Impact of Chemical Corrosion on Mechanical Properties of Boroaluminosilicate Pharmaceutical Glasses.

Boroaluminosilicate (BAS) glasses have excellent chemical durability and mechanical properties and are widely used in the pharmaceutical packaging industry. The corrosion behavior of boroaluminosilicate (BAS) glasses have been investigated for many years; however, the impact of chemical corrosion on mechanical properties of boroaluminosilicate glasses has not been well understood. In this work, the BAS glass samples were corroded in a 20 mM Glycine-NaOH buffer solution (pH = 10) at 80 °C for various durations. Within the corrosion durations, the corrosion of the glass is dominated by congruent dissolution. The results show that the elemental composition and structure of the glass surface are not altered significantly during the congruent dissolution, and the corrosion rate is mainly affected by the Si concentration in the solution. The structural change in the process of micro-crack decay is the main factor affecting the mechanical properties of the glass surface. Corrosion leads to the growth of micro-cracks and tip passivation, which causes the hardness and elastic modulus of the glass to first decrease and then increase. As corrosion proceeds, the microcracks are completely destroyed to form micropores, and the pore size and number increase with the corrosion process, resulting in the decrease in surface mechanical properties again. This work reveals the main influencing factors of congruent dissolution on mechanical properties and provides an important reference for the improvement of pharmaceutical glass strength.

Stress-Dispersed Superstructure of Sn3 (PO4 )2 @PC Derived from Programmable Assembly of Metal-Organic Framework as Long-Life Potassium/Sodium-Ion Batteries Anodes.

The structures of anode materials significantly affect their properties in rechargeable batteries. Material nanosizing and electrode integrity are both beneficial for performance enhancement of batteries, but it is challenging to guarantee optimized nanosizing particles and high structural integrity simultaneously. Herein, a programmable assembly strategy of metal-organic frameworks (MOFs) is used to construct a Sn-based MOF superstructure precursor. After calcination under inert atmosphere, the as-fabricated Sn3 (PO4 )2 @phosphorus doped carbon (Sn3 (PO4 )2 @PC-48) well inherited the morphology of Sn-MOF superstructure precursor. The resultant new material exhibits appreciable reversible capacity and low capacity degradation for K+ storage (144.0 mAh g-1 at 5 A g-1 with 90.1% capacity retained after 10000 cycles) and Na+ storage (202.5 mAh g-1 at 5 A g-1 with 96.0% capacity retained after 8000 cycles). Detailed characterizations, density functional theory calculations, and finite element analysis simulations reveal that the optimized electronic structure and the stress-dispersed superstructure morphology of Sn3 (PO4 )2 @PC promote the electronic conductivity, enhance K+ / Na+ binding ability and improve the structure stabilization efficiently. This strategy to optimize the structure of anode materials by controlling the MOF growth process offer new dimension to regulate the materials precisely in the energy field.

Controllable Exfoliation of MOF-Derived Van Der Waals Superstructure into Ultrathin 2D B/N Co-Doped Porous Carbon Nanosheets: A Superior Catalyst for Ambient Ammonia Electrosynthesis.

The electrocatalytic nitrogen reduction reaction (NRR) to synthesize NH3 under ambient conditions is a promising alternative route to the conventional Haber-Bosch process, but it is still a great challenge to develop electrocatalysts' high Faraday efficiency and ammonia yield. Herein, a facile and efficient exfoliation strategy to synthesize ultrathin 2D boron and nitrogen co-doped porous carbon nanosheets (B/NC NS) via a metal-organic framework (MOF)-derived van der Waals superstructure, is reported. The results of experiments and theoretical calculations show that the doping of boron and nitrogen can modulate the electronic structure of the adjacent carbon atoms; which thus, promotes the competitive adsorption of nitrogen and reduces the energy required for ammonia synthesis. The B/NC NS exhibits excellent catalytic performance and stability in electrocatalytic NRR, with a yield rate of 153.4 µg·h-1 ·mg-1 cat and a Faraday efficiency of 33.1%, which is better than most of the reported NRR electrocatalysts. The ammonia yield of B/NC NS can maintain 92.7% of the initial NRR activity after 48 h stability test. The authors' controllable exfoliation strategy using MOF-derived van der Waals superstructure can provide a new insight for the synthesis of other 2D materials.

Methionine sulfoxide suppresses adipogenic differentiation by regulating the mitogen-activated protein kinase signaling pathway.

