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.     

Achieving superior hydrogen storage properties via in-situ formed nanostructures: A high-capacity Mg–Ni alloy with La microalloying

Mg-based hydride is a promising hydrogen storage material, but its capacity is hindered by the kinetic properties. In this study, Mg–Mg₂Ni–LaH_x nanocomposite is formed from the H-induced decomposition of Mg₉₈Ni_1·67La_0.33 alloy. The hydrogen capacity of 7.19 wt % is reached at 325 °C under 3 MPa H₂, attributed to the ultrahigh hydrogenation capacity in Stage I. The hydrogen capacity of 5.59 wt % is achieved at 175 °C under 1 MPa H₂. The apparent activation energies for hydrogen absorption and desorption are calculated as 57.99 and 107.26 kJ/mol, which are owing to the modified microstructure with LaH_x and Mg₂Ni nanophases embedding in eutectic, and tubular nanostructure adjacent to eutectic. The LaH_2.49 nanophase can catalyze H₂ molecules to dissociate and H atoms to permeate due to its stronger affinity with H atoms. The interfaces of these nanophases provide preferential nucleation sites and alleviate the “blocking effect” together with tubular nanostructure by providing H atoms diffusion paths after the impingement of MgH₂ colonies. Therefore, the superior hydrogenation properties are achieved because of the rapid absorption process of Stage I. The efficient synthesis of nano-catalysts and corresponding mechanisms for improving hydrogen storage properties have important reference to related researches.     

Performance of BaZrO3/Y2O3 dual-phase refractory applied to TiAl alloy melting

Vacuum induction melting is a potential process for the preparation of TiAl alloys with good homogeneity and low cost. But the crucial problem is a selection of high stability refractory. In this study, a BaZrO₃/Y₂O₃ dual-phase refractory was prepared and its performance for melting TiAl alloys was studied and compared with that of a Y₂O₃ refractory. The results showed the dual-phase refractory consisted of BaZr_1-xY_xO_3-δ and Y₂O₃(ZrO₂), exhibited a thinner interaction layer (30 μm) than the Y₂O₃ refractory (90 μm) after melting the TiAl alloy. Although the TiAl alloys melted in the dual-phase and Y₂O₃ refractory exhibited similar oxygen contamination (<0.1 wt%), the alloy melted in the dual-phase refractory had smaller Y₂O₃ inclusion content and size than that in the Y₂O₃ refractory, indicating that the dual-phase refractory exhibited a better melting performance than the Y₂O₃ refractory. This study provides insights into the process of designing highly stable refractory for melting TiAl alloys.     

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.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

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     

Development of a H2-permeable Pd60Cu40-based composite membrane using a reverse build-up method

A new reverse build-up method is developed to fabricate an economical H₂-permeable composite membrane. Sputtering and electroplating are used for the formation of a membrane comprised of a 3.7-μm-thick Pd₆₀Cu₄₀ (wt.%) alloy layer and a 13-μm-thick porous Ni support layer, respectively. The H₂-permeation measurements are performed under the flow of a gaseous mixture of H₂ and He at 300–320 °C and 50–100 kPa of H₂ partial pressure. The H₂/He selectivity values exceed 300. The activation energy at 300–320 °C is 10.9 kJ mol⁻¹. The H₂ permeability of the membrane is 1.25 × 10⁻⁸ mol m⁻¹ s⁻¹ Pa^−0.5 at 320 °C after 448 h. The estimated Pd cost of the proposed membrane is approximately 1/8 of the cost for a pure Pd₆₀Cu₄₀ membrane. This study demonstrates that the proposed method allows the facile production of low-cost, Pd-based membranes for H₂ separation.