Coherency Strain-Assisted Equilibrium Segregation at Heterophase Interfaces

Theoretical work in the field of interfacial segregation is focused mainly on the sharp interface approach beginning with the Gibbs' introduction of the dividing surface. In this paper a continuum approach to the problem of interfacial segregation, which deals with continuous distributions of quantities at interfaces, is developed. The current study concentrates on heterophase interfaces in alloys as opposed to grain boundaries or antiphase domain boundaries. The important effect of coherency strains is taken into account. The Gibbs adsorption theorem is discussed in the framework of a continuum approach. A comparison is made between the sharp (Gibbsian) and diffuse interface approaches.     

Analysis of Gibbsian Segregation at Heterophase Cu-MnO Interfaces

An alternative methodology to analyze Gibbsian segregation at heterophase interfaces with transmission electron microscopy (TEM) is presented and discussed. In this approach the actual concentration of the segregating element in a monolayer at the interface is obtained. This is in contrast to line scans or maps where the concentrations determined are a convolution of the concentration profiles with the electron probe and where for general interfaces the deconvolution problem can not be solved accurately. This is possible because the present approach uses explicitly the information offered by hetero-interfaces. The method is tested on the possible segregation of indium and gallium dissolved in a Cu matrix to interfaces between MnO precipitates and the Cu matrix. The occurrence of indium segregation is clearly demonstrated and the In concentration in the terminating Cu monolayer at the parallel {111} Cu/MnO interface is determined to be 15 ± 3 at.%, whereas the average In concentration in the Cu matrix is 3.8 ± 0.4 at.%. Further it was found that indium effectively blocks gallium segregation towards the oxide side of the interface. On the other hand, the presence of gallium does not influence the segregation of indium. Explanation for the gallium segregation at the oxide side relies on a thin spinel type Ga _x Mn _y O₄, which reduces the misfit at the metal-oxide interface.     

Segregation of Aluminium at Nickel-Sapphire Interfaces

Sessile drop experiments of pure liquid Ni on the basal surface of pure sapphire were conducted under controlled atmosphere and temperature. This system has been traditionally considered as non-reactive, based on thermodynamic assessments. However, the results of this study demonstrate that a capillary driven interaction exists between the pure liquid Ni and the sapphire, which causes the dissolution of the sapphire substrate mainly at the triple junction. Oxygen and Al resulting from the dissolution process diffuse into Ni and segregate at its interfaces with the atmosphere and the sapphire (probably as Al _x O _y clusters), which reduces the interface energy. It is considered that this reduction is beneficial for the adhesion of both liquid and solid Ni on sapphire. The amount of Al introduced into the drop, and hence the segregation of Al that affects the interface energy (and adhesion), are related to the size of the sessile drop.     

A Subnanoscale Investigation of Sb Segregation at MnO/Ag Ceramic/Metal Interfaces

We have studied Sb segregation at MnO/Ag(Sb) ceramic/metal heterophase interfaces employing three-dimensional atom-probe (3DAP) microscopy. Specimens are prepared by the internal oxidation of Ag(Mn) alloys, leading to the formation of nanometer-size MnO precipitates within a Ag(Mn) matrix. Sb is introduced into the internally oxidized specimens with a vapor diffusion treatment. Appreciable Sb segregation is observed only after a subsequent segregation anneal is performed, and the measured interfacial excess of Sb at the MnO/Ag(Sb) interfaces, _Sb ^MnO/Ag, is determined directly. The temporal evolution of the MnO precipitates is followed for the different processing steps employed. It is shown that the concentration of silver within the MnO precipitates decreases from an initial value of 45–50 at.% Ag to less than 5 at.% Ag with increasing annealing time at the different processing temperatures. Thus the MnO precipitates form under paraequilibrium conditions and the precipitates inherit Ag from the matrix. With increasing aging time orthoequilibrium conditions prevail and the MnO precipitates reject the silver atoms they inherited from the matrix.     

