Formation mechanisms of colloidal silica via sodium silicate

Colloidal silica is formed by titrating active silicic acid into a heated KOH with seed solution. The colloidal silica formation mechanisms are investigated by sampling the heated solution during titration. In the initial stage, the added seeds were dissolved. This might due to the dilution of seed concentration, the addition of potassium hydroxide (KOH) and the heating at 100°C. Homogenous nucleation and surface growth occur simultaneously in the second stage of colloidal silica formation. Homogenous nucleation is more important when the seed concentration is relatively low. On the other hand, surface growth plays an important role when the seed concentration is increased. In the middle seed concentration, the seed particles grow up and some new small particles are born by the homogenous nucleation process to form a bimodal size distribution product. As the titrating volume of active silicic acid exceeds a specific value in the last stage the particle size increases rapidly and the particle number decreases, which may be caused by the aggregation of particles. The intervals between each stage were varied with the seed concentration. Increasing the seed concentration led to the formation of uniform particle size colloidal silica.     

Phase diagrams of decomposing nanoalloys

The thermodynamics of nucleation and decomposition in small isolated particles are considered. There exist three possibilities: phase separation, prohibition of decomposition and a metastable state. We investigate the peculiarities of phase diagrams related to depletion of the nanosize parent phase even at the nucleation stage. For small particles the equilibrium diagram becomes split (and shifted and size dependent). Concentration, size and temperature hystereses take place. Size-dependent ‘critical supersaturation’, increasing with decreasing size, has been analysed.     

Structural features of Ag-Cu alloy films produced by the codeposition of sputtered metals

Solid solutions in the form of alloy coatings are obtained in the entire concentration range of binary system using ion-plasma sputtering and the codeposition of Ag and Cu ultrafine particles. Sstudying the structure of solid solutions shows a change in the FCC-lattice parameters from silver to copper with a characteristic bend corresponding to the eutectic composition of the equilibrium phase diagram. Solid-solution decay begins at 100°C, and their complete decomposition occurs at 250°C. The surface structure of the initial solutions is presented by crystallites 20–30 nm in cross section; after decomposition, their size is less than 100 nm. For the latter, the distortions of the lattice parameters are 0.32% for a solution of Cu in Ag and 0.29% for a solution of Ag in Cu. The method of alloy production can be extended to the systems of metals immiscible in the solid phase.     

Thermodynamic analysis of the decomposition of a supersaturated solid solution of the Fe-Cu system

The structure of Fe-5.5% Cu alloy is studied after eutectoid reaction and aging of the martensite. The thermodynamic analysis of decomposition of the supersaturated solid solution with copper release is peformed for different types of crystal lattice. The free energy of solid solutions and phase separation diagrams of the BCC and FCC phases of copper is calculated. Barriers for the nucleation of copper particles with BCC and FCC lattices are evaluated. The factors that favor the appearance of intermediate structural forms of copper preceding the formation of stable FCC phase are discussed.     

Molecular dynamics study of the role of material properties on nanoparticles formed by rapid expansion of a heated target

Rapid expansion of a heated target and its decomposition into fragments is investigated by using molecular dynamics simulations. Particular attention is focused on the void formation and nucleation that governs the target disintegration. The cluster formation process is investigated as a function of material properties (initial temperature, interaction potential and composition). Calculation results demonstrate the influence of these properties on void nucleation and growth and on the characteristic parameters of nanoparticles to be formed. In particular, larger initial temperature and expansion rate lead to the formation of smaller fragments. These effects are found to be similar for three different materials (silicon, nickel and metal alloy). In addition, the stoichiometrical cluster composition obtained in the expansion of a binary alloy is found to be fairly well preserved. The calculation results can be used for the interpretation of the experimental findings showing the formation of nanoparticles by short and ultra-short pulse laser ablation of both simple and more complex materials.     

