<Emphasis Type="Italic">In-situ</Emphasis> reactive processing of nickel aluminides by laser-engineered net shaping

Nickel aluminide intermetallics (e.g., Ni₃Al and NiAl) are considered to be attractive materials for high-temperature structural applications. Laser-engineered net shaping (LENS) is a rapid prototyping process, which involves laser processing fine metal powders into three-dimensional shapes directly from a computer-aided design (CAD) model. In this work, an attempt has been made to fabricate aluminide intermetallic compounds via reactive in-situ alloying from elemental powders using the LENS process. In-situ reactive alloying was achieved by delivering elemental Ni and Al powders from two different powder feeders, eliminating segregation observed in the samples deposited by using the premixed elemental powders. Nickel aluminides of various compositions were obtained easily by regulating the ratio of their feed rates. The aluminide deposits exhibited a high solidification and subsolidus cracking susceptibility and porosity formation. The observed porosity resulted from a water-atomized Ni powder and can be minimized or eliminated by the use of a N₂-gas-atomized Ni powder of improved quality. Cracking was due to the combined effect of the high thermal stresses generated from the LENS processing and the brittleness of the intermetallics. Crack-free deposits were fabricated by preheating the substrate to a temperature of 450 °C to 500 °C during LENS processing. Compositionally graded Ni-Al deposits with a gradient microstructure were also produced by the in-situ reactive processing.     

Process efficiency measurements in the laser engineered net shaping process

A study of laser energy transfer efficiency, melting efficiency, and deposition efficiency has been conducted for the laser-engineered net-shaping process (LENS) for H-13 tool steel and copper powder deposits on H-13 tool steel substrates. This study focused on the effects of laser deposition processing parameters (laser power, travel speed, and powder mass flow rate) on laser beam absorption by the substrate material. Measurements revealed that laser energy transfer efficiency ranged from 30 to 50 pct. Laser beam coupling was found to be relatively insensitive to the range of processing parameters tested. Melting efficiency was found to increase with increasing laser input power, travel speed, and powder mass flow rate. A dimensionless parameter model that has been used to predict melting efficiency for laser beam welding processing was investigated for the LENS process. From these results, a semiempirical model was developed specifically for the LENS processing window. Deposition efficiency was also investigated and results show that under optimum processing conditions, the maximum deposition efficiency was approximately 14 pct. A semiempirical relation was developed to estimate deposition efficiency as a function of process efficiencies and LENS processing parameters. Knowledge of LENS process efficiencies measured in this study is useful to develop accurate heat flow and solidification models for the LENS process.     

Fabrication of carbide-particle-reinforced titanium aluminide-matrix composites by laser-engineered net shaping

TiAl-based titanium aluminide alloys and their composites reinforced with ceramic particles are considered to be important candidate materials for high-temperature structural applications. Laser-engineered net shaping (LENS) is a layered manufacturing process, which involves laser processing fine powders into three-dimensional components directly from a computer-aided design (CAD) model. In this work, the LENS process was employed to fabricate carbide-particle-reinforced titanium aluminide-matrix composites using TiC and gas-atomized Ti-48Al-2Cr-2Nb powders as the feedstock materials. The composites deposited by the LENS process were susceptible to solid-state cracking due to high thermal stresses. The microstructures of the laser-deposited monolithic and composite titanium aluminide materials were characterized using light optical microscopy (LOM), scanning electron microscopy (SEM), X-ray energy-dispersive spectroscopy (EDS) analysis, electron-probe microanalysis (EPMA), and X-ray diffraction (XRD) techniques. Effects of the LENS processing parameters on the cracking susceptibility and microstructure were studied. Crack-free deposits were fabricated by preheating the substrate to 450 °C to 500 °C during LENS processing. The fabricated composite deposits exhibit a hardness of more than twice the value of the Ti-6Al-4V alloy.     