In this study, methionine sulfoxide (MetO) was identified as an active metabolite that suppresses adipogenesis after screening obese individuals versus the normal population. MetO suppressed the gene and protein expression of CCAAT/enhancer binding protein (C/EBP) α, adipocyte fatty acid binding protein 4 (FABP4), and the nuclear receptor peroxisome proliferator-activated receptor γ (PPARγ) during human preadipocyte (HPA) differentiation. Adipogenesis decreased following MetO treatment; however, the preadipocyte number, proliferation, and apoptosis were unaffected. The activity of phosphorylated extracellular signal-related kinase (P-ERK) of the mitogen-activated protein kinase (MAPK) pathway was significantly inhibited in HPA after MetO treatment. Furthermore, treatment of preadipocytes with the selective P-ERK1/2 agonist Ro 67-7476 abolished the effect of MetO against adipogenesis suggesting that MetO function is dependent on the MAPK pathway. The mechanistic insights of adipogenesis suppression by MetO presented in this study shows its potential as an antiobesity drug.

Preparation and Characterization of High-Strength Glass-Ceramics via Ion-Exchange Method.

Lithium aluminosilicate glass-ceramics (LAS GCs) are ideal shell materials for mobile phones; however, the mechanical properties of LAS GCs are comparatively lower than that of other shell materials. In this work, the impact of TiO2/(TiO2 + ZrO2) ratio on properties of LAS GCs was studied and the ion-exchange methods were applied to improve the mechanical properties of LAS GCs. The results show that LAS GCs with TiO2/(TiO2 + ZrO2) = 1/2 exhibit the best flexural strength (109 MPa) and Vickers hardness (525 Kg/mm2). The as-prepared glass was nucleated at 560 °C for 1 h and crystallized at 720 °C for 0.5 h. The main crystalline phases of LAS GCs are ß-quartz solid solution, ß-spodumene solid solution, and Li2SiO3. Moreover, the flexural strength and Vickers hardness of LAS GCs with TiO2/(TiO2 + ZrO2) = 1/2 further increased to 356 MPa and 838 Kg/mm2 after an ion-exchange at 420 °C for 6 h in pure KNO3 molten salt. The LAS GCs with enhanced mechanical strength have the potential to be applied as mobile phone back panels.

Topological Origins of the Mixed Alkali Effect in Glass.

The mixed alkali effect, the deviation from expected linear property changes when alkali ions are mixed in a glass, remains a point of contention in the glass community. While several earlier models have been proposed to explain mixed alkali effects on ionic motion, models based on or containing discussion of structural aspects of mixed-alkali glasses remain rare by comparison. However, the transition-range viscosity depression effect is many orders in magnitude for mixed-alkali glasses, and the original observation of the effect (then known as the Thermometer Effect) concerned the highly anomalous temperature dependence of stress and structural relaxation time constants. With this in mind, a new structural model based on topological constraint theory is proposed herein which elucidates the origin of the mixed alkali effect as a consequence of network strain due to differing cation radii. Discussion of literature models and data alongside new molecular dynamics simulations and experimental data are presented in support of the model, with good agreement.

Understanding Glass through Differential Scanning Calorimetry.

Differential scanning calorimetry (DSC) is a powerful tool to address some of the most challenging issues in glass science and technology, such as the nonequilibrium nature of the glassy state and the detailed thermodynamics and kinetics of glass-forming systems during glass transition, relaxation, rejuvenation, polyamorphic transition, and crystallization. The utility of the DSC technique spans across all glass-forming chemistries, including oxide, chalcogenide, metallic, and organic systems, as well as recently discovered metal-organic framework glass-forming systems. Here we present a comprehensive review of the many applications of DSC in glass science with focus on glass transition, relaxation, polyamorphism, and crystallization phenomena. We also emphasize recent advances in DSC characterization technology, including flash DSC and temperature-modulated DSC. This review demonstrates how DSC studies have led to a multitude of relevant advances in the understanding of glass physics, chemistry, and even technology.

Variability in the relaxation behavior of glass: Impact of thermal history fluctuations and fragility.

Glasses are nonequilibrium materials that continuously relax toward the metastable supercooled liquid state. As such, the properties of a glass depend on both its composition and thermal history. When an initially cooled glass is subjected to additional thermal cycles, relaxation during the heat treatment is accelerated, leading to changes in the macroscopic properties of the glass. This relaxation behavior is intrinsic to the glassy state and of critical interest to the high-tech glass industry. In many practical cases, the magnitude of the relaxation is less important than the variability of the relaxation effects due to slight variations in the thermal history experienced by the glass. These fluctuations in thermal history can occur either during the initial glass formation or during the subsequent heat treatment cycle(s). Here we calculate the variation in relaxation behavior using a detailed enthalpy landscape model, showing that the relaxation variability can be reduced dramatically by increasing the fragility of the system.