A Finite Difference Method for Determining Interdiffusivity of Aluminide Coating Formed on Superalloy

A numerical method has been developed to extract the composition-dependent interdiffusivity from the concentration profiles in the aluminide coating prepared by pack cementation. The procedure is based on the classic finite difference method (FDM). In order to simplify the model, effect of some alloying elements on interdiffusivity can be negligible. Calculated results indicate the interdiffusivity in aluminide coating strongly depends on the composition and give the formulas used to calculate interdiffusivity at 850, 950 and 1050癈. The effect on interdiffusivity is briefly discussed.

RELATION BETWEEN EFFECTIVE INTERDIFFUSIVITY AND MODULATION WAVELENGTH IN Fe-Ti MULTILAYERS

One-dimensional artificial scattering planes can form in the direction perpendicular to the surface of the films when the compositional modulation period is shorter. Similar to real crystal lattice planes, these artificial scattering planes produce Bragg diffraction with X-ray radiation. Since the modulation period is longer than the general lattice period, the Bragg diffraction peak appears at the position of lower angle (2θ is generally lower than 10°). The diffraction peaks produced by compositional modulation are called modulation peaks.

Interdiffusion behavior between Cr and Zr and its effect on the microcracking behavior in the Cr-coated Zr-4 alloy

High-temperature chromium(Cr)-zirconium(Zr)interdiffusion commonly occurs in Cr-coated zircaloys applied for enhanced accident-tolerant fuel(ATF)claddings.Such interdiffusion changes the interfacial microstructure and thus the fracture mechanism of the coating under external loading.In this study,the interdiffusion behavior in a magnetron sputtered Cr coating deposited on a Zr-4 alloy was studied in a vacuum environment at 1160C.In addition,the effect of interdiffusion on the microcracking behavior of the Cr coating was determined by in situ three-point bending tests.The experimental results show that the interdiffusion behavior resulted in the formation of a ZrCr2 layer,accompanied by the consumption of Cr coating and interfacial roughening.The growth of the diffusion layer followed a nearly parabolic law with respect to annealing time,and the residual stress of the annealed coating decreased with increasing annealing time.Under external loading,a large number of cracks were generated in the brittle interlayer,and some interfacial cracks were formed and grew at the ZrCr2/Zr-4 interface.Despite the remarkable microcracks in the ZrCr2 layer,the vacuum-annealed Cr coating has significantly fewer cracks than the original coating,mainly because of the recrystallization of the coating during annealing.

Oxidation and interdiffusion behavior of a germanium-modified silicide coating on an Nb–Si-based alloy

To investigate the interdiffusion behavior of Ge-modified silicide coatings on an Nb–Si-based alloy substrate,the coating was oxidized at 1250°C for 5,10,20,50,or 100 h.The interfacial diffusion between the(Nb,X)(Si,Ge)_2(X = Ti,Cr,Hf) coating and the Nb–Si based alloy was also examined.The transitional layer is composed of(Ti,Nb)_5(Si,Ge)_4 and a small amount of(Nb,X)_5(Si,Ge)_3.With increasing oxidation time,the thickness of the transitional layer increases because of the diffusion of Si from the outer layer to the substrate,which obeys a parabolic rate law.The parabolic growth rate constant of the transitional layer under oxidation conditions is 2.018 μm×h^(-1/2).Moreover,the interdiffusion coefficients of Si in the transitional layer were determined from the interdiffusion fluxes calculated directly from experimental concentration profiles.

Improvement on the Oxidation Resistance of a Ti_3Al Based Alloy by Cr1-xAl_xN (0≤x≤0.47) Coatings

Cr1-xAlxN coatings have been deposited on a Ti3Al based alloy by reactive sputtering method. The results of the isothermal oxidation test at 800-900℃ showed that Cr1-xAlxN coatings could remarkably reduce the oxidation rate of the alloy owing to the formation of Al2O3＋Cr2O3 mixture oxide scale on the surface of the coatings. No spallation of the coatings or oxide scales took place during the cyclic oxidation at 800℃. Ti was observed to diffuse into the coatings, the diffusion distance of which was very short, and the diffusion ability of it was proportional to the AI content in the coatings. Compared to Ti, Nb can diffuse much more easily through the whole coatings and oxide scales.