Segregation of Oxygen at Metal/Oxide-Interfaces

By internal oxidation of AgMg- and PdMg-alloys small precipitates ofMgO are formed within the Ag- or Pd-matrix. Thetotal area of the metal/oxide interface produced this way becomes severalsquare meters in one cubic centimeter of metal. Segregation of oxygen at theinterface is determined by desorption of gaseous oxygen for theAg/MgO-interface and by trapping of hydrogen for the Pd/MgO-interface. At673 to 873 K the oxygen coverage of the Ag/MgO boundary does not obey aLangmuir-McLean relation. At the highest oxygen pressure of10⁵ Pa O-coverage reached a maximum value of about2.2·10¹⁴ O-atoms/cm². The average freeenthalpy of segregation is about -70 kJ/mol O. The results are interpretedin terms of a structural model, where the interface contains vacancies inthe terminating oxygen (111)-plane of MgO. Segregation, i.e., filling of thevacancies with oxygen from solid solution, leads to the formation of a twodimensional silver oxide. For Pd/MgO condition were less favorable andoxygen segregation can be determined indirectly by irreversible hydrogentrapping. Oxygen segregation does not occur if the sample is rapidlyquenched from 1273 K by drooping it into liquid nitrogen. In order tounderstand the kinetics of segregation, the diffusion coefficient of oxygenwas determined in Pd by measuring solubility and permeability. Measuredvalues can be described by the following relationD = 2.3;10 ^-3 exp[-12,300/T] cm²/s.     

Monte Carlo Simulation of the Concentration Dependence of Segregation at Vicinal Grain Boundaries

Using the Metropolis algorithm Monte Carlo technique solute-atom segregation is studied at two vicinal grain boundaries (GBs)—the = 5/(002)/ = 36.89° symmetrical twist and the = 5/(310)/ = 53.13° symmetrical tilt—at 850 K on the Ni-rich side of the Ni-Pt phase diagram, over the concentration range 0–10 at.% Pt. Unlike the Pt-rich side of the phase diagram the structures of both GBs remain stable in this concentration range. The dilute limit behavior for most GB sites extends to at least 0.1 at. %. At higher concentrations the effective segregation energies steadily decrease with increasing solute concentrations, due to solute-solute interactions between segregated atoms, until saturation occurs. It is argued that simple statistical mechanical models, e.g., the Fowler-Guggenheim model do not work well, even in the case of simple vicinal GBs.     

Segregation at the surface of an Au/Pd alloy exposed to CO

We use density functional theory (DFT) with the generalized gradient approximation (GGA) and the revised Perdew-Burke-Ernzerhoff (rPBE) functional, to study the surface composition of the (1 1 1) and (1 0 0) dilute Pd/Au alloy. We find that the energy of Pd atoms is lower when they substitute an Au atom in the bulk than when they substitute an Au atom in the surface layer, or when they are adsorbed on the surface. Whether they are in the surface layer or in the bulk, the Pd atoms interact very weakly with each other. CO adsorbs on the Pd atom in the surface layer and the energy of this complex is lower than that of CO in gas and Pd atom in the bulk. The interaction between the PdCO complexes formed when CO adsorbs on a Pd atom imbedded in the surface layer, is also negligible. We use these energies, equilibrium thermodynamics, and a simple lattice-gas model to examine the equilibrium composition of the surface layer, as a function of temperature, CO pressure and the Pd/Au ratio. We find that the surface Pd concentration for a nanoparticle of an Au/Pd alloy differs from that in a bulk sample. The difference is due mainly to the fact that in a nanoparticle the migration of Pd atoms to the surface depletes the bulk concentration while in a large sample; the bulk provides an infinite source of Pd atoms to populate the surface sites. This system is of interest because Pd/Au alloys are selective catalysts for vinyl acetate synthesis when the Pd concentration on the surface is very low.     

