Grain refinement in aluminum alloyed with titanium and boron

The aluminum corner of the ternary Al-B-Ti diagram was explored. A eutectic: Liq — Al + TiAl₃ + (Al, Ti)B₂ was found at approximately 0.05 wt pct Ti, 0.01 wt pct B; 659.5‡C. TiB₂ and A1B₂ form a continuous series of solid solutions, but no distinct ternary phase was found. The addition of boron to aluminum-titanium alloys expands the field of primary crystallization of TiAl₃ toward lower titanium contents and steepens the liquidus. In equilibrium conditions, pronounced grain refinement is found only in alloys in which TiAl₃ is primary and nucleates the aluminum solid solution before any other impurity can act. The peritectic reaction facilitates this priority but it is not necessary for grain refinement. Because of the low diffusivity of titanium and boron in aluminum, equilibrium is seldom attained and in commercial practice grain refinement by TiAl₃ is found also outside its equilibrium field of primary crystallization.     

Microstructure evolution in tial alloys with b additions: Conventional solidification

Solidification microstructures of arc-melted, near-equiatomic TiAl alloys containing boron additions are analyzed and compared with those of binary Ti-Al and Ti-B alloys processed in a similar fashion. With the exception of the boride phase, the matrix of the ternary alloy consists of the same α₂ (DO₁₉) and γ (Ll₀) intermetallic phases found in the binary Ti-50 at. pct Al alloy. On the other hand, the boride phase, which is TiB (B27) in the binary Ti-B alloys, changes to TiB₂ (C32) with the addition of Al. The solidification path of the ternary alloys starts with the formation of primary α (A3) for an alloy lean in boron (∼1 at. pct) and with primary TiB₂ for a higher boron concentration (∼5 at. pct). In both cases, the system follows the liquidus surface down to a monovariant line, where both α and TiB₂ are solidified concurrently. In the final stage, the α phase gives way to γ, presumably by a peritectic-type reaction similar to the one in the binary Ti-Al system. Upon cooling, the α dendrites order to α₂ and later decompose to a lath structure consisting of alternating layers of γ and α₂.     

Study of the mechanism of grain refinement of aluminum after additions of Ti- and B-containing master alloys

A highly sensitive thermal analysis technique has been used to study the mechanisms of grain refinement in high-purity aluminum. Additions of Al-Ti-B master alloys were made both below and above the peritectic concentration in reference to the Al-rich corner of the binary Al-Ti phase diagram (0.15 pct Ti in solution). The experiments were conducted at various times after the addition of grain refiner. From the results, except for formation of TiB₂, no effect of boron on the Al-rich portion of the binary Al-Ti phase diagram can be observed. With hypoperitectic additions of Al-Ti-B master alloys, TiB₂ particles are the most frequent nucleant for aluminum grains. Also, when Al-5Ti-lB additions are made, nucleation frequently occurs above the equilibrium liquidus temperature. From a thermodynamic point of view, this phenomenon can occur only if regions of the melt (which contain bondes and nucleate new grains) have a higher Ti concentration than is present in the bulk of the liquid. A mechanism has been proposed to account for this observation. When hyperperitectic additions of grain refiner were made, a metastable formation of Al solid was often observed to occur at 2 to 5 deg above the equilibrium peritectic temperature. Other researchers have made this observation and proposed that a metastable aluminide phase was formed, even though no X-ray evidence of this phase was found. The experiments reported here show that the metastable nucleation occurs on boride particles when cooling from high temperature, which allow high (metastable) quantities of dissolved Ti to be retained in portions of the melt.     