Fabrication of carbide-particle-reinforced titanium aluminide-matrix composites by laser-engineered net shaping

TiAl-based titanium aluminide alloys and their composites reinforced with ceramic particles are considered to be important candidate materials for high-temperature structural applications. Laser-engineered net shaping (LENS) is a layered manufacturing process, which involves laser processing fine powders into three-dimensional components directly from a computer-aided design (CAD) model. In this work, the LENS process was employed to fabricate carbide-particle-reinforced titanium aluminide-matrix composites using Tic and gas-atomized Ti−48Al−2Cr−2Nb powders as the feedstock materials. The composites deposited by the LENS process were susceptible to solid-state cracking due to high thermal stresses. The microstructures of the laser-deposited monolithic and composite titanium aluminide materials were characterized using light optical microscopy (LOM), scanning electron microscopy (SEM), X-ray energy-dispersive spectroscopy (EDS) analysis, electron-probe microanalysis (EPMA), and X-ray diffraction (XRD) techniques. Effects of the LENS processing parameters on the cracking susceptibility and microstructure were studied. Crack-free deposits were fabricated by preheating the substrate to 450 °C to 500 °C during LENS processing. The fabricated composite deposits exhibit a hardness of more than twice the value of the Ti−6Al−4V alloy.     

Composition control in the direct laser-deposition process

Laser-engineered net shaping (LENS) is a solid freeform fabrication process that has the capability of producing functionally graded material (FGM) components by selectively depositing different powder materials in the melt pool at specific locations in the structure during part buildup. The composition in each layer of an FGM is dependent upon the degree of dilution between the substrate (or previous layer) and powder material. A study on the effects of LENS processing parameters (laser power, travel speed, and powder mass flow rate) on dilution was conducted for deposits of H-13 tool steel and copper powder on H-13 tool steel substrates. When varying a single processing parameter while holding all others constant, the dilution was found to increase with increasing laser input power and travel speed and decrease with increasing powder mass additions into the melt pool. A method for estimating dilution in LENS deposits was developed from knowledge of LENS process efficiencies and material thermophysical properties. A reasonable correlation was shown to exist between the experimentally measured dilution and the dilution calculated from the model.     

Experimental evidence of crystal fragmentation from highly undercooled Ni<Subscript>99</Subscript>B<Subscript>1</Subscript> melts processed on an electrostatic levitator

Employing an electrostatic levitator (ESL) equipped with a CO₂ laser heating setup, we solidified Ni₉₉B₁ bulk crystals through containerless processing at high undercoolings and observed grain-refined microstructures. The electron backscatter diffraction pattern (EBSP) and analysis of the twin directions were accomplished, from which the primary growth traces with a cellular-like structure were revealed on a macro-millimeter scale. In comparison with the strong mechanical electromagnetic stirring in a sample processed on an electromagnetic levitator, the ESL provides a quite quiescent state for the melt, which enables identification of the primary growth traces after solidification. The present observation supplied experimental evidence that the refined microstructure in the Ni₉₉B₁ alloys at the high undercooling regime was due to fragmentation of the primary growth crystal, rather than dynamic nucleation.     

Non-equilibrium transformations involving L1<Subscript>2</Subscript>-Al<Subscript>3</Subscript>Zr in ternary Al-X-Zr alloys

The metastable L1₂-Al₃Zr phase has been obtained as a solidification product on melt-spinning ternary Al-X-Zr (X = Cu, Ni) alloys. Different non-equilibrium effects of the metastable Al₃Zr phase (L1₂) have been observed in the as-solidified and heat-treated alloys. The solidification sequence begins with the formation of the L1₂-Al₃Zr (cubic) phase as a primary phase, followed by heterogeneous nucleation of α-Al. Morphological changes in the primary phase result in a shape transformation from a faceted cube to one with concave interfaces and protrusions along the corners, having a preferential growth along the 〈111〉 direction. This is brought about by a kinetic effect taking place during the growth of the L1₂-Al₃Zr phase into the surrounding liquid, as the alloy is quenched. In another instance, the primary L1₂-Al₃Zr phase nucleates as solid-state precipitates of the same L1₂-Al₃Zr phase on annealing, by dissolution and reprecipitation of solute, under the influence of moving grain boundaries. A third case shows the metastable L1₂ phase nucleating on the equilibrium DO₂₃-Al₃Zr phase, upon solidification. This is attributed to the sluggish growth kinetics of the latter.     