Small-angle x-ray scattering study of the formation and growth of δ' in binary Al－7.87at% Li alloy

The formation and growth of δ' particles in an alloy of Al－7.87at% Li have been investigated using the small angle x-ray scattering technique. It has been shown that a transition zone, which exists between the δ' phase and the matrix after ageing for 16 h, disappears after ageing for 32 h. The existence of a transition zone indicates that the δ' phase is precipitated in the process of spinodal decomposition. This result also indicates that the growth of δ' particles should be divided into two stages. During the first stage, the δ' phase increases eating up the transition zone before ageing for 32 h, and in the second stage it grows by swallowing up each other after ageing for 32 h. In the latter stage, the larger and smaller δ' particles can coexist in the alloy.     

Phase transitions in condensed media at a finite rate of formation of a metastable state

The influence of the finite rate of formation of a metastable state on the kinetics of the first-order phase transition is analyzed. The conditions determined by the thermodynamic parameters and the cooling rate of the system under consideration are derived. Under these conditions, the formation of the metastable state can be treated either as an instantaneous process, when nucleation occurs at the end of the cooling stage, or as a slow process, when intensive nucleation of a new phase proceeds within the cooling stage. An equation describing the time and temperature that correspond to intensive nucleation of new-phase particles is obtained. The nucleation stage of the new phase takes place in the immediate vicinity of the temperature determined from this equation. All the other parameters, which determine the kinetics of the initial and transient stages of the phase transition, are calculated with respect to this temperature. As an example, all the relationships for a weak solid solution are presented.     

Formation of NI80P20 solid solution phase under pressure

A Ni-P solid solution phase was obtained by quenching of melts under a pressure of 4.5 GPa. This was considered as a metastable high pressure phase. Despite the lack of thermodynamic parameters for Ni₈₀, P₂₀ alloy under pressure, the degree of undercooling, nucleation frequency and crystal growth velocity were calculated. We conclude that metastable phases with the same composition as the melting phase, such as supersaturated solid solution phase and amorphous phase, are easily prepared by high-pressure quenching.     

Decomposition kinetics of a solid solution with the formation of a new phase of complex stoichiometric composition

The evolution of a metastable solid solution containing impurities of different sorts is investigated at the nucleation and transient stages upon precipitation of new-phase particles of a stoichiometric composition. The flux of new-phase particles in the size space, their maximum number, and the size distribution are determined.     

Kinetics of nucleation of the solid phase in supercooled solutions or liquids under heat-insulating conditions: Intensive nucleation stage

The kinetics of decomposition of a supercooled melt or a viscous fluid under heat-insulating conditions during intensive nucleation has been investigated. Particles of a new phase have been studied, whose size is larger than the critical value, and for which the times are longer than the settling time of the classical quasi-steady state, which is characteristic of subcritical nuclei. The heat removal from the phase boundary is assumed to be the key process in the vicinity of a growing particle. The estimates of the duration of the stage of intensive nucleation, the maximum number of nucleated particles, and their average “size” have been obtained. Numerical simulations have been performed for nickel.     

Implementation of an advanced fixed sectional aerosol dynamics model with soot aggregate formation in a laminar methane/air coflow diffusion flame

An advanced fixed sectional aerosol dynamics model describing the evolution of soot particles under simultaneous nucleation, coagulation, surface growth and oxidation processes is successfully implemented to model soot formation in a two-dimensional laminar axisymmetric coflow methane/air diffusion flame. This fixed sectional model takes into account soot aggregate formation and is able to provide soot aggregate and primary particle size distributions. Soot nucleation, surface growth and oxidation steps are based on the model of Fairweather et al. Soot equations are solved simultaneously to ensure convergence. The numerically calculated flame temperature, species concentrations and soot volume fraction are in good agreement with the experimental data in the literature. The structures of soot aggregates are determined by the nucleation, coagulation, surface growth and oxidation processes. The result of the soot aggregate size distribution function shows that the aggregate number density is dominated by small aggregates while the aggregate mass density is generally dominated by aggregates of intermediate size. Parallel computation with the domain decomposition method is employed to speed up the calculation. Three different domain decomposition schemes are discussed and compared. Using 12 processors, a speed-up of almost 10 is achieved which makes it feasible to model soot formation in laminar coflow diffusion flames with detailed chemistry and detailed aerosol dynamics.     

