Effect of hydrogen on magnetic properties in MgO studied by first-principles calculations and experiments.

We investigated the effects of both intrinsic defects and hydrogen atom impurities on the magnetic properties of MgO samples. MgO in its pure defect-free state is known to be a nonmagnetic semiconductor. We employed density-functional theory and the Heyd-Scuseria-Ernzerhof (HSE) density functional. The calculated formation energy and total magnetic moment indicated that uncharged [Formula: see text] and singly charged [Formula: see text] magnesium vacancies are more stable than oxygen vacancies (VO) under O-rich growth conditions and introduce a magnetic moment to MgO. The calculated density of states (DOS) results demonstrated that magnetic moments of VMg result from spin polarization of an unpaired electron of the partially occupied valence band, which is dominated by O 2p orbitals. Based on our calculations, VMg is the origin of magnetism and ferromagnetism in MgO. In contrast, the magnetic moment of the magnetic VMg-MgO crystal is suppressed by hydrogen (H) atoms, and unpaired electrons are donated to the unpaired electronic states of VMg when the defect complex Hi-VMg is formed. This suggests that H causes a reduction in magnetization of the ferromagnetic MgO. We then performed experimental studies to verify the DFT predictions by subjecting the MgO sample to a thermal treatment that creates Mg vacancies in the structure and intentionally doping the MgO sample with hydrogen atoms. We found good agreement between the DFT results and the experimental data. Our findings suggest that the ferromagnetism and diamagnetism of MgO can be controlled by heat treatment and hydrogen doping, which may find applications in magnetic sensing and switching under different environmental conditions.

Bio-strengthening of cementitious composites from incinerated sugarcane filter cake by a calcifying bacterium Lysinibacillus sp. WH.

This study investigated Microbially Induced Calcite Precipitation (MICP) technology to improve the mechanical properties of cementitious composites containing incinerated sugarcane filter cake (IFC) using a calcifying bacterium Lysinibacillus sp. WH. Both IFC obtained after the first and second clarification processes, referred to as white (IWFC) and black (IBFC), were experimented. This is the first work to investigate the use of IBFC as a cement replacement. According to the X-ray fluorescence (XRF) results, the main element of IWFC and IBFC was CaO (91.52%) and SiO2 (58.80%), respectively. This is also the first work to investigate the use of IBFC as a cement replacement. We found that the addition of strain WH could further enhance the strength of both cementitious composites up to ~ 31%, while reduced water absorption and void. Microstructures of the composites were visualized using a scanning electron microscope (SEM). The cement hydration products were determined using X-ray diffraction (XRD) followed by Rietveld analysis. The results indicated that biogenic CaCO3 was the main composition in enhancing strength of the IBFC composite, whereas induce tricalcium silicate (C3S) formation promoting the strength of IWFC composite. This work provided strong evidence that the mechanical properties of the cementitious composites could be significantly improved through the application of MICP. In fact, the strength of IFC-based cementitious composites after boosting by strain WH is only 10% smaller than that of the conventional Portland cement. While using IFC as a cement substitute is a greener way to produce environmentally friendly materials, it also provides a solution to long-term agro-industrial waste pollution problems.

Kinetic model of a newly-isolated Lysinibacillus sp. strain YL and elastic properties of its biogenic CaCO3 towards biocement application.

