Thermodynamic Aspects of the Increased Thermal Stability of Silicon by Doping with Transition or Rare-earth Metals

The main reason of the degradation of silicon monocrystals at heating is a structural transformation connected with a partial transition of the diamond-like structure into the structure of white tin. The reason for this transformation being observed under high pressures is the appearance of stress zones at the boundaries of variously oriented crystal microvolumes due to heat expansion anisotropy. The high stress concentration in the microvolumes provides sufficient pressure for the indicated phase transformation which results in the observed degradation of the electrophysical properties of silicon. The prevention of the structural transformation is considered to be possible by doping of Si by transition or rare-earth metals which increases the interatomic energy and decreases the thermal expansion coefficient. The choice of the doping additions is based on the bonding energy and the charge density calculated for a system of non-polarised ionic radii. The technology to increase the thermal stability of silicon has been patented^#.     

Thermal performance of poly(ethylene disulfide)/expanded graphite nanocomposites

In this study, the influences of expanded graphite oxide (EG) nanosheets presence with and without surfactant on structural and thermal performance of poly(ethylene disulfide) (PEDS)-based nanocomposites are investigated. Sodium dodecylbenzenesulfonate (SDBS) is used as a surfactant for the preparation of modified-EG nanosheets. The structural, morphological, and thermal properties of prepared nanocomposites are studied using X-ray diffraction (XRD), scanning electron microscopy, and differential scanning calorimetry techniques, respectively. XRD patterns of nanocomposites reveal that a high degree of expanded graphite nanosheets dispersion is achieved with and without surface modification using in situ polymerization method. Moreover, the presence of immobilized polysulfide chains near the interface region of nanosheets is suggested as a possible reason for the observed increase in the number of semi-crystalline organic fractions in the structure of PEDS via EG nanosheets incorporation. In addition, the morphology of SDBS-modified-EG loaded nanocomposite shows a smoother fracture surface than unmodified-nanosheets reinforced nanocomposite. Therefore, more interactions between nanosheets and polysulfide chains are expected in the structure of unmodified-EG reinforced nanocomposite. Moreover, thermal resistance and degradation kinetics of prepared nanocomposites are studied using thermogravimetric analysis results and degradation activation energy calculations, respectively. The required activation energy for the degradation process of SDBS-EG loaded nanocomposite is about 140 kJ mol^?1 lower than the required degradation activation energy of unmodified-nanosheets reinforced nanocomposite.     

Synergistic effect of ferric chloride and silicon mixtures on the thermal stabilization enhancement of ABS

A previous study from this laboratory has shown that Lewis acid-type transition metal chlorides (NiCl₂, CoCl₂, ZnCl₂, and FeCl₃) are effective char forming catalysts for ABS terpolymer in an inert atmosphere [Jang J, Kim JH, Bae JY. Polym Degrad Stab 2005;88(2):324.]. However, transition metal chloride catalysed char formation (and flame-retardance enhancement) of ABS in air was unsuccessful due to the oxidative degradation of the char at a higher temperature. In order to overcome these undesirable phenomena, we incorporated silicon with transition metal chlorides as co-catalyst and a series of ABS/transition metal chloride/silicon compounds were made from them and their flame retardancy was evaluated by measuring the limiting oxygen index (LOI) values. Our results showed that among various transition metal chloride/silicon catalyst systems the incorporated mixture of ferric chloride and silicon is very effective in enhancing the thermal stabilization of ABS and LOI value as high as 33 is obtained. The reason for this synergistic effect by ferric chloride and silicon was postulated to come from the interaction between ferric chloride and silicon at elevated temperatures, probably generating silicon tetrachloride and hydrogen chloride.     

双金属(Sn/Ni)掺杂多孔硅微球的液相合成与电化学储锂性能

使用廉价的硅铝合金前驱体,通过简单的化学沉积方法制备了新型双金属(Sn/Ni)掺杂多孔硅微球(pSi@SnNi)。pSi@SnNi复合材料的三维多孔结构可以缓冲硅在锂化过程中的巨大体积膨胀,增加储锂活性位点。双金属(Sn/Ni)的掺杂可以提高硅的电子导电性,改进pSi的结构稳定性。由于其独特的组成和微观结构,具有适当Sn/Ni含量的pSi@SnNi复合材料显示了较大的可逆储锂容量(0.1 A·g^-1下为2 651.7 mAh·g^-1)、较高的电化学循环稳定性(1 A·g^-1下400次循环后为1 139 mAh·g^-1)和优异的倍率性能(2.5 A·g^-1下为1 235.8 mAh·g^-1)。     

