The Kinetic Model of Diffusion and Reactions in Powder Catalysts during Temperature Programmed Oxygen Isotopic Exchange Process

The mathematical model of diffusion in powder oxide catalysts during the process of temperature programmed oxygen isotopic exchange is proposed. The diffusion is considered together with the homogeneous and heterogeneous oxygen isotopic exchange processes. The matrix forms of exchange rate equations of simple and complex heteroexchange, and homoexchange reactions which obtain symmetrical forms are analyzed. The quantitative values of model parameters are found from the fitting of experimental data taken from literature of temperature programmed oxygen isotopic exchange process in catalysts ZrO2 and CeO2. The fittings show a good matching of model results with experimental data. The shapes of kinetic curves registered during temperature programmed oxygen isotopic exchange process are analyzed and the influence of various process parameters such as activation energies of simple and complex heteroexchange, oxygen surface concentration of catalyst, ratio of catalysts surface and volume of reactor, diffusion activation energy is considered. The depth profiles of diffusing oxygen species in oxide catalysts powder are calculated.

Forming feasibility and interface microstructure of Al/Cu bimetallic structure fabricated by laser powder bed fusion

Purpose The purpose of this paper is to analyze and investigate heat accumulation caused by temperature changes and interface microstructure effected by element diffusion. Design/methodology/approach Al/Cu bimetallic structure is initially manufactured through laser powder bed fusion process. To minimize trial and error, finite element modeling is adopted to simulate temperature changes on the Al-based and Cu-based substrate. Findings The results show that forming pure copper on Al-based substrate can guarantee heat accumulation, providing enough energy for subsequent building. The instantaneous laser energy promotes increase of diffusion activation energy, resulting in the formation of transition zone derived from interdiffusion between Al and Cu atoms. The interface with a thickness of about 22 µm dominated by Kirkendall effect moves towards Al-rich side. The interface microstructure is mainly composed of a-Al, a-Cu and CuAl2 phase. Originality/value The bonding mechanism of Al/Cu interface is atom diffusion-induced chemical reaction. The theoretical basis provides guidance for structural design and production application.

Hydration layer of only few molecules controls lipid mobility in biomimetic membranes

Self-assembly of biomembranes results from the intricate interactions between water and the lipids' hydrophilic head groups. Therefore, the lipid-water interplay strongly contributes to modulating membranes architecture, lipid diffusion, and chemical activity. Here, we introduce a new method of obtaining dehydrated, phase-separated, supported lipid bilayers (SLBs) solely by controlling the decrease of their environment's relative humidity. This facilitates the study of the structure and dynamics of SLBs over a wide range of hydration states. We show that the lipid domain structure of phase-separated SLBs is largely insensitive to the presence of the hydration layer. In stark contrast, lipid mobility is drastically affected by dehydration, showing a 6-fold decrease in lateral diffusion. At the same time, the diffusion activation energy increases approximately twofold for the dehydrated membrane. The obtained results, correlated with the hydration structure of a lipid molecule, revealed that about 6-7 water molecules directly hydrating the phosphocholine moiety play a pivotal role in modulating lipid diffusion. These findings could provide deeper insights into the fundamental reactions where local dehydration occurs, for instance during cell-cell fusion, and help us better understand the survivability of anhydrobiotic organisms. Finally, the strong dependence of lipid mobility on the number of hydrating water molecules opens up an application potential for SLBs as very precise, nanoscale hydration sensors.

Excess Li2O Additives to Promote Grain Boundary Growth and Improve Ionic Conductivity of LiTa2PO8 Solid Electrolytes