Development of TiB<Subscript>2</Subscript> reinforced in-situ Ti aluminide matrix composite through reaction synthesis

TiB₂ reinforced in-situ titanium aluminide matrix composite was made through reaction synthesis process using high purity elemental powders of Ti, Al, Cr, Nb and B. XRD of the synthesized block showed presence of mainly Al₃Ti and TiB₂ phases. To obtain γ Ti aluminide based matrix, the material was homogenized in two phase region (α₂+γ). Presence of γ phase matrix alongwith α₂ was confirmed through XRD, SEM and TEM. Uniform distribution of TiB₂ phase was confirmed through elemental mapping and by analyzing specimens of different locations. Differential scanning calorimetry of powder mixture showed presence of endothermic peak for Al melting and exothermic peak of Ti aluminide and TiB₂ formation.     

The nucleation of aluminum grains in alloys of aluminum with titanium and boron

The microstructure of a ternary alloy, Al-5 wt pct Ti, 1 wt pct B, has been examined by optical and electron transmission microscopy, by selected area diffraction, and electron probe microscopy, by selected area diffraction, and electron probe microanalysis. Particles of Al₃Ti are found at the center of grains and there exist preferred epitaxial orientations between this compound and the surrounding aluminum. Particles containing titanium and boron occur at aluminum grain boundaries and have no preferred configurations with respect to the aluminum or to one another. It is concluded that the active heterogeneous nuclei are therefore Al₃Ti and that particles of TiB₂, AlB₂, or a ternary compound are not active in this alloy. Grain size measurements in binary Al-Ti alloys suggest that particles of a nucleating phase must be present at concentrations as low as 0.01 wt pct Ti, and it is suggested that these could be Al₃Ti if the existing binary phase diagram Al-Ti is in error.     

Evolution of boride morphologies in TiAl-B alloys

The solidification of γ-TiAl alloys with relatively low (<2 at. pct) additions of boron is discussed. Binary Ti-Al alloys containing 49 to 52 at. pct Al form primary α-(Ti) dendrites from the melt, which are subsequently surrounded by γ segregate as the system goes through the peritectic reactionL + α →γ. Alloys between 45 and 49 at. pct Al go through a double peritectic cascade, forming primary β-(Ti) surrounded by α-(Ti) and eventually by γ in the interdendritic spaces. Boron additions to these binary alloys do not change the basic solidifi-cation sequence of the matrix but introduce the refractory compound TiB₂ in a variety of mor-phologies. The boride develops as highly convoluted flakes in the leaner alloys, but needles, plates, and equiaxed particles gradually appear as the B content increases above ∼1 at. pct. Increasing the solidification rate initially promotes the formation of flakes over plates/needles and ultimately gives way to very fine equiaxed TiB₂ particles in the interdendritic spaces of the metallic matrix. Furthermore, the primary phase selection in the 49 to 52 at. pct Al range changes from α-(Ti) to β-(Ti) at supercoolings of the order of 200 K. The different boride morphologies are fully characterized, and their evolution is rationalized in terms of differences in their nucleation and growth behavior and their relationship to the solidification of the inter-metallic matrix. Formerly Research Assistant, University of California-Santa Barbara (UCSB) Formerly Professor of Materials and Dean of the College of Engineering at UCSB     

Solidification paths and carbide morphologies in melt-processed MoSi2-SiC In Situ composites

The present investigation was undertaken to elucidate the microstructural evolution of MoSi₂-SiC in situ composites produced by melt processing. An assessment of the existing liquidus projection was performed by a combination of thermodynamic modeling, analysis of solidification microstructures, and measurements of the thermal history during solidification. Results show that the quasibinary MoSi₂-SiC eutectic occurs at ∼2 at. pct C and 2283 K, rather than 8 at. pct C and 2173 K, as previously reported. The ensuing L+MoSi₂+SiC monovariant line runs almost parallel to the SiMoSi₂ binary and terminates at a ternary L ↔ Si+MoSi₂+SiC eutectic calculated at 1.5Mo-0.84C (at. pct) and ∼1670 K. The maximum amount of SiC that may be produced by solidification along the quasibinary isopleth is ∼37 vol pct, of which ∼35 vol pct grows as primary. Analysis of solidification microstructures shows SiC grows with the cubic β polytype structure (B3), while MoSi₂ grows with the tetragonal C11 _b structure. Primary SiC may grow as equiaxed particles, platelets, and hopper crystals. Coupled growth with MoSi₂ leads to SiC in the shape of thin ribbons, sheets, and needles. The facets of the SiC crystals were identified to be of the {111} and {002} type, in agreement with the periodic bond chain analysis. The predominant platelike morphology was shown to develop due to a re-entrant twin mechanism similar to that observed in Si and Ge.     