Study on interface between titanium-coated diamond and metal matrices

The XRD spectrum of titanium coated diamond showed the existence of titanium ca rbide on the interface between diamond and its titanium coating. The diffusions between titanium coating and metal matrices were stud ied by SEM. The SEM photographs revealed that titanium can interdiffuse with nic kel, cobalt, copper,iron and copper based alloy to a great extent to lead to th e disappearance of pure titanium layer and the formation of titanium diffusion l ayer. The results from transverse rupture strength test showed that ti tanium coating on diamond improved the bonding strength between diamond and metal matrices by 3.2% for Co based segment and 4.1% for Cu 10Sn based segment respectively.

Interdiffusion in the Fe_2O_3-TiO_2 system

Interdiffusion in the Fe203-TiO2 system was investigated by the diffusion couple method in the temperature range of 1323 to 1473 K. The diffusion concentration curves of Ti4＋ cations were obtained by electron probe microanalysis, according to which the Boltzmann-Matano method optimized by Broeder was used to calculate the interdiffusion coeffi- cients. The interdiffusion coefficients almost increased linearly with the mole fraction of Ti4＋ cations increasing, and they were in the range of 10-12-10-11cm2-s-1. The increase of temperature could also lead to the increase of the interdiffusion coefficients at a constant concentration of Ti4＋ cations. It was also found that the thickness growth of the diffusion layer obeyed the parabolic rate law.

Effect of Substrate Characteristics on Interdiffusion Coefficients of Ni and Al Atoms in β-NiAl Phase of Aluminide Coatings

Interdiffusion coefficients at 950℃ and 1050℃ are calculated by Wagner analysis method as a function of composition of β-NiAI phase. The β-NiAI phase is formed by pack cementation on surface of superalloy. Results of the calculation show that interdiffusion coefficients in β-NiAI phase strongly depend on the compositions and vary over several orders of magnitude. Compared with the interdiffusion coefficients in the stoichiometric β-NiAI phase, the interdiffusion coefficients in β-NiAI phase formed on superalloy is obviously small, probably due to the composition, complicated microstructure and precipitates. However, it could be seen clearly that the shapes of the diffusivity curves are very similar to each other. The similarity of the diffusion curves and the difference between interdiffusion coefficients imply that the compositions, microstructures and precipitates of superalloy have a distinctly adverse effect on the interdiffusion of Ni and Al atoms during aluminization, but do not change the essential characteristics of β-NiAI phase.

Behavior of NiCrAlY coating on the TC6 titanium alloy

A NiCrAlY coating was deposited on the TC6 titanium substrate by arc ion plating （ALP）. The structure and morphologies of the NiCrAlY coating were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）, and the influence of vacuum heat treatment on the element diffusion behavior was studied. The results showed that the y＇-Ni3Al phase was precipitated on the NiCrAlY coating after heat treatment. The Ni3（AI,Ti）, TiNi, and Ti2Ni intermetallic layers appeared at the interface from the outside to the inside at 700℃, and the thickness of the intermetallic layers increased with the increase in temperature. At 700℃ Ti and Ni were the major diffusion elements, and the diffusion of Cr was observed when the heat treatment temperature increased up to 870℃. The violent inward diffusion of Ni at 950℃ resulted in the degradation of the NiCrAlY coating.

Interfacial characteristics and properties of a low-clad-ratio AA4045/AA3003 cladding billet fabricated by semi-continuous casting

A low-clad-ratio AA4045/AA3003 cladding billet was fabricated using a semi-continuous casting process and was subsequently extruded indirectly into a cladding pipe. The temperature distribution near the interface was measured. The microstructures, elemental distribution, Vickers hardness around the bonding interface, and the interfacial shear strength were examined. The results showed that the interface temperature rebounded when AA4045 melt contacted the supporting layer. The two alloys bonded well, with few defects, via the diffusion of Si and Mn in the temperature range from 569℃ to 632℃. The mean shear strength of the bonding interface was 82.3 MPa, which was greater than that of AA3003（75.8 MPa）, indicating that the two alloys bonded with each other metallurgically via elemental interdiffusion. Moreover, no relative slip occurred between the two alloys during the extrusion process.

