Phase separation in monotectic alloys as a route for liquid state fabrication of composite materials

The mechanism of liquid–liquid phase separation and factors determining the solid-state microstructure of monotectic alloys are discussed. The effect of the cooling rate on the phase-separated morphology is shown in examples of Al–In, Al–Pb, Ni–Nb–Y and Zr–Gd–Co–Al alloys solidified by different techniques. A remarkable improvement of the microstructure for the Al₉₁Pb₉ hypermonotectic alloy cast with TiB₂ particles, which catalyze the phase separation, is demonstrated.     

Assessment of B4C reaction with liquid iron alloys

The degree of reaction achieved when B₄C powders are brought into contact with liquid iron alloys has been assessed by a levitation dispersion test. Reaction occurs rapidly, leading to boron carbide dissolution and iron boride formation. In carbon-free iron alloys borocarbide, Fe₂₃(C, B)₆, also forms and in low-carbon iron alloys free graphite was also formed. Highcarbon alloys reacted to form both Fe₃(C, B) and free graphite. Attempts to provide protection for the B₄C by forming a TiC coating on its surface byin situ reactions with liquid Fe-Ti and Fe-Ti-C alloys proved unsuccessful, with TiC forming as a dispersed phase throughout the iron matrix     

Amalgamation mechanism in dental amalgam alloys

Model experiments to explore the amalgation mechanism in conventional Ag₃Sn and high copper single-composition dental alloys have been conducted by rotating alloy roda in liquid mercury at different speeds and for different durations. After removing the rod from the mercury, the vacuum volatilization technique was used to accelerate the supersaturation of dissolved elements in the liquid mercury. The surface and sectional scanning electron microscope (SEM) views give direct evidence for new amalgamation mechanism in high copper dental alloys. The amalgamation reaction begins with the selective dissolution of the Ag₃Sn phase in mercury, tin gettering to the crumbled-off Cu₃Sn phase, heterogeneous nucleation of the Cu₆Sn₅ phase on the seed of the crumbled-off Cu₃Sn phase and was followed by the nucleation of the Ag₂Hg₃ phase. The unexplained phenomena, the formation of the -2 phase (Sn_7-8Hg) in higher content of mercury and the nonexistence of the -2 phase in higher content of copper alloys such as Sybralloy, were clearly understood by applying the new model.     

Grain boundary wetting in the NdFeB-based hard magnetic alloys

Since the end of 1980s, NdFeB-based hard magnetic alloys have been the materials with the highest available magnetic performance. NdFeB-based magnets are produced either by liquid-phase sintering or by melt spinning. In the present investigation, NdFeB alloys quenched after annealing in the semi-liquid state are used to study the wetting of Nd₂Fe₁₄B grain boundaries by a Nd-rich liquid phase. It is shown that a transition from partial wetting to complete wetting occurs with increasing temperature. The results are compared with the data in the literature for NdFeB-based alloys processed by liquid-phase sintering. The relation between wetting properties and magnetic performance of these alloys is also discussed.     

Surface Tension,Phase Separation,and Solidification of Undercooled Cobalt–Copper Alloys

By using electromagnetic levitation, liquid Cu–Co alloys can be undercooled below their liquidus temperature into the metastable miscibility gap, leading to a phase separation into a cobalt‐rich L₁ phase and a cobalt‐poor L₂ phase. This paper reports on experimental and theoretical investigations into the properties of this system, including equilibrium shape, surface, and interfacial tension, phase separation, as well as solidification behavior. Solidification experiments were performed in microgravity in order to minimize the effect of convection on the resulting microstructure.     

Investigation of ordering phenomenon in Me–Pt (Me=Fe,Ni) liquid alloys

The phase diagrams of Fe–Pt and Ni–Pt liquid alloy systems show the existence of FePt and NiPt intermetallic compounds, respectively, in their solid intermediate states, and the associative tendency between unlike atoms in these liquid alloys has been analysed using the self-association model. The concentration dependences of mixing properties such as the free energy of mixing, G_M; the concentration fluctuations, S_cc(0), in the long-wavelength limits; the chemical short-range order (CSRO) parameter, α₁; as well as the chemical diffusion, enthalpy and entropy of the mixing of Fe–Pt and Ni–Pt liquid alloys have been investigated to determine the nature of ordering in the liquid alloys. The results show that heterocoordination occurs in the alloys at all concentrations. The effect of CSRO on S_cc(0), chemical diffusion, D, and the order parameter, α₁, has been considered. The ordering phenomenon in the liquid alloys is also related to the effect of the atomic size mismatch volume on S_cc(0).     