The Fe-rich corner of the metastable C-Cr-Fe liquidus surface

The liquidus surface of the C-Cr-Fe system has been experimentally determined in the Fe-rich region —C ≤6 wt pct, Cr ≤40 wt pct —using a sensitive differential thermal analysis technique, along with optical and scanning electron microscopy and X-ray diffraction. Previous liquidus surfaces for this system have differed on the extent of the (Cr,Fe)₂₃C₆ liquidus field, with one version reporting its existence at ∼20 wt pet Cr, and others finding that it did not occur at Cr levels of less than ∼60 wt pct. The present investigation provides evidence in favor of the second contention, with the (Cr,Fe)₂₃C₆ field not being detected at Cr ≤40 wt pct. Changes are proposed to the accepted liquidus surface in respect of the compositions of the invariant reactions—L + αδFe ⇌γFe + (Cr,Fe)₇C₃ andL + (Cr,Fe)₇C₃ ⇌γFe + (Fe,Cr)₃C —and of the monovariant eutectic valley—L⇌ γFe + (Cr,Fe)₇C₃.     

Boron removal by titanium addition in solidification refining of silicon with Si-Al melt

In order to effectively remove B from Si for its use in solar cells, a process involving B removal by solidification refining of Si using a Si-Al melt with Ti addition was investigated. For clarifying the effect of Ti addition on B removal from the Si-Al melt, TiB₂ solubilities in Si-64.6 at. pct Al melt at 1173 K and Si-60.0 at. pct Al melt at 1273 K were determined by measuring the equilibrium concentrations of B and Ti in the presence of TiB₂ precipitates. The small solubilities of TiB₂ in the Si-Al melt indicate the effective removal of B from the Si-Al melt by Ti addition. Further, solidification experiments of Si-Al alloys containing B by Ti addition were performed, and the effect of Ti addition on the solidification refining of Si with the Si-Al melt was successfully confirmed.     

Reaction Scheme and Liquidus Surface of the Ternary System Aluminum-Chromium-Titanium

The constitution of the ternary system Al-Cr-Ti is investigated over the entire composition range using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), differential thermal analysis (DTA) up to 1500 °C, and metallography. Solid-state phase equilibria at 900 °C are determined for alloys containing ≤75 at. pct aluminum and at 600 °C for alloys containing >75 at. pct Al. A reaction scheme linking these solid-state equilibria with the liquidus surface is presented. The liquidus surface for ≤50 at. pct aluminum is dominated by the primary crystallization field of bcc β(Ti,Cr,Al). In the region >50 at. pct Al, the ternary L1₂-type phase τ forms in a peritectic reaction p _max at 1393 °C from L + TiAl. Furthermore, with the addition of chromium, the binary peritectic L + α(Ti,Al) = TiAl changes into an eutectic L = α(Ti,Al) + TiAl. This eutectic trough descends monotonously through a series of transition reactions and ternary peritectics to end in the binary eutectic L = Cr₇Al₄₅ + (Al).     