金属-砷化镓界面的电调制反射光谱与Franz-Keldysh效应研究

通过调制光谱这种基础的光学方法来研究Au-GaAs,Al-GaAs,Ni-GaAs的金属半导体界面的一些电学性质,并且加以比较,其中包括电场、费米能级扎钉和界面态密度等情况。这些界面是通过在SIN+ GaAs样品上沉积金属(Au,Al,Ni)生长成的。通过观察电反射谱来研究金属GaAs的界面电场和费米能级扎钉的情况,然后通过傅里叶变换这些所取得的电反射谱来分析这些材料的界面性质。通过测量氦氖激光器诱导产生的光电压和激光器光强之间的关系来得到这些材料的界面态密度情况,从而进行进一步的研究。     

B对Mo等元素在奥氏体钢/Cr2O3界面占位倾向影响的理论研究

超级奥氏体不锈钢中因含有更高铬、钼含量,具有极高的耐点蚀、晶间腐蚀性能,这与Mo等合金元素对钝化膜结构的影响密切相关,尤其含硼超奥钢钝化层表面Cr、Mo含量明显增加,但其原子层次的微观作用机制尚不清楚.本文采用第一性原理方法,研究了置换原子(Mo、Mn、Ni、Si),及间隙原子B在fcc-Fe/Cr₂O₃界面占位倾向,并分析了可稳定存在于界面B对这些元素偏析倾向的影响.结果表明:Mo、Mn、Ni、Si、B均可与fcc-Fe/Cr₂O₃界面结构体系形成稳定结构;Mo、Ni倾向分布于界面基体侧,Mo有向氧化层扩散的趋势,B处于fcc-Fe/Cr₂O₃界面基体侧更稳定,Mn、Si易分布于氧化层中;存在于界面B对四种元素在fcc-Fe/Cr₂O₃界面体系中的占位影响不同,有利于Mn、Mo偏析于界面基体侧,但抑制Mo向界面基体侧的偏析程度,使得Si、Ni更均匀的分布于基体. Mo等合金元素分布于界面时的态密度来看,界面处M...     

Segregation of silicone acrylate from acrylate mixture at resin-mold interface and its effect on UV embossing

When silicone diacrylate was added in small amount (<5 wt.%) to ultraviolet (UV) curable formulations containing other oligomeric diacrylates, there was segregation of the silicone additive at the solid substrate-formulation interface. The amount was quantified by X-ray photoelectron spectroscopy measurement of the UV cured film surface composition. The effect of silicone diacrylate concentration, resin formulation and substrate polarity on silicone surface excess was systematically studied. Young's-Gibbs adsorption theory was applied to the prediction of the silicone surface excess at the solid substrate interface for these oligomeric mixtures. Further, we proposed a simplified Young's-Gibbs adsorption theory equation to predict the variation of surface excess from only formulation surface tension and substrate critical surface tension. The selective segregation is beneficial to demolding in UV embossing since only small amount of release added can result in large decrease of the mold-resin interfacial energy difference leading to easy demolding and high replication fidelity.     

Structure and magnetism of Ni/Ti multilayers on annealing

Neutron reflectometry study has been carried out in unpolarized (NR) and polarized (PNR) mode to understand the structure and magnetic properties of alloy formation at the interfaces of Ni/Ti multilayers on annealing. The PNR data from annealed sample shows a noticeable change with respect to the as-deposited sample. These changes are: a prominent shift of the multilayer Bragg peak to a higher angle and a decrease in the intensity of the Bragg peak. The PNR data from annealed sample revealed the formation of magnetically dead alloy layers at the interfaces. Changes in roughness parameters of the interfaces on annealing were also observed in the PNR data.      

基于第一性原理的Si/SiC、Al/SiC界面成键特性和结合强度对比研究

采用半固态搅拌铸造法制备Al Si7-Si C复合材料,并利用真空压铸工艺实现了其近净成形,结合第一性原理计算方法研究了共晶Si对Si C颗粒和基体界面结合强度的影响.结果显示,在Al Si7-Si C复合材料中,发现较为严重的共晶Si偏析现象,当Si C颗粒同时处于共晶Si和α-Al边界时,形成了少量的共晶Si夹杂、被大量共晶Si包裹、完全被共晶Si包裹三种典型的界面.第一性原理计算结果显示,在C端和Si端的Si/Si C界面中,弛豫后top Si¹配位方式具有最大的粘附功,与Al/Si C界面相比,Si/Si C界面具有更高的结合强度.Si偏析相提高了界面处的电荷密度,因而具有更好的界面结构稳定性.     