Investigation of ordering phenomenon in Me–Pt (Me=Fe,Ni) liquid alloys

Abstract

The phase diagrams of Fe–Pt and Ni–Pt liquid alloy systems show the existence of FePt and NiPt intermetallic compounds, respectively, in their solid intermediate states, and the associative tendency between unlike atoms in these liquid alloys has been analysed using the self-association model. The concentration dependences of mixing properties such as the free energy of mixing, G_M; the concentration fluctuations, S_cc(0), in the long-wavelength limits; the chemical short-range order (CSRO) parameter, α₁; as well as the chemical diffusion, enthalpy and entropy of the mixing of Fe–Pt and Ni–Pt liquid alloys have been investigated to determine the nature of ordering in the liquid alloys. The results show that heterocoordination occurs in the alloys at all concentrations. The effect of CSRO on S_cc(0), chemical diffusion, D, and the order parameter, α₁, has been considered. The ordering phenomenon in the liquid alloys is also related to the effect of the atomic size mismatch volume on S_cc(0).     

Evolution of the structure and phase composition of MeVa-MeIVa alloys under the action of liquid lithium

We present the results of a thorough investigation of the processes occurring on the surface and inside Me_VA-Me_IVA alloys as a result of their long-term contact with liquid lithium. With V-Ti alloys as an example, we determine the role of nonmetallic impurities (O, N, C) in corrosion processes and suggest a mechanism of the formation of structure and phase composition of the investigated alloys under the action of liquid lithium. In general, the redistribution of interstitials in Me_VA-Me_IVA alloys leads to the formation of a heterogeneous structure that consists of three zones: (I) a zone where lithium interacts with a base metal, (II) a single-phase zone of a V-Ti-O (C, N) solid solution formed as a result of the dissolution of the oxide phase, and (III) a two-phase zone of internal nitriding with particles of oxynitrides of variable stoichiometry. It is also demonstrated that the directions and rates of diffusive flows of nonmetallic atoms on the melt-metal interface are controllable by rational alloying.Karpenko Physicomechanical Institute, Ukrainian Academy of Sciences, L'viv. Translated from Fiziko-Khimicheskaya Mekhanika Materialov, Vol. 30, No. 6, pp. 58–63, November – December, 1994.     

Microstructures and liquid phase separation in multicomponent CoCrCuFeNi high entropy alloys

The microstructures of high entropy alloys of the system CoCrCuFe_xNi and CoCrCuFeNi_x (where x indicates the molar ratio, which, where not specified, is 1) have been investigated. Many Cu rich spheres were evident in the microstructure of CoCrCuFe_0.5Ni and CoCrCuFeNi_0.5 alloys, which indicates that liquid phase separation had occurred before solidification. During liquid phase separation, the original liquids separated into two liquids: Cu rich and Cu depleted. In contrast, in other alloys (x?=?1.0, 1.5 and 2.0), typical dendritic and interdendritic structures are obtained. Cu and/or Cr rich precipitates, with various morphologies, can be seen in the interdendritic region. Additionally, Cu rich nanoparticles and Cr rich bird shaped structures can be observed in the Cu rich spheres. Sluggish cooperative diffusion causes the element segregation and formation of nanoprecipitates in the microstructures. The calculated positive mixing enthalpies of CoCrCuFe_0.5Ni and CoCrCuFeNi_0.5 alloys are likely reasons for their liquid phase separation.     