The Al-Cu-Fe phase diagram: 0 to 25 At. pct Fe and 50

Isothermal sections of the Al-Cu-Fe equilibrium phase diagram at temperatures from 680 °C to 800 °C were determined in the region with 50 to 75 at. pct Al and 0 to 25 at. pct Fe using scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) techniques. This re- gion includes the face-centered icosahedral phase (Ψ-Al₆Cu₂Fe) which has unprecedented struc- tural perfection and no apparent phason strain. The icosahedral phase has equilibrium phase fields with four distinct phases at 700 °C and 720 °C (β-Al(Fe, Cu), λ-Al₁₃Fe₄, ω-Al₇Cu₂Fe, and liquid) and three phases at 680 °C(β, ω, and λ) and 800 °C (β, λ, and liquid). The B2 ordered β phase has considerably greater solubility for Cu than previously reported, extending from AlFe to ∼Al₅₀Fe₅Cu₄₅. The equilibrium range of composition for the icosahedral phase at these temperatures was determined, and a liquidus projection is proposed.     

Combustion characteristics of the Ni3Ti-TiB2 intermetallic matrix composites

Combustion synthesis (SHS) of Ni₃Ti-TiB₂ metal matrix composites (MMCs) was selected to investigate the effect of gravity in a reaction system that produced a light, solid ceramic particle (TiB₂) synthesized in situ in a large volume (>50 pct) of the liquid metallic matrix (Ni₃Ti). The effects of composition, green density of pellets, and nickel particle size on the combustion characteristics are presented. Combustion reaction temperature, wave velocity, and combustion behavior changed drastically with change in reaction parameters. Two types of density effects were observed when different nickel particle sizes were used. The structures of the combustion zones were characterized using temperature profile analysis. The combustion zone can be divided into preflame, reaction, and after-burning zones. The combustion mechanism was studied by quenching the combustion front. It was found that the combustion reactions proceeded in the following sequence: formation of liquid Ni-Ti eutectic at 940 °C → Ni₃Ti+NiTi phases → reduction of NiTi with B→TiB₂+Ni₃Ti.     

Co-deformation processing and modeling of <Emphasis Type="Italic">In-Situ</Emphasis> multiphase composites

A series of in-situ, deformation-processed metal matrix composites were produced by direct powder extrusion of blended constituents. The resulting composites are comprised of a metallic Ti-6Al-4V matrix containing dispersed and co-deformed discontinuously reinforced-intermetallic matrix composite (DR-IMC) reinforcements. The DR-IMCs are comprised of discontinuous TiB₂ particulate within a titanium trialuminide or near-γ Ti-47Al matrix. Thus, an example of a resulting composite would be Ti-6Al-4V+40 vol pct (Al₃Ti+30 vol pct TiB₂) or Ti-6Al-4V+40 vol pct (Ti-47Al+40 vol pct TiB₂), with the DR-IMCs having an aligned, high aspect ratio morphology as a consequence of deformation processing. The degree to which both constituents deform during extrusion has been examined using systematic variations in the percentage of TiB₂ within the DR-IMC, and by varying the percentage of DR-IMC within the metal matrix. In the former instance, variation of the TiB₂ percentage effects variations in relative flow behavior; while in the latter, varying the percentage of DR-IMC within the metallic matrix effects changes in strain distribution among components. The results indicate that successful co-deformation processing can occur within certain ranges of relative flow stress; however, the extent of commensurate flow will be limited by the constituents’ inherent capacity to plastically deform.     

Microstructure/processing relationships in reaction-synthesized titanium aluminide intermetallic matrix composites

Near-γ TiAl- and Al₃Ti-based intermetallic matrix composites have been produced using in-situ reaction-synthesis techniques. The intermetallic matrices have been reinforced with relatively high loadings (e.g., 20 to 50 vol pct) of dispersed TiB₂ particulates. It is shown that the as-synthesized TiB₂ size is strongly dependent on the specific alloy formulation; specifically, the TiB₂ size tends to increase as the nominal volume percent of TiB₂ in the composite increases. The observed size effect is determined to be associated with the temperature that is attained during the synthesis event, which is established primarily by the net exothermicity of the participating synthesis reaction(s). The exothermicity of the reactions can be assessed through the calculation of a formulations’s adiabatic temperature, which is found to increase with the percentage of TiB₂ over the range of approximately 10 to 60 vol pct. The coupling of a composite’s characteristic adiabatic temperature with the resulting reinforcement size provides direct links among composition, processing, and mechanical performance, since the size of a reinforcing particle is influential in establishing the interparticle spacing, which, in turn, establishes the strengthening potency of the dispersed phase within the composite.     