Determination of size and concentration of critical clusters of silicon carbide in the vapour phase in homogeneous nucleation process

The concentrations of clusters of various size in the atmosphere during silicon carbide crystal growth have been calculated on the basis of fundamental ideas of homogeneous nucleation theory, taking into account the specific parameters of silicon carbide. It has been shown that the cluster concentration are sufficiently high to conclude that this is the dominant influence during the initial stages of crystal growth. In this way the assumption of the polymer theory of polytypism, namely that the polytype properties of silicon carbide can be determined from the composition of the gas phase, containing sufficiently large clusters with various polytype structures, has been confirmed.     

Characterization of the spinodal decomposition of Fe−Cr alloys by Mössbauer spectroscopy

Addition of 5%Ni to an Fe?28%Cr alloy causes a transition of the aging behavior from the nucleation and growth to the spinodal decomposition. Very rapid increase in the average internal magnetic field and a broadening of the internal magnetic field distribution occur in the spinodal decomposition. Mössbauer spectra are synthesized by assuming a rectangular and a sinusoidal wave for the composition fluctuation, and the internal magnetic field distributions obtained from those are compared with the experimental results to estimate a time evolution of the amplitude of the composition wave.     

Production and decay of subcritical nuclei in a solid solution

The decay of “subcritical” nuclei in a solid solution has been revealed in the investigation of the CuCl phase nucleation kinetics in glass. As soon as “supercritical” nuclei with an average radius R = 1.1 nm are created at 500°C, a sharp temperature increase up to 650°C transforms most nuclei created in the first annealing stage into “subcritical” ones, and this results in the decay of 80% of the nuclei in 5 min, while the remaining 20% of the nuclei grow in size to 2.4 nm. Their growth provides a sixfold increase in the CuCl phase growth rate against that in conventional annealing at 650°C. The kinetic dependences of the nucleation parameters—the amount of the phase and the average radius and concentration of the particles—were determined by the intrinsic absorption spectra of the CuCl nanocrystals. The critical radius of the CuCl nanomelt at 650°C has been estimated as 1.3 nm and the evaporation heat of the CuCl phase molecules in glass, as 13 kJ/mol. It is shown that multistage annealing makes it possible not only to control the parameters of the particles of the new phase, but also to determine the critical parameters of the initial nucleation stage.     

Theory of switching of multiaxial ferroelectrics (Initial stage)

The classical theory of nucleation and growth is used to study the thermodynamics and kinetics of switching of multiaxial ferroelectrics. The initial stage of 180°-and 90°-domain switching is studied in the tetragonal, orthorhombic, and trigonal phases. The multidimensional kinetic theory of first-order phase transitions is applied to describe the initial stage of switching of ferroelectric crystals in the general case where three-dimensional growth (along the radius and height) of repolarized domains occurs. The energy of nucleus formation is calculated in the vicinity of the saddle point of an activation barrier in the space of sizes and shapes, and the dependence of the critical domain size on the switching field is found. The two-dimensional Fokker-Planck kinetic equation is reduced to a one-dimensional Zel’dovich equation, and a stationary solution to the Zel’dovich equation is obtained. The diffusion coefficients are derived in the size space for the normal and layer-by-layer mechanisms of domain growth. The main characteristic of the initial switching stage, namely, the steadystate flux of repolarized domains, is found as a function of the applied field.