Influence of the Interfaces on Magnetic Properties of Fe/Ag and Fe/Cu Multilayers Prepared by Sputtering

Hyperfine Interactions - Dependence of magnetic behavior of ultrathin Fe layers on the width of the interfaces was investigated by using dc-magnetron sputtering to grow (Fe(110)/Ag(111))...     

Segregation of alloying atoms at a tilt symmetric grain boundary in tungsten and their strengthening and embrittling effects

We investigate the segregation behavior of alloying atoms （Sr, Th, In, Cd, Ag, Sc, Au, Zn, Cu, Mn, Cr, and Ti） near Z3 （ 111 ） [1]-0] tilt symmetric grain boundary （GB） in tungsten and their effects on the intergranular embrittlement by performing first-principles calculations. The calculated segregation energies suggest that Ag, Au, Cd, In, Sc, Sr, Th, and Ti prefer to occupy the site in the mirror plane of the GB, while Cu, Cr, Mn, and Zn intend to locate at the first layer nearby the GB core. The calculated strengthening energies predict Sr, Th, In, Cd, Ag, Sc, Au, Ti, and Zn act as embrittlers while Cu, Cr, and Mn act as cohesion enhancers. The correlation of the alloying atom＇s metal radius with strengthening energy is strong enough to predict the strengthening and embrittling behavior of alloying atoms; that is, the alloying atom with larger metal radius than W acts as an embrittler and the one with smaller metal radius acts as a cohesion enhancer.     

Structural and Thermodynamic Peculiarities of Core-Shell Particles at Fluid Interfaces from Triangular Lattice Models

A triangular lattice model for pattern formation by core-shell particles at fluid interfaces is introduced and studied for the particle to core diameter ratio equal to 3. Repulsion for overlapping shells and attraction at larger distances due to capillary forces are assumed. Ground states and thermodynamic properties are determined analytically and by Monte Carlo simulations for soft outer- and stiffer inner shells, with different decay rates of the interparticle repulsion. We find that thermodynamic properties are qualitatively the same for slow and for fast decay of the repulsive potential, but the ordered phases are stable for temperature ranges, depending strongly on the shape of the repulsive potential. More importantly, there are two types of patterns formed for fixed chemical potential—one for a slow and another one for a fast decay of the repulsion at small distances. In the first case, two different patterns—for example clusters or stripes—occur with the same probability for some range of the chemical potential. For a fixed concentration, an interface is formed between two ordered phases with the closest concentration, and the surface tension takes the same value for all stable interfaces. In the case of degeneracy, a stable interface cannot be formed for one out of four combinations of the coexisting phases, because of a larger surface tension. Our results show that by tuning the architecture of a thick polymeric shell, many different patterns can be obtained for a sufficiently low temperature.     

Segregation of Pt at clean surfaces of (Pt, Ni)3Al

Experimental evidence for surface segregation of Pt at (1 1 1) surfaces of ternary (Pt, Ni)₃Al alloys is presented, based upon Auger electron spectroscopy, low energy ion scattering, and angle-resolved X-ray photoelectron spectroscopy. Density functional calculations in the dilute limit confirm that Pt segregation is energetically favored.     

Bonding at Compatible and Incompatible Amorphous Interfaces of Polystyrene and Poly(Methyl Methacrylate) Below the Glass Transition Temperature