Dispersion and reaction of TiB2 in liquid iron alloys

Abstract

The degree of reaction and dispersion achieved when TiB₂ powders are melted in contact with liquid iron based alloys has been assessed via a levitation dispersion test which had been developed earlier. Both Fe₂B and TiC were observed to form as a result of dissolution and reaction of TiB₂. The formation of TiC occurs during the reaction of commercial grade TiB₂ with liquid iron alloys containing as little as 0·08 wt-%C. The reaction of high purity TiB₂ with liquid iron alloys containing 0·24 wt-%C does not however lead to TiC formation. The formation of Fe₂B was observed for all conditions tested, owing to the effectively zero solubility of boron in solid iron. The TiB₂ remaining after dissolution and reaction was found to produce relatively good dispersions in the iron matrix and therefore additions of TiB₂ to liquid iron alloys may provide a means of producing Fe–TiB₂ composite materials. However, the brittle properties of Fe₂B will mean that, whereas such materials may be very hard, they are likely to lack toughness.

MST/1477     

Studies of ceramic-liquid metal reaction interfaces

An investigation has been made of the nature and extent of chemical reactions between various liquid metals and a range of engineering-grade ceramics typically used as cutting tool inserts. Such possible reactions are relevant to chemical wear effects during metal cutting but also relate to liquid metal containment by ceramics and ceramic-metal joining. The experimental procedure has involved immersing pre-polished ceramic sections in liquid metals for controlled times with subsequent sectioning and examination of the reaction interface. The ceramics studied were two alumina-based materials and five silicon nitrides and sialons. The metals were pure iron, pure nickel and four iron-nickel alloys (a mild steel, a stainless steel and two nickel-based superalloys) and span a range of Fe-Ni compositions. The reaction rates of the alumina materials were found to be much lower than those of the silicon nitride-based materials and reflect the chemical stability of the Al-O bond array. Zirconia-toughened alumina showed little evidence of reaction with clean iron alloys but substantial attack by oxygen-containing iron-based materials was found resulting in the formation of iron-aluminium spinel reaction products. Al₂O₃-TiC/N exhibited preferential metal attack of the carbonitride phase with dissolution and/or replacement of the TiC/N dispersion. Within the silicon nitride-based group, ferrous alloys were found to be more damaging than mainly nickel alloys and silicon nitrides were more readily attacked than sialons. The difference in behaviour between the sialons and silicon nitrides is attributed to alumina additions in the former group of materials increasing resistance to attack by molten metals. A detailed mechanism of attack for these mixed-phase ceramics is proposed whereby a silicon concentration gradient is established from the crystalline ceramic phases, through the glassy binding phase, to the metal. The result is dissolution of the crystalline phase and an increase in volume fraction of the glassy binder at the metal-ceramic interface with concomitant progressive disruption of the ceramic microstructure.     

A method for the calculation of interfacial energies in Al2O3 and ZrO2/liquid-metal and liquid-alloy systems

A method is proposed by which the interfacial energy, γ_SL, of polycrystalline solid oxides (Al₂O₃, ZrO₂) in contact with liquid metals and certain binary liquid alloys can be calculated from the values of the surface energy of the oxides, γ_SV, and the liquid metals or liquid alloys, γ_LV, respectively. According to this method, the interfacial energy depends on the geometric mean of surface interactions, (γ_SV γ_LV)^1/2, the molar volumes, V, of the solid and liquid phases, and a parameter, K, which depends on the geometric details of the oxide surface defined by the ion sites in the oxide as well as the stoichiometry of the elements in the oxide and is given by the equation, $$\gamma _{SL} = \left( {K\frac{{V_{metal} }}{{V_{oxide} }} + 1} \right)^{2/3} (\gamma _{SV} \gamma _{LV} )^{1/2}$$ The method was verified using interfacial energy data obtained by measurements of the contact angle, θ, formed between the oxides and the liquid metals and liquid alloys with the sessile drop technique. A good agreement was observed between the calculated and the experimentally estimated values of γ_SL at the melting point of the metals and alloys.     

Effects of processing parameters on aluminide morphology in aluminium grain refining master alloys

Abstract

An investigation has been made of the effects of processing parameters on the microstructure of Al–Ti and Al–Zr alloys produced by the reduction of potassium fluorotitanate and potassium fluorozirconate by aluminium. Blocky aluminides (TiAl₃ and ZrAl₃ respectively) are produced when the reduction is performed in the liquid+solid phase region and flaky aluminides are produced when it is performed in the liquid phase region. The use of Na₂TiF₆ rather than K₂TiF₆ has no apparent effect on the alloy structure. The microstructure and the size of aluminide blocks or flakes produced are further influenced by the subsequent cooling rate experienced by the alloy. Post-fabrication heat treatment of Al–5Ti–0·2B (wt-%) alloys (produced by combined reduction of potassium fluqrotitanate and potassium fluoroborate by aluminium) causes boride particles to precipitate on the aluminide surfaces. These borides grow in size and decrease in number with heat treatment time.

