Analysis of suitability of TPP ash-slag waste as materials for hydrogen fuel storage

The current trends in energy were described, the main of which is the use of alternative energy sources, especially hydrogen. The most common methods of hydrogen accumulation were proposed: accumulation of compressed gaseous hydrogen in high-pressure tanks; accumulation of liquid hydrogen in cryogenic tanks; storing hydrogen in a chemically bound state; accumulation of gaseous hydrogen in carriers with a high specific surface area. Based on the combination of advantages and disadvantages, the most promising methods of accumulation were selected: storage of liquid hydrogen and storage of hydrogen in carriers with a high specific surface area. The main requirement for materials for hydrogen storage by these methods was revealed – a high specific surface area. Prospects for the development of waste-free low-emission technologies due to the recycling of secondary raw materials and the development of low-temperature technologies for the synthesis of functional and structural materials were substantiated. The applicability of large-scale ash and slag waste from coal-fired thermal power plants as a raw material for obtaining materials by low-temperature technologies was shown. The traditional ways of using ash and slag waste as a raw material, active additive and filler in the production of cements were described. Modern technologies for the production of innovative materials with a unique set of properties were presented, namely carbon nanotubes, silica aerogel and geopolymer materials. The prospect of using geopolymer matrices as a precursor for the synthesis of a number of materials was described; the most promising type of materials was selected – geopolymer foams, which are mainly used as sorbents for purifying liquids and gases or accumulating target products, as well as heat-insulating materials. The possibility of obtaining products of any shape and size on the basis of geopolymer matrices without high-temperature processing was shown. The special efficiency of the development of the technology of porous granules and powders obtained from a geopolymer precursor using various methods was substantiated. The obtained granules can be used in the following hydrogen storage technologies: direct accumulation of hydrogen in porous granules; creation of insulating layers for liquid hydrogen storage units.     

Preparation,structural and photocatalytic activity of Sn/Fe co-doped TiO2 nanoparticles by sol-gel method

Pure and Sn/Fe co-doped (0.2 at.% Sn and 0.6 at.% Fe, 0.6 at.% Sn and 0.2 at.% Fe, 1.0 at.% Sn and 1.0 at.% Fe) TiO₂ nanoparticles were synthesized via a sol-gel method and subsequently calcined at different temperatures. Furthermore, the particles were analyzed by TG-DSC, XRD, TEM, HRTEM, EDS, SAED and UV–Vis for investigating the influences of dopant and calcination temperature on the thermal effect, composition, morphology, energy band gap (E_g) and the degradation efficiency of methyl orange (MO) under various light irradiations respectively. Results indicated that Sn/Fe co-doping inhibited the crystallization transformation from anatase to rutile phase of TiO₂ and decreased the E_g. The increased calcination temperature and Sn/Fe co-doped effect brought about the abnormal grain growth of TiO₂ nanoparticles. 0.6 at.% Sn/0.2 at.% Fe and 1.0 at.% Sn/1.0 at.% Fe co-doped TiO₂ nanoparticles presented better photocatalytic performance than pure and 0.2 at.% Sn/0.6 at.% Fe co-doped TiO₂ nanoparticles under visible light irradiation mainly due to the decreased E_g. On the contrary, 0.2 at.% Sn and 0.6 at.% Fe co-doped TiO₂ nanoparticles calcined at 650 °C showed the most excellent photocatalytic performance under UV light irradiation, which was about twice as large as that of pure TiO₂ possibly due to the formed hybrid structure of anatase and rutile phase as well as the h⁺-mediated decomposition pathway.     

Fabrication of alumina ceramics with functional gradient structures by digital light processing 3D printing technology

Alumina ceramics with different unit numbers and gradient modes were prepared by digital light processing (DLP) 3D printing technology. The side length of each functional gradient structure was 10 mm, the porosity ratio was controlled to 70%, and the number of units were (1 × 1 × 1 unit) and (2 × 2 × 2 unit) respectively. The different gradient modes were named FCC, GFCC-1, GFCC-2 and GFCC-3. SEM, XRD, and other characterization methods proved that these gradient structures of alumina ceramics had only α-Al2O3 phase and good surface morphology. The mechanical properties and energy absorption properties of alumina ceramics with different functional gradient structures were studied by compression test. The results show that the gradient structure with 1 × 1 × 1 unit has better mechanical properties and energy absorption properties when the number of units is different. When the number of units is the same, GFCC-2 and GFCC-3 gradient structures have better compressive performance and energy absorption potential than FCC structures. The GFCC-2 gradient structure with 1 × 1 × 1 unit has a maximum compressive strength of 19.62 MPa and a maximum energy absorption value of 2.72 × 105 J/m3. The good performance of such functional gradient structures can provide new ideas for the design of lightweight and compressive energy absorption structures in the future.     