BACKGROUND: Biocement, calcifying bacteria-incorporated cement, offers an environmentally-friendly way to increase the cement lifespan. This work aimed to investigate the potential use of Lysinibacillus sp. strain YL towards biocement application in both theoretical and experimental ways. METHODS AND RESULTS: Strain YL was grown using calcium acetate (Ca(C2 H3 O2 )2 ), calcium chloride (CaCl2 ) and calcium nitrate (Ca(NO3 )2 ). Maximum bacterial growth of ~0.09 hr-1 and the highest amount of CaCO3 precipitation of ~8.0 g/L were obtained when using Ca(C2 H3 O2 )2 . The SEM and XRD results confirmed that biogenic CaCO3 were calcites. The bulk, Young's and shear moduli of biogenic CaCO3 calculated via the VRH approximation were ~1.5-2.3 times larger than those of ordinary Portland cement. The Poisson's ratio was 0.382 and negative in some directions, suggesting its ductility and auxetic behaviors. The new model was developed to explain the growth kinetic of strain YL in the presence of Ca(C2 H3 O2 )2 , whose concentration was optimized for biocement experiments. Strain YL could increase the compressive strength of cement up to ~50% higher than that of the uninoculated cement. CONCLUSION: Strain YL is a promising candidate for biocement applications. This work represents the trials of experiments and models allowing quantitatively comparison with large-scale production in the future.

Electronic and thermodynamic properties of native point defects in V2O5: a first-principles study.

The formation of native point defects in semiconductors and their behaviors play a crucial role in material properties. Although the native defects of V2O5 include vacancies, self-interstitials, and antisites, only oxygen vacancies have been extensively explored. In this work, we carried out first-principles calculations to systematically study the properties of possible native defects in V2O5. The electronic structure and the formation energy of each defect were calculated using the DFT+U method. Defect concentrations were estimated using a statistical model with a constraint of charge neutrality. We found that the vanadyl vacancy is a shallow acceptor that could supply holes to the system. However, the intrinsic p-type doping in V2O5 hardly occurred because the vanadyl vacancy could be readily compensated by the more stable donor, i.e., the oxygen vacancy and oxygen interstitial, instead of holes. The oxygen vacancy is the most dominant defect under oxygen-deficient conditions. However, under extreme O-rich conditions, a deep donor of oxygen interstitial becomes the major defect species. The dominant oxygen vacancy under synthesized conditions plays an important role in determining the electronic conductivity of V2O5. It induces the formation of compensating electron polarons. The polarons are trapped at V centers close to the vacancy site with the effective escaping barriers of around 0.6 eV. Such barriers are higher than that of the isolated polaron hopping (0.2 eV). The estimated polaron mobilities obtained from kinetic Monte Carlo simulations confirmed that oxygen vacancies act as polaron-trapping sites, which diminishes the polaron mobility by 4 orders of magnitude. Nevertheless, when the sample is synthesized at elevated temperatures, a number of thermally activated polarons in samples are quite high due to the high concentrations of oxygen vacancies. These polarons can contribute as charge carriers of intrinsic n-type semiconducting V2O5.

Investigating mechanical properties and biocement application of CaCO3 precipitated by a newly-isolated Lysinibacillus sp. WH using artificial neural networks.

A newly-isolated Lysinibacillus sp. strain WH could precipitate CaCO3 using calcium acetate (Ca(C2H3O2)2), calcium chloride (CaCl2) and calcium nitrate (Ca(NO3)2) via non-ureolytic processes. We developed an algorithm to determine CaCO3 crystal structures by fitting the simulated XRD spectra to the experimental data using the artificial neural networks (ANNs). The biogenic CaCO3 crystals when using CaCl2 and Ca(NO3)2 are trigonal calcites with space group R3c, while those when using Ca(C2H3O2)2 are hexagonal vaterites with space group P6522. Their elastic properties are derived from the Voigt-Reuss-Hill (VRH) approximation. The bulk, Young's, and shear moduli of biogenic calcite are 77.812, 88.197, and 33.645 GPa, respectively, while those of vaterite are 67.082, 68.644, 25.818 GPa, respectively. Their Poisson's ratios are ~ 0.3-0.33, suggesting the ductility behavior of our crystals. These elastic values are comparable to those found in limestone cement, but are significantly larger than those of Portland cement. Based on the biocement experiment, the maximum increase in the compressive strength of Portland cement (27.4%) was found when Ca(NO3)2 was used. An increased strength of 26.1% was also found when Ca(C2H3O2)2 was used, implying the transformation of less-durable vaterite to higher-durable calcite. CaCO3 produced by strain WH has a potential to strengthen Portland cement-based materials.