LiTa2PO8 (LTPO) is a new solid-state lithium ion electrolyte material reported in the latest research, which has high bulk ionic conductivity and low grain boundary ion conductivity. However, it is difficult to density with conventional sintering methods. Herein, in this work, the solid-phase synthesis method was used to prepared the LTPO solid-state electrolyte, and the influence of the amount of lithium on the structure and performance of LTPO electrolyte material was investigated. The results show that the excess Li2O does not increase other impurities and does not change the structure of the material, but the liquid phase produced by the excess Li2O can promote the elimination of interfacial pores, accelerate the direct bonding of grains and improve the ionic conductivity of grain boundary, thus improving the overall ionic conductivity of the material. Considering the volatilization of lithium and the impact of liquid phase sintering at high temperatures and the content restructuring, after adding 20 wt% excess formulation of Li2O, the resultant of LTPO density is 5.0 g/cm3, the density reaches 85.58%. As a result, the total ionic conductivity of the electrolyte is 3.28 × 10–4 S/cm at 25°C, and the Li-ion diffusion activation energy is 0.27 eV. In addition, after loading this electrolyte into a Li–Li symmetric battery, it is proved that the electrolyte has lithium ion transport performance and can be used in all-solid-state batteries. However, it is also found from cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) analysis that the interface between LTPO material and Li is unstable, and Ta5+ ions are reduced, which will be another key issue to be addressed in the future.

Diffusion of oxygen in hypostoichiometric uranium dioxide nanocrystals. A molecular dynamics simulation

A molecular dynamic simulation of diffusion of intrinsic oxygen anions in the bulk of hypostoichiometric UO2-x nanocrystals with a free surface was carried out. The main diffusion mechanism turned out to be the migration of oxygen by the anionic vacancies. It is shown that in the range of values of the non-stoichiometry parameter 0.05 £x £ 0.275 the oxygen diffusion coefficient D is weakly dependent on temperature, despite the uniform distribution of the vacancies over the model crystallite. The reliable D values calculated for the temperature T = 923 K are in the range from 3×10-9 to 7×10-8 cm2/s, in quantitative agreement with the experimental data. The corresponding diffusion activation energy is in the range from 0.57 eV to 0.65 eV, depending on the interaction potentials used for the calculations.

Diffusion mechanism in cutting Ni-based alloy containing γ′ phase (Ni3Al) with CBN tool based on MD simulation

Ni-based alloys are widely used in aerospace because of their high strength and high temperature oxidation resistance. CBN tool is suitable for precision machining of Ni-based alloy. Diffusion wear is an important wear form of CBN tool in the process of cutting Ni-based alloy. Therefore, it is of great significance to study the diffusion phenomenon in the process of cutting Ni-based alloy with CBN tool. In this paper, the cutting model of Ni-based alloy containing γ′ phase (Ni3Al) with CBN tool is established based on the molecular dynamics (MD) simulation method. The self diffusion activation energy of all kinds of atoms in the workpiece and the formation energy of several point defects in the tool are calculated, so as to study in depth the atom diffusion mechanism according to the simulation results. The results show that the atoms in the crystal boundary of the workpiece are the most easily diffused, followed by the atoms in the phase boundary, and the atoms in the lattice are the most difficult to diffuse. When the workpiece atoms diffuse into the tool, it is easier to diffuse into the tool grain boundary than to form interstitial impurity atoms or displacement impurity atoms. It is more difficult to form the substitutional impurity atom than to form the interstitial impurity atom.

Determination of Drying Characteristics, Energy Consumption and Quality Values of Black Mulberry Fruit (Morus nigra L.) Dried Under Different Conditions

There are about 68 types of mulberry fruit with a wide ecological production area. Different mulberry species are grown in large fields in Turkey. Mulberries are largely dried-consumed, but sometimes they are used as fruit juice. In this study, black mulberry fruit was collected in two different ripening levels (semi-ripe and full-ripe) and oven-dried at 50, 60 and 70°C drying temperatures. Initial moisture contents of semi-ripe and full-ripe fruits were determined as 86.74% and 82.95%, respectively. Fruits were dried to have final moisture levels of 10-15%. Drying duration, drying models, effective diffusion, activation energy, specific energy consumption, color parameters and chemical properties of dried fruits were examined and the effect of ripening levels and drying temperatures were investigated. In terms of drying duration, while full-ripe fruits dried in a shorter time, effective diffusion, activation energy and specific energy consumption values were found to be higher than semi-ripe fruits. In terms of color parameters, semi-ripe fruits are recommended to be dried at 50 or 60°C drying temperatures and full-ripe fruits should be dried at 50°C drying temperature for better preservation of color parameters. On the other hand, a common proper drying temperature could not be identified for acidity (pH), water soluble dry matter and titratable acidity.

