Research and demonstration on hydrogen compatibility of pipelines: a review of current status and challenges

Hydrogen transportation by pipelines gradually becomes a critical engineering route in the worldwide adaptation of hydrogen as a form of clean energy. However, due to the hydrogen embrittlement effect, the compatibility of linepipe steels and associated welds with hydrogen is a major concern when designing hydrogen-carrying pipelines. When hydrogen enters the steels, their ductility, fracture resistance, and fatigue properties can be adversely altered. This paper reviews the status of several demonstration projects for natural gas-hydrogen blending and pure hydrogen transportation, the pipeline materials used and their operating parameters. This paper also compares the current standards of materials specifications for hydrogen pipeline systems from different parts of the world. The hydrogen compatibility and tolerance of varying grades of linepipe steels and the relevant testing methods for assessing the compatibility are then discussed, and the conservatism or the inadequacies of the test conditions of the current standards are pointed out for future improvement.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

Directional separation of hydrogen-containing gas mixture by hydrate-membrane coupling method

Recovery of hydrogen (H₂) from H₂-containing gas mixtures has great significance for energy conservation, cost reduction and benefit increase. However, the common separation methods have the ubiquitous problem due to phase equilibrium principle and results in the conflict between H₂ concentration and H₂ recovery rate in the product gas. Consequently, an innovative conception of hydrate-membrane coupling approach is proposed in this work. In the separation process, hydration and membrane permeation two separation driving forces coexist to achieve the aim of strengthening mass transfer kinetics. H₂ and non-H₂ components (hydrocarbons) are synchronously and directionally selected by membrane and hydrate to improve different phase compositions. Therefore, the gas in feed side could keep relatively high two separation driving forces (H₂ fugacity and hydrocarbons fugacity). The results show that the coupling method could synchronously increase both the concentration and the recovery rate of H₂ in the product gas. At the same time, the volume and concentration of the hydrocarbons in hydrate both increases effectively. It indicates that hydrate and membrane separation methods support each other in the separation process. The hydrate-membrane coupling method fundamentally solves the issue of the decreasing driving force resulting from single separation method and phase equilibrium relationship.     

Improved thermal stability of the near-infrared Al-modulated Zn3Ga2GeO8: Cr3+ phosphors for plant growth applications

The exploration of the high thermal stability near-infrared (NIR) phosphors is significantly crucial for the development of plant lighting. However, NIR phosphors suffer from the poor chemical and thermal stability, which severely limits their long-term operation. Here, the successful improvement of luminous intensity (149.5%) and thermal stability at 423 K of Zn₃Ga₂GeO₈ (ZGGO): Cr³⁺ phosphors is achieved for the introduction of Al³⁺ ions into the host. The release of carriers in deep traps inhibits the emission loss for the thermal disturbance. Furthermore, an NIR light emitting diodes (LEDs) lamp is explored by combining the optimized Zn₃Ga_1.1675Al_0.8GeO₈: 0.0325Cr³⁺ phosphors with a commercial 460 nm blue chip, and the emission band can match well with the absorption bands of photosynthetic pigments and the phytochrome (P_R and P_FR) of plants. The explored LEDs lamp further determines the growth and the pheromone content of the involved plants for the participation of the NIR emission originated from Cr³⁺ ions. Our work provides a promising NIR lamp as plant light with improved thermal stability for long-term operation.     

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study, the Bayan Obo rare earth concentrates mixed with Na₂CO₃ were used for roasting research. The phase change process of each firing stage was analyzed. The kinetic mechanism model of the continuous heating process was calculated. This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis. Using X-ray diffraction (XRD), Fourier infrared spectroscopy, scanning electron microscopy with energy dispersive spectrometry, the reaction process and the existence of mineral phases were analyzed. The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics. The phase transition results show that carbonate-like substances first decompose into fine mineral particles, and CaO, MgO, and SiO₂ react to form silicates, causing hardening. Further, REPO₄ and NaF can directly generate CeF₃ and CeF₄ at high temperatures, and a part of CeF₄ and NaF forms a solid solution substance Na₃CeF₇. Rare earth oxides calcined at a high temperature of 750 °C were separated to produce Ce_0.6Nd_0.4O_1.8, Ce₄O₇, and LaPrO_3+x. Then, BaSO₄, Na₂CO₃, and Fe₂O₃ react to form barium ferrite BaFe₁₂O₁₉; the kinetic calculation results show that during the continuous heating process, the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440–524 °C, and the reaction order n reaches the maximum, which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy. The mechanism function is F(α) = [?ln (1?α)]^1/3. The reaction order n reaches the minimum in the temperature range of 680–757 °C, and the apparent activation energy E is large. The difficulty of the reaction increases during the final stage. The reaction mechanism function is F(α) = [1?(1?α)^1/3]². Observing the entire reaction stage, the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion (spherical symmetry).     

The kinetics of copper corrosion in nitric acid

The strategy for the permanent disposal of high-level nuclear waste in Canada involves sealing it in a copper-coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X-ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).     

Form selection of concomitant polymorphs: A case study informed by crystallization kinetics modeling

Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation and concomitant crystallization are difficult to be distinguished in practice, as multiple forms can be detected at the same time. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid. Our kinetic modeling aims to understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the composition of form I in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.     

Highly oriented α-Al2O3 transparent ceramics shaped by shear force

Alumina platelets were arranged horizontally in submicron alumina particles by shear force in the flow of slurries during casting. The obtained alumina green bodies with platelets were pressureless-sintered in vacuum, producing ceramics with thoroughly oriented grains and high transmittance. The effects of sintering parameters on the densification, microstructure evolution, and orientation degree of alumina ceramics were investigated and discussed. The results showed that the densification, grain size, orientation degree, and in-line transmittance were increased with increasing sintering temperature. The enhancement of orientation degree was mainly coherent with grain growth. The grain-oriented samples exhibited a much higher in-line transmittance (at 600 nm) of 61 % than that of the grain random sample (29 %). Moreover, the transmission remained a high level in the ultraviolet range (<300 nm).