高比能锂离子电池层状富锂正极材料改性策略研究进展

层状富锂材料具有超过250 mAh∙g⁻¹的高可逆比容量,被认为是下一代高比能锂离子电池最具商业化前景的正极材料之一。然而,层状富锂材料在实际应用之前仍需解决诸多挑战,如高电压氧释放、层状到岩盐相的结构变化、过渡金属离子迁移等结构劣化,并由此带来了较低的初始库伦效率、电压/容量的衰减以及循环寿命的不足。针对以上问题,进行层状富锂材料改性无疑是一种行之有效的方法。本综述全面介绍了层状富锂材料的结构、组分以及电化学性能,在此基础上对材料改性策略进行了系统阐述,详细介绍了体相掺杂、表面包覆、缺陷设计、离子交换和微结构调控等一系列改性策略的现状以及发展趋势,最终提出了高容量和长循环层状富锂材料和高比能锂离子电池的设计思路。     

双金属(Sn/Ni)掺杂多孔硅微球的液相合成与电化学储锂性能

使用廉价的硅铝合金前驱体,通过简单的化学沉积方法制备了新型双金属(Sn/Ni)掺杂多孔硅微球(pSi@SnNi)。pSi@SnNi复合材料的三维多孔结构可以缓冲硅在锂化过程中的巨大体积膨胀,增加储锂活性位点。双金属(Sn/Ni)的掺杂可以提高硅的电子导电性,改进pSi的结构稳定性。由于其独特的组成和微观结构,具有适当Sn/Ni含量的pSi@SnNi复合材料显示了较大的可逆储锂容量(0.1 A·g^-1下为2 651.7 mAh·g^-1)、较高的电化学循环稳定性(1 A·g^-1下400次循环后为1 139 mAh·g^-1)和优异的倍率性能(2.5 A·g^-1下为1 235.8 mAh·g^-1)。     

Evidence of a two-stage thermal denaturation process in lysozyme: a Raman scattering and differential scanning calorimetry investigation

Raman spectroscopy (in the low-frequency range and the amide I band region) and modulated differential scanning calorimetry investigations have been used to analyze temperature-induced structural changes in lysozyme dissolved in 1H2O and 2H2O in the thermal denaturation process. Low-frequency Raman data reveal a change in tertiary structure without concomitant unfolding of the secondary structure. Calorimetric data show that this structural change is responsible for the configurational entropy change associated with the strong-to-fragile liquid transition and correspond to about 1/3 of the native-denaturated transition enthalpy. This is the first stage of the thermal denaturation which is a precursor of the secondary structure change and is determined to be strongly dependent on the stability of the hydrogen-bond network in water. Low-frequency Raman spectroscopy provides information on the flexibility of the tertiary structure (in the native state and the transient folding state) in relation to the fragility of the mixture. The unfolding of the secondary structure appears as a consequence of the change in the tertiary structure and independent of the solvent. Protein conformational stability is directly dependent on the stability of the native tertiary structure. The structural transformation of tertiary structure can be detected through the enhanced 1H/2H exchange inhibited in native proteins. Taking into account similar features reported in the literature observed for different proteins it can be considered that the two-stage transformation observed in lysozyme dissolved in water is a general mechanism for the thermal denaturation of proteins.     

Valence instabilities, phase transitions, and abrupt lattice expansion at 5 K in the YbGaGe system

The powder synchrotron X-ray diffraction technique was used to study the thermal expansion behavior of the mixed valence layered compound, YbGa1.05Ge0.95 in the temperature range 3-1123 K. A surprising abrupt isosymmetric phase transition, accompanied by a dramatic volume increase (negative thermal expansion), was found at 5 K induced by a sudden Yb valence transition from +(2 + epsilon) toward +2. At high temperatures, the material undergoes a transformation to a highly disordered structure until it eventually collapses at 1123 K to a structure with isovalent Yb ions and flat Ga/Ge planes (AlB2 type).     

Dehydroxylation kinetic and exfoliation of large muscovite flakes

The thermal transformations of muscovite flakes are a key point in many applications because besides dehydroxylation a significant exfoliation process occurs. Dehydroxylation kinetic is experimented by isothermal TG analyses in the 700–850°C temperature range and described with the Avrami theory. Hydroxyl condensation predominates at the onset of the process, but water diffusion is the most important process when the transformed fraction is high. The progressive transition between the two transformation stages contrast with the more accentuated transition for a ground muscovite. The activation energy varies weakly (190–214 kJ mol⁻¹) in the whole transformation process that supports the co-existence of hydroxyl condensation and diffusion phenomena. Dehydroxylation kinetic increases strongly with temperature and decreases with the reaction advancement. Exfoliation is correlated with dehydroxylation kinetic and occurs in a narrow transformation and temperature ranges. An in-situ combination process of hydroxyls occurs and water vapor favors the layer expansion.     