     

非晶一次晶化过程微观组织演化和生长动力学的相场法研究

在晶化物理模型中添加扩散系数对晶化过程的影响, 采用相场方法研究初始形核率和初始形核半径对一次晶化过程中微观组织和生长动力学的影响。结果表明: 随着初始形核率的增加, 相同时间内非晶一次晶化的晶粒数量逐渐增加, 晶粒尺寸逐渐减小。晶化分数随着演化时间和初始形核率的增加逐渐增大, 初始形核率越大, 相同演化时间内的晶化分数越高。不同初始形核半径情况下, 非晶一次晶化过程中的晶粒数量和尺寸随着演化时间的增加基本保持不变。晶化分数随着演化时间的增加而增大。不同初始形核率和初始形核半径情况下所对应的生长指数均小于1, 表明初始形核率和初始形核半径对晶化方式无影响, 均为一次晶化。改变初始形核率和初始形核半径可调控一次晶化微观组织结构, 而晶粒尺寸及晶化分数直接关系到合金性能。     

Nucleation kinetics of a solid phase in supercooled melts or liquids under heat-insulating conditions (The Initial Stage)

The initial stage of decomposition of a supercooled melt or a viscous liquid under heat-insulating conditions has been considered in terms of the method of virtual media. The heat removal from the interface is taken as the controlling process in the vicinity of a growing nucleus. In addition to the quasi-steady-state equations (which already became standard) for the nucleation rate and the distribution function of subcritical particles of a new phase, an estimating equation has been derived for the time required to reach steady-state values of these characteristics. Numerical evaluations have been performed for nickel. It has been demonstrated that the chosen model of the controlling process is valid only under the condition of weak heat removal. Attention has been drawn to the difference between the “diffusion” and “thermal” processes of nucleation.     

Microstructural evolution during containerless rapid solidification of Co-Si alloys

The Co-12%Si hypoeutectic, Co-12.52%Si eutectic and Co-13%Si hypereutectic alloys are rapidly solidified in a containerless environment in a drop tube. Undercoolings up to 207K (0.14T_E) are obtained, which play a dominant role in dendritic and eutectic growth. The coupled zone around Co-12.52%Si eutectic alloy has been calculated, which covers a composition range from 11.6 to 12.7%Si. A microstructural transition from lamellar eutectic to divorced eutectic occurs to Co-12.52%Si eutectic droplets with increasing undercooling. The lamellar eutectic structure of the Co-12.52%Si alloy consists of εCo and Co_3Si phases at small undercooling. The Co_3Si phase cannot decompose completely into εCo and αCo_2Si phases. As undercooling becomes larger, the Co_3Si phase grows very rapidly from the highly undercooled alloy melt to form a divorced eutectic. The structural morphology of the Co-12%Si alloy droplets transforms from εCo primary phase plus lamellar eutectic to anomalous eutectic, whereas the microstructure of Co-13%Si alloy droplets experiences a `dendritic to equiaxed' structural transition. No matter how large the undercooling is, the εCo solid solution is the primary nucleation phase. In the highly undercooled alloy melts, the growth of εCo and Co_3Si phases is controlled by solutal diffusion.     

On the growth of conversion chromate coatings on 2024-Al alloy

The initial growth of chromate conversion coatings on aluminium 2024-T3 alloy has been investigated by scanning Auger microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. The coating initiation is shown to be influenced by the alloy microstructure. In agreement with previously proposed growth models, Cr(VI) to Cr(III) reduction begins on the Al-Cu-Fe-Mn intermetallic second-phase particles, which act as cathodic sites, and then over the entire Al matrix surface. The less noble Al-Cu-Mg second-phase particles demonstrate dual behaviour during the initial stage of coating; some dealloy, with formation of a Cu-rich sponge-like structure, while others show no evidence for etching during the first few seconds and coating deposits on them similar to the situation for the Al-Cu-Fe-Mn particles. XPS measurements show more Cr(III) at the very initial stage of nucleation and growth, whereas the amount of Cr(VI) in the coating increases with the length of the chromating treatment. This is discussed in relation to Raman spectroscopy measurements made in a separate study.