Formation of CaS on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO inclusions during solidification of steels

In this article, the effect of CaS formation on the evolution of Al₂O₃-CaO inclusions in low-carbon Al-killed and Ca-treated steel during the solidification process is investigated through high-temperature confocal scanning laser microscopy (CSLM). The inclusions started as mostly liquid-globular inclusions that did not agglomerate with each other on the melt surface but during solidification were seen to change shape into an irregular morphology. The shape change was found to be due to the reaction between the Al₂O₃-CaO inclusions with the dissolved S and Al in the melt, resulting in the formation of dense CaS shells around the inclusions. The melt composition during solidification, estimated from the observed solid δ-front advance rate, was compared to the thermodynamic limit for CaS precipitation. The observed growth rate of the CaS shell was found to initially increase with decreasing temperature because of the higher, solid δ-front advance rates at lower temperatures, which results in higher rates of S and Al partitioning. Once CaS had precipitated, the inclusions were found to form agglomerates on the melt surface because of fluid flow, initially, and later, the capillary depression.     

Processing,microstructure, and mechanical properties of cast <Emphasis Type="Italic">in-Situ</Emphasis> Al(Mg,Mn)-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>(MnO<Subscript>2</Subscript>) composite

Cast particulate composites, containing in-situ generated reinforcing particles of alumina, have been developed by solidification of slurry obtained by dispersion of externally added manganese dioxide particles (MnO₂) in molten aluminum, and alumina is formed by reaction of manganese dioxide with molten aluminum. The chemical reaction also releases manganese into molten aluminum. Magnesium is added to the melt in order to help wetting of alumina particles by molten aluminum and to retain the particles inside the melt. The present work aims to understand the influence of key parameters such as processing temperature, time, and the amount of MnO₂ particles added on the microstructure and mechanical properties of the resulting cast in-situ composites. The sequence of addition of MnO₂ particles and magnesium has significant influence on the microstructure and mechanical properties. Increasing processing temperature and time increases the extent of reduction of MnO₂ particles, generating more alumina particles as well as releasing more manganese to the matrix alloy. Alumina helps to nucleate finer and sometimes blocky MnAl₆ in the matrix of the composite and thereby results in relatively higher ductility and increased strength in the composite as compared to the base alloy of similar composition. Even in the presence of relatively higher porosity of 8 to 9 vol pct, one observes a percent elongation not below 7 to 8 pct, which is considerably higher than those observed in cast Al(Mg)-Al₂O₃ composite synthesized by externally added alumina particles.     

Effect of Planar Flow Melt Spinning Parameters on Ribbon Formation in Soft Magnetic Fe<Subscript>68.5</Subscript>Si<Subscript>18.5</Subscript>B<Subscript>9</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript> Alloy

The effect of planar flow melt spinning (PFMS) parameters on the continuity, surface quality, and structure of 10-mm-wide Fe_68.5Si_18.5B₉Nb₃Cu₁ ribbons has been investigated. The change in shape and stability of the melt puddle as a function of the processing parameter was studied using a high-speed imaging system and was correlated to ribbon formation. A window of process parameters for obtaining continuous ribbons with good surface quality has been evaluated. It has been observed that thinner ribbons are found to be more continuous because of higher ductility. The higher melt temperature leads to the formation of crystalline phase in as-spun ribbons, and this deteriorates the soft magnetic properties on annealing. The experimental results are corroborated with the numerical estimates, which suggest that the critical thickness for amorphous phase formation decreases with increasing initial melt temperature.     