Micro-thermal analysis of NiTi shape memory alloy thin films

A novel technique of micro-thermal analysis (micro-TA) has been used to investigate martensitic to austenitic transformations of near equi-atomic NiTi shape memory alloy (SMA) thin films deposited on silicon wafer by a plasma assisted sputter deposition technique. The results demonstrate that both power and sensor deflection signal of the technique, equivalent to micro-differential thermal analysis (μDTA) and micro-thermomechanical analysis (μTMA), respectively, have a capability of locally characterising transformation temperatures of the SMA films. The phase transition temperatures can be identified as an abrupt deviation of power and thermal expansion from linearity. The change in probe deflection reveals a sample contraction of 0.44% following the martensite to austenitic transformation. This dimension change is consistent with the difference in the unit cell volumes of the different phases. The individual films investigated here show a spatial variation on the micron-scale in the martensite to austenite transition temperatures as the surface is probed. A possible reason for this may lie in the inhomogeneous distribution of Ti and Ni in the film structure as the transition temperature is very sensitive to composition, showing typically a 100 K temperature change between 50 and 51 at.% Ni in Ti. Conventional bulk DSC experiments were carried out on the same materials and the results were compared with those from the micro-TA.     

纳米SiC基光催化剂研究进展

工业化无疑促进了经济的发展,提高了生活水平,但也导致了一些问题,包括能源危机、环境污染、全球变暖等, 其中这些所产生问题主要是由燃烧煤炭、石油和天然气等化石燃料引起的。光催化技术具有利用太阳能将二氧化碳转化为碳氢化合物燃料、从水中制氢、降解污染物等优点,从而在解决能源危机的同时避免环境污染,因此被认为是解决这些问题的最有潜力的技术之一。在各种光催化剂中,碳化硅(SiC)由于其优良的电学性能和光电化学性质,在光催化、光电催化、电催化等领域具有广阔的应用前景。本文首先系统地阐述了各种SiC的合成方法,具体包括模板生长法、溶胶凝胶法、有机前驱物热解法、溶剂热合成法、电弧放电法,碳热还原法和静电纺丝等方法。然后详细地总结了提升SiC光催化活性的各种改性策略,如元素掺杂、构建Z型(S型)体系、负载助催化剂、可见光敏化、构建半导体异质结、负载炭材料、构建纳米结构等。最后重点论述了半导体的光催化机理以及SiC复合物在光催化产氢、污染物降解和CO₂还原等领域的应用研究进展,并提出了前景展望。     

纳米SiC基光催化剂研究进展

Industrialization undoubtedly boosts economic development and improves the standard of living; however, it also leads to some serious problems, including the energy crisis, environmental pollution, and global warming. These problems are associated with or caused by the high carbon dioxide (CO₂) and sulfur dioxide (SO₂) emissions from the burning of fossil fuels such as coal, oil, and gas. Photocatalysis is considered one of the most promising technologies for eliminating these problems because of the possibility of converting CO₂ into hydrocarbon fuels and other valuable chemicals using solar energy, hydrogen (H₂) production from water (H₂O) electrolysis, and degradation of pollutants. Among the various photocatalysts, silicon carbide (SiC) has great potential in the fields of photocatalysis, photoelectrocatalysis, and electrocatalysis because of its good electrical properties and photoelectrochemistry. This review is divided into six sections: introduction, fundamentals of nanostructured SiC, synthesis methods for obtaining nanostructured SiC photocatalysts, strategies for improving the activity of nanostructured SiC photocatalysts, applications of nanostructured SiC photocatalysts, and conclusions and prospects. The fundamentals of nanostructured SiC include its physicochemical characteristics. It possesses a range of unique physical properties, such as extreme hardness, high mechanical stability at high temperatures, a low thermal expansion coefficient, wide bandgap, and superior thermal conductivity. It also possesses exceptional chemical characteristics, such as high oxidation and corrosion resistance. The synthesis methods for obtaining nanostructured SiC have been systematically summarized as follows: Template growth, sol-gel, organic precursor pyrolysis, solvothermal synthesis, arc discharge, carbon thermal reduction, and electrospinning. These synthesis methods require high temperatures, and the reaction mechanism involves SiC formation via the reaction between carbon and silicon oxide. In the section of the review involving the strategies for improving the activity of nanostructured SiC photocatalysts, seven strategies are discussed, viz., element doping, construction of Z-scheme (or S-scheme) systems, supported co-catalysts, visible photosensitization, construction of semiconductor heterojunctions, supported carbon materials, and construction of nanostructures. All of these strategies, except element doping and visible photosensitization, concentrate on enhancing the separation of holes and electrons, while suppressing their recombination, thus improving the photocatalytic performance of the nanostructured SiC photocatalysts. Regarding the element doping and visible photosensitization strategies, element doping can narrow the bandgap of SiC, which generates more holes and electrons to improve photocatalytic activity. On the other hand, the principle of visible photosensitization is that photo-induced electrons move from photosensitizers to the conduction band of SiC to participate in the reaction, thus enhancing the photocatalytic performance. In the section on the applications of nanostructured SiC, photocatalytic H₂ production, pollutant degradation, CO₂ reduction, photoelectrocatalytic, and electrocatalytic applications will be discussed. The mechanism of a photocatalytic reaction requires the SiC photocatalyst to produce photo-induced electrons and holes during irradiation, which participate in the photocatalytic reaction. For example, photo-induced electrons can transform protons into H₂, as well as CO₂ into methane, methanol, or formic acid. Furthermore, photo-induced holes can convert organic waste into H₂O and CO₂. For photoelectrocatalytic and electrocatalytic applications, SiC is used as a catalyst under high temperatures and highly acidic or basic environments because of its remarkable physicochemical characteristics, including low thermal expansion, superior thermal conductivity, and high oxidation and corrosion resistance. The last section of the review will reveal the major obstacles impeding the industrial application of nanostructured SiC photocatalysts, such as insufficient visible absorption, slow reaction kinetics, and hard fabrication, as well as provide some ideas on how to overcome these obstacles.      