A repeated interdiffusion method for efficient planar formamidinium perovskite solar cells

A repeated interdiffusion method is described for phase-stable and high-quality （FA,MA）PbI3 film. The crys- tallization and growth of the perovskite films can be well controlled by adjusting the reactant concentrations. With this method, dense, smooth perovskite films with large crystals have been obtained. Finally, a PCE of 16.5% as well as a steady-state efficiency of 16.3% is achieved in the planar perovskite solar cell.

Phase-field simulation of the effect of interaction among ordered domains on interdiffusion in Ni-Al-Cr alloys

The effect of interaction among γ′ ordered domains on the interdiffusion process in γ＋γ′ and γ＋γ′/γ＋γ′ diffusion couples is investigated by using the phase-field method, in which bulk free energy and mobility are linked with thermodynamic and kinetic databases. Simulated results show that the interaction among γ′ ordered domains has great influence on the microstructure, the interdiffnsion velocity and the volume fraction ofγ′ phase on both sides of the diffusion couples.

Study on Al_xNi_y Alloys as Diffusion Barriers in Flexible Thin Film Solar Cells

Co-sputtered AlxNiy thin films were used as diffusion barriers between aluminum and hydrogenated microcrystalline silicon （μc-Si：H） for flexible thin film solar cells. The stoichiometric ratio of AlxNiy showed a significant effect on the structures of the films. The obtained Al3Ni2 film was amorphous, while polycrystalline films were obtained when the ratio of aluminum to nickel was 1：1 and 2：3. An auger electron spectroscope and four-point probe system were applied to test the resistance to the interdiffusion between aluminum and silicon, as well as the conductivities of the AlxNiy barriers. The data of auger depth profile showed that the content of silicon was the minimum in the aluminum layer after sputtering for 4 min using AlNi thin film as the barrier layer. Compared to other AlxNiy alloys, the AlNi thin film possessed the lowest sheet resistance.

Unraveling transition-metal-mediated stability of spinel oxide via in situ neutron scattering

The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal(TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM-O bonds, lattice,TM valence and the migration of the high-voltage spinel cathode LiNi_(0.5)Mn_(1.5)O_(4). The transition-metalmediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed.The formation of Mn^(3+) is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn^(3+) reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.

Fundamental Concept of Interdiffusion Problems

In accordance with the definition of diffusivity, the origin of coordinate system of the original diffusion equation is set at a point in the solvent material. Kirkendall revealed that Cu atoms, Zn atoms and vacancies move simultaneously in the interdiffusion region. This indicates that the original diffusion equation is a moving coordinate system for the experimentation system outside the diffusion region. The diffusion region space which means vacancies and interstices among atoms plays an important role in the diffusion phenomena. The theoretical equation of the Kirkendall effect is reasonably obtained as a shift between coordinate systems of the diffusion equation. The situation is similar to the well-known Doppler effect in the wave equation. Boltzmann transformed the original diffusion equation of a binary system into the nonlinear ordinary differential equation in accordance with the parabolic law. In the previous works, the solutions of the diffusion equation transformed by Boltzmann were analytically obtained and we found that the well-known Darken equation is mathematically wrong. In the present study, we found that the so-called intrinsic diffusivity corresponds in appearance to the physical solution obtained previously. However, the intrinsic diffusivity itself conceived in the diffusion research history is essentially nonexistent.

New Analytical Method of Interdiffusion Problems

The nonlinear diffusion equation for a binary system interdiffusion was analytically solved in the previous work. The theoretical relation of Kirkendall effect was also derived in the previous work. These new results have not yet been concretely applied to actual diffusion problems. In the present work, it is revealed that the previous results reproduce the experimental concentration profile by taking account of the movement of diffusion region space. It is thus actually confirmed that any problems of binary system interdiffusion can be solved by the new analytical method if even diffusivities of self-diffusion and impurity diffusion in the materials concerned are given. The method for solving interdiffusion problems of many elements system, which is extremely important for the development of new useful materials, is also reasonably discussed. Further, it is revealed that the concept of intrinsic diffusion is unsuitable for the diffusion theory. The fundamental theory of diffusion discussed here will be useful for analyzing actual diffusion problems in future.