The phosphorescence emission in undoped lead-halide Cs4PbBr6 single crystals at low temperature

Recently, all-inorganic cesium lead-halide perovskites have shown their promise for light emission applications, due to the excellent optical performance. Herein, we report that the initially nonphosphorescent undoped lead-halide Cs₄PbBr₆ single crystals (SCs) exhibit an ultralong phosphorescence emission under X-ray excitation at low temperatures. It is shown that the dramatic change has been taken place in radioluminescence spectra and the broad-band emission gradually appeared with the decrease of temperature. Below 210 K, the radioluminescence spectra can be deconvoluted into one narrow peak located at 530 nm and two broad peaks centered at 595 nm and 672 nm respectively. Subsequently, the time-dependent radioluminescence spectra in undoped lead-halide Cs₄PbBr₆ SCs were investigated. The ultralong phosphorescence emission can persist over 120 min at 70 K. We consider that ultralong phosphorescence originates from defect-related emission. To the best of our knowledge, our finding is the first time that undoped Cs₄PbBr₆ SCs exhibit the phosphorescence emission, which will offer a paradigm to motivate revolutionary applications on perovskite.     

Silver-substituted (Ag1-xCux)2ZnSnS4 solar cells from aprotic molecular inks

To battle the high open-circuit voltage deficit (V_OC,def) in kesterite (Cu₂ZnSnS₄ or CZTS) solar cells, a current field of research relates to point defect engineering by cation substitution. For example, by partly replacing Cu with an element of a larger ionic radius, such as Ag, the degree of Cu/Zn disorder decreases, and likewise does the associated band tailing. In this paper, solution-processed (Ag_1-xCu_x)₂ZnSnS₄ (ACZTS) samples are prepared through the aprotic molecular ink approach using DMSO as the solvent. The successful incorporation of silver into the CZTS lattice is demonstrated with relatively high silver concentrations, namely Ag/(Ag+Cu) ratios of 13% and 26%. The best device was made with 13% Ag/(Ag+Cu) and had an efficiency of 4.9%. The samples are compared to the pure CZTS sample in terms of microstructure, phase distribution, photoluminescence, and device performance. In the XRD patterns, a decrease in the lattice parameter c/a ratio is observed for ACZTS, as well as significant peak splitting with Ag addition for several of the characteristic kesterite XRD reflections. In addition to the improvement in efficiency, other advantageous effects of Ag-incorporation include enhanced grain growth and an increased band gap. A too high concentration of Ag leads to the formation of secondary phases such as SnS and Ag₂S as detected by XRD.     

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Dense and core-rim structured B4C-TiB2 ceramics with Mo-Co-WC additive

B₄C-TiB₂ ceramics (TiB₂ ranging 5~70 vol%) with Mo-Co-WC as the sintering additive were prepared by spark plasma sintering. In comparison with B₄C-TiB₂ without additive, the enhanced densification was evident in the sintered specimen with Mo-Co-WC additive. Core-rim structured grain was observed around TiB₂ grains. The interface of the rim between TiB₂ and B₄C phases demonstrated different feature: the inner borderline of the rim exhibited a smooth feature, whereas a sharp curved grain boundary was observed between the rim and the B₄C grain. The formation mechanism is discussed: the epitaxial growth of (Ti,Mo,W)B₂ rim around the TiB₂ core may occur as a result of the solid solution and dissolution-precipitation between TiB₂ phase and the sintering additive. It was revealed that the fracture toughness increased as the content of TiB₂ content increased, alongside the decreased hardness. B₄C-30 vol% TiB₂ specimen demonstrated the optimal combination of mechanical properties, reaching Vickers hardness of 24.3 GPa and fracture toughness of 3.33 MPa·m^1/2.     

Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry