Fengyun Yan

To clarify the deterioration behavior of magnesium oxychloride cement (MOC) under conditions of high humidity and high temperature, we first placed MOC slurry samples in a simulated environment with a relative humidity of 97 ± 1% and a temperature of 38 ± 2 °C; then, we observed the changes in the macroscopic and microscopic morphology, water erosion depth, bulk density, phase composition, and mechanical properties of the samples. The results show that, over time, under the promotion of high temperature, water molecules infiltrate the MOC samples. This results in the appearance of cracks on the macroscopic surface of the MOC samples due to the volume expansion caused by the hydrolysis of P5 (5Mg(OH)₂·MgCl₂·8H₂O) and the hydration of unreacted active MgO in the samples. The microscopic morphology of the samples changes from needle/gel-like, to flake-like, and finally leaf-like. Simultaneously, the major phase composition turns into Mg(OH)₂. Since the structure of the samples becomes looser and the content of the main strength phase decreases, the overall compressive strength and flexural strength are both reduced. The compressive strength of the MOC slurry samples (0 day) is 93.2 Mpa, and the flexural strength is 16.4 MPa. However, after 18 days of treatment, water molecules reach the center of the MOC samples, and the MOC samples completely lose their integrity. As a result, their compressive and flexural strengths cannot be obtained.

To reveal the effects of acidic environment on structure and property of magnesium oxychloride cement (MOC), the evolution of macro- and micro-morphologies, phase composition and mechanical property of MOC samples with soaking time in 5 wt.% H₂SO₄ solution were studied by using SEM, XRD, FT-IR and microelectromechanical electrohydraulic servo-pressure testing machine, respectively. The results show that the deterioration of MOC sample under acidic environment is mainly attributed to the consumption of the sample caused by the reaction between H⁺ ions and the substances in sample. The longer the soaking time, the more the sample consumed by H⁺ ions, and the more serious the deterioration of the sample. After dipping in H₂SO₄ media for 12h, the mass loss rate of MOC sample is up to 77.5%, and its volume decreases by nearly 3/4. Meanwhile, the surface morphology of MOC sample is changed from gel and needle rod to granular, and the content of P5, Mg(OH)₂ and MgO reduce, resulting in the compressive strength of MOC samples declining by 92.2%. However, due to the volume effect, H⁺ ions do not invade the inner core of the sample, so that the micro-morphology and phase composition of the inner core are almost unchanged. In short, MOC sample gradually deteriorates under acidic environment through being consumed by H⁺ ions from the outside to the inside.

金属基金刚石复合材料被广泛应用和研究，但金刚石表面预处理所导致的空位、掺杂等缺陷对金属基与金刚石界面性能有很大影响。尽管透射电镜和能谱分析等技术已用于缺陷检测，但这些方法存在局限性。通过计算金刚石中正电子湮灭寿命，可以准确评估金刚石的界面缺陷。本文利用第一性原理计算方法，采用多种正电子湮灭算法和增强因子，计算了金刚石理想晶体、单空位、掺杂B、Cr、Mo、Ti、W和Zr后的正电子湮灭寿命。结果显示，在采用局域密度泛函时，结合Boronski & Nieminen算法以及RPA限制作为湮灭增强因子时，计算得到的正电子湮灭寿命与文献的实验结果更为吻合。同时，金刚石中B和Cr的掺杂使正电子湮灭寿命从由单空位119.87ps增加为148.57和156.82ps。总体来说，金刚石中的空位和掺杂原子缺陷都会引起正电子湮灭寿命的变化。这些发现为理解和优化金刚石界面提供了有价值的理论依据。

The deterioration process and deterioration mechanism of magnesium oxychloride cement (MOC) in an alkaline environment were studied using a scanning electron microscope (SEM), an X-ray diffractometer (XRD), a Fourier transform infrared spectrometer (FT-IR) and a micro-electro-hydraulic servo pressure testing machine to investigate the effects of soaking time in 10 wt.% NaOH solution on the macro- and micro-morphology, phase composition and compressive strength of MOC samples. The results show that the deterioration of MOC samples under an alkaline environment is mainly caused by the alkaline environment providing more OH⁻ ions, which can react with 5Mg(OH)₂·MgCl₂·8H₂O (P 5) in the sample. The resulting reaction gives rise to a faster decomposition of 5Mg(OH)₂·MgCl₂·8H₂O (P 5) and a substantial reduction in the strength of the sample, and finally leads to a gradual deterioration of MOC samples. Meanwhile, immersion time exhibits a significant effect on MOC samples. The extension of immersion time coincides with more OH⁻ ions entering the sample, and the greater presence of OH ions increases the likelihood that more P 5 will produce a hydrolysis reaction, further resulting in the increased deterioration of the sample. After soaking for 6 h in alkaline media, the main phase composition of the surface layer of an MOC sample changes to MgO and Mg(OH)₂, and its microscopic morphology is also dominated by round sheets, giving rise to a sharp decrease in its compressive strength (52.2%). When the immersion time is prolonged to 72 h, OH⁻ ions have already immersed into the inner core of the sample, causing the disappearance of P 5 from the whole sample. At the same time, both the surface and inner core of the sample exhibit a disc-shaped morphology, and chalking phenomena also appear on the surface of the sample. This reduces the compressive strength of the sample to 13.5 MPa, only 20% of its compressive strength in water. The compressive strength of the sample after 120 h of immersion is as low as 8.6 MPa, which is lower than that of the sample dipped in water for 21 days (9.5 MPa). As a result, the MOC samples studied in alkaline environments exhibit a faster deterioration rate, mainly because of a faster hydrolysis reaction by P 5, caused by more OH⁻ ions.

To reveal the deterioration process of magnesium oxychloride cement (MOC) in an outdoor, alternating dry–wet service environment, the evolution of the macro- and micro-structures of the surface layer and inner core of MOC samples as well as their mechanical properties and increasing dry–wet cycle numbers were investigated by using a scanning electron microscope (SEM), an X-ray diffractometer (XRD), a simultaneous thermal analyser (TG-DSC), a Fourier transform infrared spectrometer (FT-IR), and an microelectromechanical electrohydraulic servo pressure testing machine. The results show that as the number of dry–wet cycles increases, the water molecules gradually invade the interior of the samples, causing the hydrolysis of P 5 (5Mg(OH)₂·MgCl₂·8H₂O) and hydration reactions of unreacted active MgO. After three dry–wet cycles, there are obvious cracks on the surface of the MOC samples, and they suffer from warped deformation. The microscopic morphology of the MOC samples changes from a gel state and a short, rod-like shape to a flake shape, which is a relatively loose structure. Meanwhile, the main phase composition of the samples becomes Mg(OH)₂, and the Mg(OH)₂ contents of the surface layer and inner core of the MOC samples are 54% and 56%, respectively, while the P 5 amounts are 12% and 15%, respectively. The compressive strength of the samples decreases from 93.2 MPa to 8.1 MPa and reduces by 91.3%, and their flexural strength declines from 16.4 MPa to 1.2 MPa. However, their deterioration process is delayed compared with the samples that were dipped in water continuously for 21 days whose compressive strength is 6.5 MPa. This is primarily ascribed to the fact that during the natural drying process, the water in the immersed samples evaporates, the decomposition of P 5 and the hydration reaction of unreacted active MgO both slow down, and the dried Mg(OH)₂ may provide the partial mechanical properties, to some extent.

The interface formation and properties of composite materials are very important for the preparation of composite materials, and the bonding state and charge transfer between atoms in the interface have a particularly significant effect on the interface formation. In this work, the first-principles calculation method was used to study the adsorption behavior and molecular dynamics of copper atoms on the (111) surface of H-terminated diamond, and the adsorption energy and adhesion work of Cu atoms were calculated. The results show that the adsorption of copper atoms is not sensitive to the diamond (111) surface, the adsorption work is very small at the four high symmetry positions, and the adhesion work is the largest at the T4 position and is 0.6106 J/m². Furthermore, according to the electron localization function (ELF) analysis, there is no compound formation between Cu and H atoms; only a small amount of charge transfer exists, which belongs to physical adsorption. The diamond–copper interface formed by the growth of adsorption sites is a metastable structure without energy stability. This work provides an important theoretical reference for understanding the formation mechanism of copper-based diamond composites.

In order to make full use of magnesium chloride resources, the development and utilisation of magnesium oxychloride cement have become an ecological and economic goal. Thus far, however, investigations into the effects on these cements of high temperatures are lacking. Herein, magnesium oxychloride cement was calcinated at various temperatures and the effects of calcination temperature on microstructure, phase composition, flexural strength, and compressive strength were studied by scanning electron microscopy, X-ray diffraction, and compression testing. The mechanical properties varied strongly with calcination temperature. Before calcination, magnesium oxychloride cement has a needle-like micromorphology and includes Mg(OH)₂ gel and a trace amount of gel water as well as 5 Mg(OH)₂·MgCl₂·8H₂O, which together provide its mechanical properties (flexural strength, 18.4 MPa; compressive strength, and 113.3 MPa). After calcination at 100 °C, the gel water is volatilised and the flexural strength is decreased by 57.07% but there is no significant change in the compressive strength. Calcination at 400 °C results in the magnesium oxychloride cement becoming fibrous and mainly consisting of Mg(OH)₂ gel, which helps to maintain its high compressive strength (65.7 MPa). When the calcination temperature is 450 °C, the microstructure becomes powdery, the cement is mainly composed of MgO, and the flexural and compressive strengths are completely lost.

Aiming at the problem that ordinary cement concrete is subjected to damage in heavy saline soil areas in China, a new type of magnesium oxychloride cement concrete is prepared by using the gelling properties of magnesium oxychloride cement in this study, and the erosion resistance of the synthesized magnesium oxychloride cement concrete in concentrated brine of salt lakes is studied through the full immersion test. The effects of concentrated brine of salt lakes on the macroscopic, microscopic morphology, phase composition and mechanical properties of magnesium oxychloride cement concrete are investigated by means of macro-morphology, erosion depth, SEM, XRD and strength changes. The salt erosion resistance mechanism of magnesium oxychloride cement concrete is revealed. The results demonstrate that under the environment of full immersion in concentrated brine of salt lakes, there is no macroscopic phenomenon of concrete damage due to salt crystallization, and the main phase composition is basically unchanged. The microscopic morphology mostly changes from needle-rod-like to gel-like. Due to the formation of a new 5·1·8 phase on the surface layer and the increase in compactness, its compressive strength has a gradual increase trend. Based on the engineering application of magnesium oxychloride cement concrete, it is further confirmed that magnesium oxychloride cement concrete has excellent salt erosion resistance and good weather resistance, which provides theoretical support for future popularization and application.