Water vapor transmission properties of acrylic organic coatings

In this work, we evaluate the water vapor transmission rate (WVTR), the permeability (P), solubility (S), and diffusion (D) coefficients of Paraloid B44, Paraloid B72, and Incralac coatings in the temperature range of 5–35°C. The Arrhenius function—diffusion activation energy and preexponential factor—has also been determined from the data: $$D_{B44} = 35.2\;{\text{cm}}^{2} \;{\text{s}}^{ - 1} \exp \left( { - 25\;{\text{kJ mol}}^{ - 1} /{\text{RT}}} \right)$$ D B 44 = 35.2 cm 2 s - 1 exp - 25 kJ mol - 1 / RT ; $$D_{B72} = 9.5\;{\text{cm}}^{2} \;{\text{s}}^{ - 1} \exp \left( { - 23\;{\text{kJ mol}}^{ - 1} /{\text{RT}}} \right)$$ D B 72 = 9.5 cm 2 s - 1 exp - 23 kJ mol - 1 / RT ; $$D_{\text{Incralac}} = 622.8\;{\text{cm}}^{2} \;{\text{s}}^{ - 1} { \exp }\left( { - 28\;{\text{kJ mol}}^{ - 1} /{\text{RT}}} \right)$$ D Incralac = 622.8 cm 2 s - 1 exp - 28 kJ mol - 1 / RT . These resins are important coating materials, for example, for conservators to protect metallic artifacts, such as statues, against corrosion. Despite Paraloid B44 and B72 resins being considered as reference materials in conservation practice, that is, new coating materials (either water vapor retarders or transmitters) are often compared to them, there are no comprehensive data for the quantities describing the vapor permeability (P, S, D) of these materials. The measurements are based on the ISO cup-method using substrate/coating composite samples. The strength of this technique is that it can also be used when the coating is non-self-supporting; nevertheless, P, S, and D can be deduced for the coating layer itself, and it seems to be a standardizable procedure for comparative performance testing of coating materials. Paraloid B72 layers exhibited higher WVTRs—from 39 to 315 g m−2 day−1 as the temperature increased from 5 to 35°C—compared to Paraloid B44 and Incralac coatings—from 17 to 190 g m−2 day−1, respectively. The transmission rate parameters were also compared to the results of corrosion tests. Incralac was the most effective corrosion inhibitor, and the performance of the B44 was better than the B72, which is in good agreement with the transmission rate tests.

An investigation on thermodynamics and kinetics of η phase formation in Nb-modified iron-nickel base A286 superalloy

In this study, precipitation of η phase (Ni3Ti) in conventional and Nb-modified (Nb-A286) A286 superalloys was evaluated at different aging times and temperatures. The TTP curve of the η phase formation was plotted using thermodynamic analyses, kinetics and microstructural studies. Depending on temperature and heat treatment, the η phase precipitated at the grain boundaries or twin sites, as a result of the γ′ phase or matrix austenite transformation. Heat treatment of conventional A286 superalloy and Nb-A286 was performed within a temperature range of 650 to 900 °C for 2 to 30 h. The η phase transformation was evaluated by scanning electron microscope (SEM) which is equipped to energy dispersive X-ray spectroscopy (EDS) and optical microscopy (OM). In the analyses based on thermodynamic calculations, the interaction of the Gibbs free energy of η phase formation and the diffusion activation energy of the elements, especially titanium and niobium, was considered. The microstructural studies showed that increasing the heat treatment time results in increasing the volume fraction of the η phase. By increasing the aging temperature to 840 and 860 °C for conventional A286 superalloy and Nb-A286 superalloy, respectively, the η phase volume fraction increased, however, further increase led to volume fraction decrease. The results of the thermodynamic analyses showed the tip of the TTP diagrams at temperatures of 860 and 820 °C for the A286 and Nb-A286 alloys, respectively. Investigation of kinetics calculations showed that η phase transformation depends on the diffusion of titanium, nickel, and niobium.