Abstract

Films of high‐molecular‐weight amorphous polystyrene (PS, M _w = 225 kg/mol, M _w/M _n = 3, T _g‐bulk = 97°C, where T _g‐bulk is the glass transition temperature of the bulk sample) and poly(methyl methacrylate) (PMMA, M _w = 87 kg/mol, M _w/M _n = 2, T _g‐bulk = 109°C) were brought into contact in a lap‐shear joint geometry at a constant healing temperature T _h, between 44°C and 114°C, for 1 or 24 hr and submitted to tensile loading on an Instron tester at ambient temperature. The development of the lap‐shear strength σ at an incompatible PS–PMMA interface has been followed in regard to those at compatible PS–PS and PMMA–PMMA interfaces. The values of strength for the incompatible PS–PMMA and compatible PMMA–PMMA interfaces were found to be close, both being smaller by a factor of 2 to 3 than the values of σ for the PS–PS interface developed after healing at the same conditions. This observation suggests that the development of the interfacial structure at the PS–PMMA interface is controlled by the slow component, i.e., PMMA. Bonding at the three interfaces investigated was mechanically detected after healing for 24 hr at T _h = 44°C, i.e., well below T _g‐bulks of PS and PMMA, with the observation of very close values of the lap‐shear strength for the three interfaces considered, 0.11–0.13 MPa. This result indicates that the incompatibility between the chain segments of PS and PMMA plays a negligible negative role in the interfacial bonding well below T _g‐bulk.     

Correlation of grain boundary extra free volume with vacancy and solute segregation at grain boundaries: a case study for Al

Grain boundary extra free volume (GB EFV) can be considered as fundamental microstructural parameter for polycrystalline or nano-crystalline materials. Here, we present a systematic first principles study on a group of representative symmetric tilt grain boundaries of Al with various EFVs subjected to vacancy formation and Mg segregation. All grain boundaries were constructed using the coincident site lattice (CSL) and the structural unit (SU) models. It was found that the SU model is superior to the CSL in describing FCC-Al GBs, the same as we previously revealed for BCC-Fe. The predicted relation between GB misorientation angle and EFV, and the predicted EFV criteria for a stable GB, both agree with available experimental observations. Vacancy formation and Mg segregation show stronger preference to those GBs with high EFV values, due to the resultant high levels of atomic disorder. These findings not only provide a new, atomistic perspective on the significance of EFV, but also suggest a viable means of predicting GB properties based on direct experimental characterisation of GB EFVs.     

Structure, magnetism, and adhesion at Cr/Fe interfaces from density functional theory

Properties of the Cr(1 0 0)/Fe(1 0 0) and Cr(1 1 0)/Fe(1 1 0) interfaces are investigated with spin-polarized density functional theory within the generalized gradient approximation (DFT-GGA) for electron exchange and correlation. Contrary to earlier predictions for a monolayer of Cr on bulk Fe, we find intermixing of Cr and Fe at the interface of thick films to be endothermic; hence here we focus on characterizing abrupt, unalloyed interfaces. The ideal work of adhesion for both the (1 0 0) and (1 1 0) abrupt interfaces is predicted to be ∼5.4 J/m². We propose that this anomalously strong adhesion between heterogeneous interfaces is derived from significant spin correlations and d-d bonding at the interface.     

Fluorescence Analysis of Acridine Orange Adsorbate at the Water/N-Heptane Interface, Bulk and Interface

The amphiphilic nature of 3, 6-bisdimethylaminoacridine (trivial name, acridine orange) can be used to characterize (polar/nonpolar) interfaces. This paper studies the properties of acridine orange and its dodecyl derivative at a solvent interface by internal reflection and tension determinations. In the case of absorbance measurements of crystallized acridine orange, the potenz value of the conventional acid dissociation constant pK _a was found to be 9.6. A clear isosbestic point could be obtained after purification at a unique pH for different concentrations. In contrast, in the absorbance measurements of acridine orange dodecyl, no isosbestic point was observed; this was attributed to the free long dodecyl chain. The overlap in the absorbance spectrum and the normalized fluorescence spectrum was found in many solvents around 500 nm. Neutral species were more likely to transfer into organic phase upon shaking. For fluorescence measurements both steady-state and time-resolved spectra were investigated. Results showed that at the interface a bathochromic shift happened to the maxima. This means that chromophore species aggregated at the interface as the dimer or trimer or the macro oligomer. Fluorescence polarization in bulk was calculated and found to be ca. 0.4. For interfacial measurements a dynamic volume method was applied to obtain the interfacial tension. An extrapolated Gibbs plot was obtained. Increasing bulk concentration increased the concentration at the interface to a finite value representing saturation.