P2‐Na0.67AlxMn1−xO2: Cost‐Effective,Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

Sodium layered P2‐stacking Na_0.67MnO₂ materials have shown great promise for sodium‐ion batteries. However, the undesired Jahn–Teller effect of the Mn⁴⁺/Mn³⁺ redox couple and multiple biphasic structural transitions during charge/discharge of the materials lead to anisotropic structure expansion and rapid capacity decay. Herein, by introducing abundant Al into the transition‐metal layers to decrease the number of Mn³⁺, we obtain the low cost pure P2‐type Na_0.67Al_xMn_1?xO₂ (x=0.05, 0.1 and 0.2) materials with high structural stability and promising performance. The Al‐doping effect on the long/short range structural evolutions and electrochemical performances is further investigated by combining in situ synchrotron XRD and solid‐state NMR techniques. Our results reveal that Al‐doping alleviates the phase transformations thus giving rise to better cycling life, and leads to a larger spacing of Na⁺ layer thus producing a remarkable rate capability of 96 mAh g^‐1 at 1200 mA g^‐1.     

Substitution clustering in a non-stoichiometric celsian synthesized by the thermal transformation of barium exchanged zeolite X

The thermal transformation of Ba exchanged zeolite X to celsian has been studied by ²⁷Al and ²⁹Si MAS NMR spectroscopy. Evidence for the degradation of the zeolite framework is present in the ²⁹Si NMR spectra after thermal treatment at 850 °C. Confirmation is provided by the ²⁹Si NMR data that synthesis of celsian via the decomposition of Ba exchanged zeolite leads to a single defect phase. Clustering of the isomorphous replacement of aluminium by silicon must occur to explain the observed ²⁹Si chemical shifts. The ²⁷Al NMR data show distorted aluminium co-ordination sites upon the thermal transformation of Ba exchanged zeolite X. The distortions present in the amorphous matrix are greater than those present in the monoclinic and hexagonal crystalline phases of celsian.     

P2‐Na0.67AlxMn1−xO2: Cost‐Effective,Stable and High‐Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility

Sodium layered P2‐stacking Na_0.67MnO₂ materials have shown great promise for sodium‐ion batteries. However, the undesired Jahn–Teller effect of the Mn⁴⁺/Mn³⁺ redox couple and multiple biphasic structural transitions during charge/discharge of the materials lead to anisotropic structure expansion and rapid capacity decay. Herein, by introducing abundant Al into the transition‐metal layers to decrease the number of Mn³⁺, we obtain the low cost pure P2‐type Na_0.67Al_xMn_1?xO₂ (x=0.05, 0.1 and 0.2) materials with high structural stability and promising performance. The Al‐doping effect on the long/short range structural evolutions and electrochemical performances is further investigated by combining in situ synchrotron XRD and solid‐state NMR techniques. Our results reveal that Al‐doping alleviates the phase transformations thus giving rise to better cycling life, and leads to a larger spacing of Na⁺ layer thus producing a remarkable rate capability of 96 mAh g^‐1 at 1200 mA g^‐1.     