Fe-Mn interdiffusion in aluminosilicate garnets

Precise determination of cation diffusivity in garnet can provide critical information for quantitatively understanding the timescales and thermodynamics of various geological processes,but very few studies have been performed for Fe-Mn interdiffusion.In this study,Fe-Mn interdiffusion rates in natural single crystals of Mn-bearing garnet with 750 ppm H2O are determined at 6 GPa and 1273-1573 K in a Kawai-type multi-anvil apparatus.Diffusion profiles were acquired by electron microprobe and fitted using Boltzmann-Matano equation.The experimental results show that the Fe-Mn interdiffusion coefficient(DFe-Mn)slightly decreases with increasing XFe.The experimentally determined DFe-Mn in Mn-bearing garnet can be fitted by the Arrhenius equation:DFe-Mn(m2/s)=D0XFenexp(-E*/RT),where E*=(1-XFe)E*Mn+XFeE*Fe,D0=8.06-6.04+9.87×10-9 m2/s,E*Mn=248±27 KJ/mol,E*Fe=226±59 KJ/mol,n=-1.36±0.51.The comparing the present results with previous experimental data suggest that water can greatly enhance the DFe-Mn in garnet.Our results indicate that the time required for homogenization of the compositional zoning of a garnet is much shorter than previously thought.

Perovskite films with gradient bandgap for self-powered multiband photodetectors and spectrometers

Bandgap-graded materials present varying spectral responses at different positions,making them possible to be used as an alternative to photoactive materials array in multi-spectral responsive devices,thus miniaturizing the apparatus.However,the preparation of bandgap-graded materials usually requires complicated deposition process.Here we report a facile lowtemperature solution process to make films with lateral bandgap gradients,which form spontaneously via self-spreading and interdiffusion of solutions.We show lead halide perovskite films with MAPbCl_(3)-MAPbBr_(3)and MAPbBr_(3)-MAPbI_(3)gradients,which exhibit light absorption onsets ranging from 410 to 781 nm.The bandgap-graded films were used to make self-powered multiband photodetectors,which show different spectral responses at different positions without applying bias voltage.Furthermore,self-powered spectrometers were made by using the multiband photodetectors.

Triggering heteroatomic interdiffusion in one-pot-oxidation synthesized NiO/CuFeO_(2) heterojunction photocathodes for efficient solar hydrogen production from water splitting

Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limit its PEC activity for water reduction.Here,we developed a heterostructure photocathode consisting of the Cu-doped NiO(Cu:NiO)hole selective layer(HSL)and Ni-doped CuFeO_(2)(Ni:CuFeO_(2))active layer by simply annealing a homogeneous Cu-Fe oxalate layer grown on the Ni film deposited on the fluorine doped tin oxide(FTO)substrate.The obtained heterostructure of Cu:NiO/Ni:CuFeO_(2) with enhanced charge carrier transportability and high-quality interface greatly promotes the separation of photogenerated carriers.Accordingly,the Cu:NiO/Ni:CuFeO_(2) photocathode exhibits a high photocurrent density of~0.9 mA·cm^(-2 )at 0.2 V(vs.reversible hydrogen electrode,RHE),outperforming most of the reported bare CuFeO_(2) photocathodes in the literature.And the photocurrent density can be further improved to 1.2 mA·cm^(-2) after decorating NiSx cocatalyst.

Microstructure evolution and diffusion mechanism of Nb/TiAl alloy diffusion-bonded joints

The interdiffusion behavior in Nb/TiAl alloy diffusion couples was studied.The process was carried out in the temperature range of 950-1400℃for 8 h in the vacuum hot-pressure sintering furnace.The microstructural evolution was observed by optical microscopy(OM),electron backscattered diffraction(EBSD),X-ray diffraction(XRD)technique and transmission electron microscopy(TEM).The element concentration distribution at the bonded interface was obtained by scanning electron microscopy with an energy-dispersive X-ray spectroscopy(EDS)apparatus.The thickness of reaction interface increases with bonding temperature increasing.The formed phases in diffusion interface are found to be O-Ti_(2)AlNb,σ-Nb_(2)Al,δ-Nb_(3)Al and Nb solid solution(Nbss)at 1350℃.The average interdiffusion coefficient of the interface elements was calculated by the theory of Dayananda.The results indicate that Al diffuses faster than Nb and Nb diffuses faster than Ti in the Ti-Al-Nb system.Meanwhile,it is found that Ti promotes the diffusion of Al and Nb and Nb inhibits the diffusion of Ti and Al in the process of diffusion.