Fundamentals of hydrogen evolution reaction and its implications on near-neutral pH stress corrosion cracking of pipelines

In this work, electrochemical techniques were utilized to investigate the hydrogen evolution reaction on X-70 pipe steel and the hydrogen permeation through the steel in near-neutral pH environmental condition. The results demonstrate that the steel has always been in an active-dissolution state in near-neutral pH solution and there is no film formed on the steel surface. Hydrogen evolution is inhibited by anodic polarization of the steel, which is attributed to the alternation of hydrogen evolution mechanism and kinetics on the anodially polarized steel. Combined with slow strain rate tensile tests, it is found that the high susceptibility of steel to stress corrosion cracking (SCC) is always associated with a high hydrogen permeation current. A thermodynamic model was developed, by analyzing the change in free-energy of the steel in the presence and absence of hydrogen and stress, to determine the interactions of hydrogen, stress and anodic dissolution at the crack-tip. The role of hydrogen involvement in pipeline near-neutral pH SCC could be determined quantitatively by characterizing the effect of hydrogen concentration on the dissolution rate of steel and the synergism of hydrogen and stress to promote crack growth.     

Enhancing the oxygen permeability of Ba0.5Sr0.5Co0.8Fe0.2O5 + δ membranes by coating RBaCo2O5 + δ(R= Pr, Nd, Sm, Gd) layers

The effects of a thin RBaCo₂O_5 + δ (R= Pr, Nd, Sm, Gd) layer coating on the oxygen permeation flux through Ba_0.5Sr_0.5Co_0.8Fe_0.2O_5 + δ(BSCF) membrane were investigated. Due to the high oxygen adsorption and desorption rate constants k_a and k_d of the RBaCo₂O_5 + δ (R112) materials and the porous structure of the coating layers, the oxygen permeation flux through the BSCF membranes can be enhanced remarkably. It was found that the reaction between Pr112 and BSCF also has significant influence on the oxygen permeation flux. The reaction between Pr112 and BSCF forms impurities which may block oxygen permeation flux. However, Nd112, Sm112, and Gd112 do not react seriously with BSCF, therefore, coating layers of these materials can significantly enhance the oxygen permeation flux of BSCF membranes.     

Hydrogen separation and stability study of ceramic membranes based on the system Nd5LnWO12

This contribution presents the preparation, permeation and stability study of mixed protonic-electronic conducting membranes based on the system Nd₅LnWO₁₂. The tungstates Ln₆WO₁₂ are proton conducting crystalline materials, which show sufficient protonic and electronic mixed conductivity and stability in moist CO₂ environments to consider them as potential candidates for the separation of hydrogen at high temperatures. Hydrogen separation properties of A-substoichiometric Nd₆WO₁₂ and Nd₅LaWO₁₂ were systematically analyzed, i.e. the influence of the H₂ concentration in feed stream, humidification degree and operating temperature on the hydrogen separation was studied. Finally, the stability of these materials at different temperatures and CO₂-rich and sulfur-containing environments was evaluated.     

Frequency response of continuous-flow adsorber for multicomponent system

In this paper, we present a theoretical analysis of the frequency response of a continuous-flow adsorber with periodic modulation of the inlet flow-rate to measure multicomponent diffusion kinetics in porous media. Micropore diffusion kinetics is assumed for the intraparticle mass transfer mechanism and three different shapes of microparticle are considered: slab, cylinder, and sphere. Simulation results for a binary system show that the frequency response of the faster diffusing component is strongly influenced by the slower component. The out-of-phase characteristic function of the frequency response of the faster diffusing component shows maximum and minimum points. The deviation between these maximum and minimum values becomes smaller when the cross-terms of diffusivity go to zero, while the deviation becomes larger when the cross-terms of the adsorption equilibrium constant go to zero. Contrary to the behaviour of the out-of-phase function of the faster diffusing component, the out-of-phase function of the slower diffusing component shows no extrema at all. The in-phase characteristic function of the frequency response of the continuous-flow adsorber is not affected by the overflow parameter.     