Multi-Color Fluorescent Carbon Dots: Graphitized sp2 Conjugated Domains and Surface State Energy Level Co-Modulate Band Gap Rather Than Size Effects

Four types of carbon dots (CDs) with various color (blue, green, yellow, and red) emissions have been synthesized under solvent-free conditions from citric acid and different nitrogen sources (DMF, urea, ethanamide, and formamide). By detailed characterization and comparison, it is confirmed that the graphitized sp² conjugated domain and surface functional groups such as C−O and C=N play synergetic roles in adjusting the fluorescence properties. Notably, the size effect is not the dominant mechanism to achieve multi-color fluorescence emissions in this work. The structural configuration of the carbon dots further influences the energy band structure, as demonstrated in simplified energy level diagrams. An absorption peak at approximately 560 nm appears in the visible light region for red-emitting CDs, assigned to an n→π* transition of the aromatic structure, thus introducing a new surface state energy level, resulting in a reduction in the energy of electron transition and the expansion into the visible region of the UV/Vis spectrum. Taking advantage of the diverse absorption and emission properties, different CDs/TiO₂ binary composites are obtained for photocatalytic degradation of organic dyes, and it is found that the absorption range in terms of visible light and the band gap of the carbon dots make a difference to the photocatalytic performance of the composites.     

Spectral, optical, and thermal studies of pure and Zn(II)-doped l-histidine hydrochloride monohydrate (LHHC) crystals

The influence of doping the transition metal Zn(II) on the growth, spectral, optical, and thermal properties of l-histidine hydrochloride monohydrate (LHHC) crystals grown by slow solvent evaporation method has been investigated. Structural characterizations of the grown crystals were carried out by single crystal X-ray diffraction analysis and it shows slight structural changes as a result of doping. The FT-IR spectral study reveals the presence of various functional groups and confirms the slight distortion of the structure of the crystals due to doping. The energy dispersive X-ray analysis reveals the incorporation of Zn(II) in the crystalline matrix of LHHC crystal. The UV?CVis spectral study was carried out to analyze the optical transmittance of the grown crystals and found that the transmittance is very high in the visible and UV regions for both pure and doped crystals. The second harmonic generation (SHG) for the grown crystals was confirmed by Nd:YAG laser. The scanning electron microscopy reveals the presence of defect centers and crystal voids. The thermal stability and purity of the grown crystals were analyzed by thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques.     

Degradation of inter-atomic bonds during structural phase change in intermediate Ni-clusters (Ni39-Ni49)

Results based on a symmetry- and spin-unrestricted tight-binding molecular-dynamics study are presented for the ground-state geometries of intermediate Ni(n), n in [39,49], clusters. A structural phase change is found to take place around n=43 during which a structural transition from fcc/hcp structure to icosahedral one is observed. This is in good agreement with recent experimental findings. This structural transition is found to be associated with a degradation of the inter-atomic bond energy which indicates that the inter-atomic bond does not only depend on the coordination number of each atom but also on its point group symmetry.     

High surface area of porous silicon drives desorption of intact molecules

The surface structure of porous silicon used in desorption/ionization on porous silicon (DIOS) mass analysis is known to play a primary role in the desorption/ionization (D/I) process. In this study, mass spectrometry and scanning electron microscopy (SEM) are used to examine the correlation between intact ion generation with surface ablation and surface morphology. The DIOS process is found to be highly laser energy dependent and correlates directly with the appearance of surface ions (Si(n)(+) and OSiH(+)). A threshold laser energy for DIOS is observed (10 mJ/cm(2)), which supports that DIOS is driven by surface restructuring and is not a strictly thermal process. In addition, three DIOS regimes are observed that correspond to surface restructuring and melting. These results suggest that higher surface area silicon substrates may enhance DIOS performance. A recent example that fits into this mechanism is the surface of silicon nanowires, which has a high surface energy and concomitantly requires lower laser energy for analyte desorption.     

The Thermal Expansion of GeS and GeTe

The thermal expansion of GeS has been studied above room temperature up to the melting point of 658 ± 5°C by X-ray diffraction techniques using a 190 mm diameter Unicam high temperature camera. The thermal expansion of the crystallographic axes is linear with distinct changes in the rate of expansion at about 250°C, 370°C and 510°C. No first-order structural transformation was observed for this system up to the melting point. The results of additional studies on GeTe are in general agreement with those of others and confirm trends in the thermal expansion behavior of the germanium monochalcogenide series.