MST/1355     

The microstructure and mechanical properties of yttria-stabilized zirconia prepared by arc-melting

The microstructure of ZrO₂-Y₂O₃ alloys prepared by arc-melting was examined mainly by electron microscopy. It was found that the microstructure changed markedly with yttria content between 0 and 8·7 mol%. Pure zirconia was a single monoclinic phase, while ZrO₂-8·7 mol% Y₂O₃ alloy was single cubic phase as expected from ZrO₂-Y₂O₃ phase diagram. Tetragonal phase was found in alloys with 1 to 6 mol% Y₂O₃ together with monoclinic or cubic phase. The tetragonal phase found in present alloys normally had a lenticular shape with a length 1 to 5m and a width 0.1 to 0.3m, which is much larger than that formed by annealing. The phase with a herring-bone appearance was found in alloys with Y₂O₃ between 2 and 3 mol%, which was recognized to be a metastable rhombohedral phase. The structure of the present alloys is likely to be formed by martensitic or bainitic transformation during fairly rapid cooling from the melt temperature. The change in hardness and toughness with yttria content of the alloys is discussed on the basis of microstructural observations.     

High formability of glass plus fcc-Al phases in rapidly solidified Al-based multicomponent alloy

A multicomponent Al₈₄Y₉Ni₄Co_1.5Fe_0.5Pd₁ alloy was found to keep a mixed glassy + Al phases in the relatively large ribbon thickness range up to about 200 μm for the melt-spun ribbon and in the diameter range up to about 1100 μm for the wedge-shaped cone rod prepared by injection copper mold casting. The glassy phase in the Al-based alloy has a unique crystallization process of glass transition, followed by supercooled liquid region, fcc-Al + glass, and then Al + Al₃Y + Al₉ (Co, Fe)₂ + unknown phase. It is also noticed that the primary precipitation phase from supercooled liquid is composed of an Al phase instead of coexistent Al + compound phases, being different from the crystallization mode from supercooled liquid for ordinary Al-based glassy alloys. In addition, it is noticed that the mixed Al and glassy phases are extended in a wide heating temperature range of 588–703 K, which is favorable for the development of high-strength nanostructure Al-based bulk alloys obtained by warm extrusion of mixed Al + amorphous phases. The Vickers hardness is about 415 for the glassy phase and increases significantly to about 580 for the mixed Al and glassy phases. The knowledge of forming Al + glassy phases with high hardness in the wide solidification and annealing conditions through high stability up to complete crystallization for the multicomponent alloy is promising for future development of a high-strength Al-based bulk alloy.     

Investigation of mechanical properties and devitrification of Cu-based bulk glass formers alloyed with noble metals

The mechanical properties, glass-forming ability, supercooled liquid region and devitrification behaviour of the Cu–Zr–Ti–(Pd, Ag, Pt and Au) bulk glass formers were studied by using a mechanical testing machine, X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and isothermal calorimetry. The bulk glassy alloys of diameter 2 mm were formed in the Cu₅₅Zr₃₀Ti₁₀Pd₅ and Cu₅₅Zr₃₀Ti₁₀Ag₅ alloys while Cu₅₅Zr₃₀Ti₁₀Au₅ bulk alloy showed mixed glassy and crystalline structure. No glassy phase was formed in the Cu₅₅Zr₃₀Ti₁₀Pt₅ bulk alloy whereas the glassy phase was formed in all of the ribbon samples prepared by rapid solidification. The studied alloys except for the Pt-bearing one have slightly increased compressive fracture or yield strength values compared to ternary Cu₆₀Zr₃₀Ti₁₀ glassy alloy. At the same time Pd and Au addition significantly expand the supercooled liquid region of Cu–Zr–Ti glassy alloy and increase Young's modulus. A nanoicosahedral phase is primarily formed in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ glassy alloys in the initial stage of the devitrification process by nucleation and three-dimensional diffusion-controlled growth. Nearly the same quasilattice constant obtained in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ alloys illustrates the same type of the icosahedral phase in these alloys. However, no icosahedral phase was found in the Cu₅₅Zr₃₀Ti₁₀(Ag,Pt)₅ alloys.     

