantified as the amount of lysophospholipids. This physicochemical liposome instability was even more pronounced in acid storage conditions, i.e., α-tocopherol incorporation into liposome membranes accelerated the structural rearrangements and increased the rate of phospholipid hydrolysis. In particular, giant vesicles incubated at pH 1.5 underwent complex irreversible shape transformations including invaginations. In parallel, the absorption rate of α-tocopherol was measured in lymph-cannulated rats when α-tocopherol was administrated, as liposome suspension or added to sardine oil, through a gastrostomy tube. α-Tocopherol recovery in lymph was increased by almost threefold, following liposome administration. This may be related to phospholipids that should favor α-tocopherol solubilization and to liposome instability in the case of a high amount of α-tocopherol in the membranes. A need to correlate results obtained from in vitro liposome behavior with in vivo lipid absorption was demonstrated by this study.     

Regime II–III transition in isotactic polybutene-1 tetragonal crystal growth

The lateral growth rate and growth shape morphology of isotactic polybutene-1 tetragonal crystals were investigated for crystallization from the melt at temperatures of 68–101 °C. The growth rate of tetragonal crystals shows supercooling dependence derived from the nucleation theory, and a regime II–III transition is observed at temperatures of 77–82.2 °C. The morphology of single crystals is rounded below temperatures of 77–85 °C, while the growth shape has a faceted morphology at a higher crystallization temperature of 100 °C. The kinetic roughening transition occurs between 77 and 85 °C. The regime II growth mode is observed above 82.2 °C and proceeds by multiple nucleation on the faceted growth front, while the regime III growth mode is observed below 77 °C and proceeds by rough surface growth on the kinetically roughened growth front. The observed regime II–III transition can therefore be explained by the morphology transition of crystal growth shape.     

Bandwidth controlled metal-insulator transition in Au–VO2 nanocomposite thin films

Recognizing and controlling the metal-insulator transition (MIT) in VO₂ transition-metal oxides is interesting for the future electronic devices. However, the effect of the electron correlation for the structure-coupled MIT in VO₂ is as yet an open question. In this study, we present for the first time direct spectroscopic evidence for the charge-transfer assistance bandwidth controlled MIT (BC-MIT) in Au–VO₂ nanocomposite thin films (NCTFs). A significantly enhancement of the MIT temperature (about 350 K) is realized in Au–VO₂ films with Au volume ratio of 1.1 mol%. However, by further increasing Au ratios, the MIT temperature in Au–VO₂ NCTFs is downward shifted by ~16 K and forward shifted 6 K. The V L-edge and O K-edge have been investigated. The basic electronic parameters such as the covalency (W) have been tuned. The relationship between bandwidth and the MIT temperature has been clearly elucidated a linear relationship. The experimental results demonstrate that MIT in VO₂ is BC-MIT which improved our understanding of the electron correlation effect in VO₂ systems.     

Dirac cone in α-graphdiyne: a first-principles study

We investigate the Dirac cone in α-graphdiyne, which is a predicted flat one-atom-thick allotrope of carbon using first-principles calculations. α-graphdiyne is derived from graphene where two acetylenic linkages (-C ≡C-) are inserted into the single bonds (-C-C-). Thus, α-graphdiyne possesses a larger lattice constant which subsequently affects its electronic properties. Band structures show that α-graphdiyne exhibits similar Dirac points and cone to graphene. Further, the tight-binding method is used to exploit the linear dispersion in the vicinity of Dirac points. Thanks to the larger lattice constant, α-graphdiyne yields a lower Fermi velocity, which might make itself an ideal material to serve the anomalous integer quantum Hall effect.     

Cathodic reduction of α-bromopropiophenone in an aprotic medium

The cathodic reduction in an aprotic medium of α-bromopropiophenone produces 1,4-diphenyl-2,3,-dimethyl-1,4-butanedione. This product is transformed by dehydration in 2,5-diphenyl-3,4-dimethylfuran. The reduction process is rationalized via anionic intermediates.     

Versatile α-oxoketene dithioacetals and analogues in heterocycle synthesis

The synthetic utility of ketene dithioacetals is reported in a formal way. The title compounds are used as precursors for the synthesis of many heterocyclic rings. The reactions of the title compounds are subdivided into groups that cover reactions yielding monoheterocycles e.g., thiophenes, imidazolidines, pyrimidines, pyridines, pyrazoles and even fused heterocyclic e.g., pyrroloimidazoles, pyrazolopyridines and imidazopyridines.     

Oxidative catabolism of α-tocopherol in rat liver microsomes

The goal of this study was to clarify the mechanism responsible for the catabolism of α-tocopherol. The vitamin, bound to albumin, was incubated with rat liver microsomes and appeared to be broken down. Optimal production of the metabolite was obtained when 1 mg of microsomal protein was incubated with 36 μM of α-tocopherol in the presence of 1.5 mM of NADPH. Chromatographic and mass spectrometric analyses of the metabolite led to the conclusion that it consists of an ω-acid with an opened chroman ring, although we could not perform nuclear magnetic resonance analysis to confirm this. Our data show that α-tocopherol is ω-oxidized to a carboxylic acid and that this process can occur in rat liver microsomes in the presence of NADPH and O₂. The oxidation to the quinone structure appears to be a subsequent event that may be artifactual and/or catalyzed by a microsomal enzyme(s).     

Terminal Alkynes as Raman Probes of α-Synuclein in Solution and in Cells

Conformational changes in α-synuclein (α-syn) are central to its biological function and Parkinson's disease pathology. Here, terminal alkynes (homopropargylglycine) were employed as environmentally sensitive Raman probes at residues 1, 5, 116, and 127 to characterize soluble (disordered), micelle-bound (α-helical), and fibrillar (β-sheet) α-syn. Along with the full-length protein, a disease-related C-terminal truncation (1–115) was also studied. For the first time, β-sheet α-syn amyloid structure was detected by the amide-I band in N27 dopaminergic rat cells, where a reciprocal relationship between levels of fibrils and lipids was seen. Site-specific spectral features of the terminal alkynes also revealed the heterogeneity of the cellular environment. This work shows the versatility of Raman microspectroscopy and the power of unnatural amino acids in providing structural and residue-level insights in solution and in cells.     

Effect of brookite phase on the anatase–rutile transition in titania nanoparticles

Nanosized TiO₂ powders were prepared from the precipitation in the TiCl₄ precursor under various pH values. The prepared titania existed in the form of nanocrystalline anatase with some brookite, which was evidenced by X-ray diffraction analysis and Raman spectroscopy. The average crystallite sizes of the TiO₂ particles heat treated at 450 °C for 2 h are in the range of 7–9 nm. The lattice constant c of anatase increased with increasing the synthesized pH value, whereas the volume fraction of the brookite phase increased with decreasing the synthesized pH value. The beginning and ending temperatures for the anatase–rutile transformation were found to decrease with increasing the volume fraction of the brookite phase. The brookite phase in the powder is responsible for enhancing the anatase–rutile transition.