On the temperature distribution in the counter flow heat exchanger with multicomponent non-azeotropic mixtures

The influence of mixture composition on the temperature distribution in the counter flow heat exchanger used in mixture Joule–Thomson refrigerators is investigated in this paper. A perfect heat capacity matching between the supply and the return streams can be achieved by optimizing the mixture composition. The deeper reason is that in two-phase state the latent heat makes a very important contribution in the overall heat capacity for multicomponent non-azeotropic mixtures. The theoretical results are compared with experimental data; both theoretical and experimental results agree well with each other. The results show that the temperature profile as well as the locations of the pinch points is determined by the mixture compositions. Therefore, it is possible to get a perfect temperature distribution using optimal mixture. This becomes another criterion of the optimization of mixture composition.     

Modern mass spectrometry for coatings

For the analysis of polymers soft ionization mass spectrometry, in which only molecular ions are observed, can provide the complete distribution of chains (length, composition, end-groups) in under ten minutes on microgram quantities of material. Moreover, molecular ion information of neat organic pigments or those present in crosslinked networks can also be furnished. No other analytical technique can supply these data in such a short time. The application of mass spectrometry to the characterization of materials used in today's high performance automotive coatings is presented. These include functional monomers, several acrylic copolymers, organic pigments and an epoxide prepolymer. While there are a variety of mass spectrometric techniques, in this paper we will highlight the techniques that we have found useful for the characterization of organic coating components. The selection of the mass spectrometric technique is dictated by the molecular weight of the material and to a lesser extent the chemical composition. We used potassium ionization of desorbed species (K⁺IDS) performed on a quadrupole mass spectrometer for materials under 1000 Daltons (Da). However, many of the ingredients used in current automotive finishes fall between 1000 and 10 000 Da. For these materials we used a Fourier transform mass spectrometer (FTMS) which is well suited for this mass range and boasts the highest resolution and mass accuracy available. Direct desorption/ionization using a carbon dioxide laser is our standard method of sample introduction. Recently, we coupled a gel permeation chromatograph to our FTMS using an electrospray ionization interface. This hyphenated technique offers one of the most powerful characterization methods for the coatings chemist.     

相干纤维束及其在我国的应用

本文主要介绍多组分玻璃光纤相干纤维束的特性及其在我国的应用。     

Temperature influence on transport parameters characteristic of Knudsen and Poiseuille flows

Single gas permeation experiments results using neon, argon, nitrogen and methane are reported. From gas permeation experiments the characteristic parameters of the Knudsen and Poiseuille transport mechanisms were determined by means of an equation derived from the “Dusty-Gas” model. The experiments were performed at different temperatures from 303.15 to 323.15 K, in order to study the temperature influence on those parameters. For PVDF and PCTE membranes the influence of the temperature on K_o and B_o parameters was not significant. Gas influence was also investigated for both types of membrane, a slight tendency of K_o to decrease with increase in molar mass and a very slight tendency of B_o to increase with increase in molar mass, although these trends were not fulfilled by neon gas.     

Characterization and In-vitro Permeation Study of Stearic Acid Nanoparticles containing Hinokitiol

Lipid nanoparticles containing hinokitiol (HKL) were prepared by a melt–emulsification method. Stearic acid was used as a lipid for the matrix material of the nanoparticles. According to results from transmission electron microscopy (TEM) and dynamic light scattering (DLS), most of the nanoparticles were less than 100 nm. When nanoparticles containing HKL were scanned on a differential scanning calorimeter, no endothermic peak of HKL was observed. This means that HKL in the lipid matrix of the nanoparticles is in a dissolved state. In an 18-h permeation study using hairless mouse skin mounted on a diffusion cell, the amount of HKL encapsulated in the nanoparticles transported to the receptor cell was five to ten times more than for HKL dissolved either ethanol or propylene glycol. Therefore, stearic acid nanoparticles strongly enhanced permeation of the skin by HKL.     

Hydrogen permeation in Fe-40 at.% Al alloy at different temperatures

The electrochemical permeation technique for studying transport and trapping of hydrogen in Fe-40 at.% Al alloy at temperatures of 5, 25, 45 and 65 °C was used in the paper. The influence of temperature on the effective hydrogen diffusion coefficient, hydrogen permeation rate and hydrogen solubility was determined. The activation energy of hydrogen diffusion in iron aluminide in the studied temperature range was also determined.