Composites ofγ + TaC in the Ni−Ta−C ternary system

The Ni−Ta−C ternary system has been studied at the Ni-rich end of the phase diagram. The investigation was directed toward developing a detailed picture of γ+TaC composites. Alloys were melted with Ta/C atomic ratios of 0.79 to 3.33 in an attempt to define the composition range that would produce two-phase γ+TaC eutectics. The liquidus trough rises in temperature across the ternary diagram moving away from the Ni−C eutectic (1320°C) and toward the Ni−Ni₃Ta eutectic (1380°C). Bulk chemistries were determined for aligned regions to map the liquidus trough compositions. Ratios of Ta/C atoms varied from 1.3 to 8.8 in the aligned regions. Matrix composition was determined by electron microprobe analysis, and lattice parameters of extracted TaC fibers were measured by X-ray diffraction. Fiber compositions ranged from TaC_0.99 to TaC_0.97 as the Ta/C ratio of the aligned region increased. The matrix compositions and TaC stoichiometries were used to map tie-lines across the ternary diagram. Volume fraction and microstructural features of the TaC phase were also studied. The volume fraction of TaC decreased from 6.7 vol pct to 1.7 vol pct as Ta/C increased from 1.3 to 8.8. The decreasing volume fraction can be explained by a lever-arm rule application for the ternary phase diagram, based on the liquidus trough and tie-line compositions determined in this study. The TaC growth axis was <111> in each case, but the carbide morphology changed progressively across the phase diagram. The change in morphology is primarily a consequence of the change in volume fraction. Implications of the findings of this study for more complex γ+MC eutectics will be discussed.     

The role of iron in the formation of porosity in Al-Si-Cu-based casting alloys: Part II. A phase-diagram approach

The mechanism by which iron causes casting defects in the AA309 (Al-5 pct Si-1.2 pct Cu-0.5 pct Mg) may be related to the solidification sequence of the alloy. Superimposing calculated segregation lines on the liquidus projection of the ternary Al-Si-Fe phase diagram suggests that porosity is minimized at a critical iron content when solidification proceeds directly from the primary field to the ternary Al-Si-βAl₅FeSi eutectic point. Solidification via the binary Al-βAl₅FeSi eutectic is detrimental to casting integrity. This hypothesis was tested by comparing the critical iron content observed in the standard AA309 alloy to that of a high-silicon (10 pct Si) variant of this alloy.     

The incorporation of self-propagating,high-temperature synthesis-formed Fe-TiB2 into ferrous melts

Steel-matrix particulate composites were processed by direct addition of an Fe-TiB₂ master alloy powder to a BS970:080M30 medium-carbon steel. This powder was produced using a self-propagating, high-temperature synthesis (SHS) reaction and consisted of a dispersion of fine TiB₂ particles (2 to 5 μm), respectively, in an iron binder. The addition of the Fe-TiB₂ powder resulted in the formation a parasitic Fe₂B phase and TiC within the steel microstructure. In response to this, an SHS master alloy composed of Fe-(50 pct TiB₂+50 pct Ti) was manufactured, which, when added to the steel, prevented the formation of Fe₂B and resulted in a composite containing a mixture of TiB₂ and TiC particles. The effect of master alloy composition and addition level on the microstructural phases generated is discussed in detail. The response to heat treatment of composite materials manufactured in this way was also investigated. It was found that an isothermal hold at 840 °C leads to a substantial softening of the material processed using the Fe-TiB₂ additive, while at 1000 °C, a hardness level equivalent to that of the as-cast material was maintained. The same heat treatment of samples in which the formation of Fe₂B was suppressed resulted in no appreciable difference in hardness level or microstructure.     