Investigation of mechanical properties and devitrification of Cu-based bulk glass formers alloyed with noble metals

The mechanical properties, glass-forming ability, supercooled liquid region and devitrification behaviour of the Cu–Zr–Ti–(Pd, Ag, Pt and Au) bulk glass formers were studied by using a mechanical testing machine, X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and isothermal calorimetry. The bulk glassy alloys of diameter 2 mm were formed in the Cu₅₅Zr₃₀Ti₁₀Pd₅ and Cu₅₅Zr₃₀Ti₁₀Ag₅ alloys while Cu₅₅Zr₃₀Ti₁₀Au₅ bulk alloy showed mixed glassy and crystalline structure. No glassy phase was formed in the Cu₅₅Zr₃₀Ti₁₀Pt₅ bulk alloy whereas the glassy phase was formed in all of the ribbon samples prepared by rapid solidification. The studied alloys except for the Pt-bearing one have slightly increased compressive fracture or yield strength values compared to ternary Cu₆₀Zr₃₀Ti₁₀ glassy alloy. At the same time Pd and Au addition significantly expand the supercooled liquid region of Cu–Zr–Ti glassy alloy and increase Young’s modulus. A nanoicosahedral phase is primarily formed in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ glassy alloys in the initial stage of the devitrification process by nucleation and three-dimensional diffusion-controlled growth. Nearly the same quasilattice constant obtained in the Cu₅₅Zr₃₀Ti₁₀(Pd,Au)₅ alloys illustrates the same type of the icosahedral phase in these alloys. However, no icosahedral phase was found in the Cu₅₅Zr₃₀Ti₁₀(Ag,Pt)₅ alloys.     

Effect of Al2O3 particles on the growth kinetics of molybdenum grains in liquid nickel

Grain growth inhibition by inert third phase particles during liquid phase sintering has been investigated in Mo-Ni alloys containing Al₂O₃ particles sintered at 1460° C. The grain growth is inhibited slightly by the Al₂O₃ particles, and this result is explained in terms of the shielding of material precipitation at the contact area and of the suppression of material precipitation around the contact area, which is determined by the dihedral angle between the molybdenum grain and the Al₂O₃ particle. The result is compared to those obtained earlier with specimens containing highly soluble third phase particles.     

Effect of Ti-Zr addition on the microstructure and the arc chopping current of melt-spun CuCr ribbon

The microstructure and the arc chopping current of melt-spun Cu₇₁Cr₂₉ ribbon added by Ti-Zr are studied in the article. The results reveal that the melt spinning could partly restrain the liquid phase separation of CuCr alloys because it has a high cooling rate (about 10⁶ K/s), the size of the Cr rich phase from liquid phase separation in the Cu₇₁Cr₂₉ microstructure can be decreased from the micron-scale to about 250 nm by using melt spinning. On the melt-spun base, alloying by Ti-Zr could further decrease the size of the Cr rich phase from 250 nm to about 100 nm. For nano-grained CuCr alloys, its lower arc chopping current is advantageous to the use of contact and the circuitry protect, its long arc trace route and high velocity of spot direction motion could mitigate the partial ablate of cathode surface and the lifetime of contact could be prolonged.     

Structure and microstructure of leached Raney-type Al–Ni powders

The structure and microstructure of some leached Raney-type Al–Ni alloys of different compositions have been investigated by neutron diffraction and by small-angle neutron scattering. It was found that all alloys contain a crystalline face-centred cubic (fcc) Ni phase as well as an Al₃Ni₂ phase, the amount of which is decreasing with increasing Al content of the initial alloy. Both the Ni and the Al₃Ni₂ phases are conjectured to be non-stoichiometric. There is no indication of any other crystalline phase. The size of the Ni crystallites in all leached alloys has been found to be of the order of 30 Å, whereas the size of the Al₃Ni₂ ones varies with initial alloy composition and is found to be in the range of 100–250 Å. The change in structure by doping the initial alloys with small amounts of Ti and Cr is after leaching marginal.