Some phase-diagram aspects of the manganese-carbon system

In the present work, differential thermal analysis (DTA) and electromotive force (emf ) methods were employed to investigate the Mn-C phase diagram around the eutectoid decomposition of Mn(γ). The eutectoid temperature and the composition were estimated to be 1031 K and 9.62 mol pct carbon, respectively. The temperature for the eutectoid decomposition of ε-carbide to Mn(γ) and Mn₂₃C₆ was found to be 1260 K, and the equilibrium composition of Mn(γ) corresponding to this three-phase reaction was 14.89 mol pct carbon. From the experimental data, the solubility of Mn₂₃C₆ in Mn(γ) was evaluated in the temperature range of 1031 to 1260 K using a two-sublattice model. On the basis of the present results, the relevant part of the Mn-C diagram was redrawn. Microscopic and X-ray analyses of quenched samples appear to be in support of the suggested phase diagram.     

Effects of Pr-Cu-Ti intergranular addition on microstructure and magnetic properties of heavy-rare-earth-free Nd-Fe-B sintered magnets

By intergranular addition of Pr-Cu-Ti alloy powders in the Nd-Fe-B sintered magnets with the normal B component, we propose an approach to the optimization of grain boundary and local Nd-Fe-B composition system. The coercivity is enhanced from 1.42 to 1.86 T, while further addition leads to a reduction in remanence and coercivity. The analyses of phase composition reveal that Ti mainly exists in the form of metallic Ti alloy, and part of Ti combines with B to form the TiB₂ phase after the liquid phase sintering process. This process results in a consumption of B in the local Nd-Fe-B composition system and a change of the grain boundary component, which contributes to the formation process of the RE₆(Fe,M)₁₄ phase after the annealing process. Therefore, with the modification of grain boundary and composition system, the intergranular addition of Pr-Cu-Ti induces the generation of continuous thin grain boundary phases. It promotes the intergrain exchange decoupling, increasing the coercivity in the annealed magnet. While the excess addition results in the segregation of TiB₂, as well as the precipitation of TiB₂ into the Nd-Fe-B phase, which leads to structural defects. Thus, the further effort for the addition alloy with Ti to reduce the deterioration of the microstructure will lead to further improvement in magnetic properties.     

Experimental Determination of the Liquidus in the High-Basicity Region in the Al2O3(25?mass?pct)-CaO-MgO-SiO2 and Al2O3(35?mass?pct)-CaO-MgO-SiO2 Systems

Liquidus in the Al₂O₃(25 mass pct)-CaO-MgO-SiO₂(<20 mass pct) and Al₂O₃(35 mass pct)-CaO-MgO-SiO₂(<20 mass pct) systems were determined experimentally in the high-CaO-containing region at 1873 K (1600 °C). For the Al₂O₃(35 mass pct)-CaO-MgO-SiO₂(<20 mass pct) system, liquidus data were also determined for 1773 K (1500 °C). The equilibrating and quenching technique with subsequent electron probe microanalyzer (EPMA) microanalysis were employed. Based on the data, liquidus lines were constructed for the 25 and 35 mass pct alumina planes at silica contents generally below 20 mass pct. The current results showed a slightly lower solubility of CaO and a higher solubility of MgO at 1873 K (1600 °C) for the 25 mass pct Al₂O₃ section compared with the existing phase diagram. At 1773 K (1500 °C), the result showed a slightly lower solubility of both CaO and MgO in the 35 mass pct Al₂O₃ section compared with the existing phase diagram. In addition, the activities of MgO, CaO, and Al₂O₃ were estimated at 1773 K and 1873 K (1500 °C and 1600 °C) using the phase diagram information.