The Interface of TiB<Subscript>2</Subscript> and Al<Subscript>3</Subscript>Ti in Molten Aluminum

In the grain refinement of aluminum, Al₃Ti and TiB₂ particles are introduced to reduce the casting grain size down to 200 micrometer level, which makes cold working possible. The particles are brought in by the addition of Al-Ti-B-type master alloys. It is generally believed that TiB₂ particles are stable and nucleate α-Al grains in solidification in the presence of titanium in solution from the dissolution of Al₃Ti particles in the master alloys. The titanium in solution either forms Al₃Ti layers on the surface of TiB₂ particles to promote the nucleation of α-Al grains or remains as solute to restrict the growth of α-Al grains in solidification. However, a consensus on a grain refinement mechanism is still to be reached due to the lack of direct observation of the three phases in castings. This paper presents finding of the TiB₂/Al₃Ti interfaces in an Al-Ti-B master alloy. It demonstrates a strong epitaxial growth of Al₃Ti on the surface of TiB₂ particles, a sign of the formation of an Al₃Ti layer on the surface of TiB₂ particles in grain refinement practice. The Al₃Ti layer has a crystal coherency with α-Al and hence offers a substrate for heterogeneous nucleation of α-Al grains. However, the layer must be dynamic to avoid the formation of compounded Al₃Ti and TiB₂ particles leading to the loss of efficiency in grain refinement.     

Quantitative characterization of the microstructure of two-phase TiB<Subscript>2</Subscript>+Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics using mean integral curvature

Two-phase TiB₂+Al₂O₃ ceramics with an interconnected or dispersed TiB₂ (minor)-phase microstructure can be produced by variations in processing parameters. A standard method of quantitative characterization of the microstructural bias, i.e., the degree of TiB₂ phase connectivity relative to its dispersion, is necessary to comprehend the mechanism(s) controlling the evolution of microstructure during processing. In this work, techniques derived from stereology were used to quantitatively characterize the microstructural bias on the basis of the connectivity and dispersion of the minor phase (TiB₂), in addition to the size of the TiB₂- and Al₂O₃-phase regions. The mean integral curvature calculated using the area particle-count and area tangent-count methods was determined to quantitatively describe the connectivity of the TiB₂ minor phase around the Al₂O₃ major phase. The results illustrate that, in spite of partial and mixed bias, integral curvature measurements (particularly those based on the area tangent-count method) provide a reliable and reproducible means for quantitative characterization of the two-phase biased microstructure.     

The Ca(SO<Subscript>4</Subscript>)-Na<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)-Ca<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript>-Na<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>) phase diagram

The phase diagram of the CaSO₄-Na₂SO₄-Ca₃(AsO₄)₂-Na₃(AsO₄) system was measured by differential thermal analysis and by an equilibration and quenching technique. Thermodynamic models were developed giving the Gibbs energies of all phases as functions of temperature and composition. Optimized model parameters were obtained by assessment of all available thermodynamic and phase equilibrium data. The models, which reproduce all the data within experimental error limits, were used to calculate the liquidus surface of the system. The modified quasi-chemical model in the quadruplet approximation was used for the liquid solution. For the various solid solution phases, the modified quasi-chemical model, which accounts simultaneously for short-range-ordering among first-nearest-neighbor (FNN) and second-nearest-neighbor (SNN) pairs, was used for the first time within the framework of the compound energy formalism. The distinction between true model parameters and formalism parameters is made. Implications of the work for the potential use of sulfate fluxes for copper refining are discussed.     

Examination of Multiphase (Zr,Ti)(V,Cr,Mn,Ni)<Subscript>2</Subscript> Ni-MH Electrode Alloys: Part I. Dendritic Solidification Structure

The solidification microstructures of three nine-element Zr-Ni–based AB₂ type C14/C15 Laves hydrogen storage alloys are determined. The selected compositions represent a class of alloys being examined for usage as an MH electrode in nickel metal-hydride batteries that often have their best properties in the cast state. Solidification is accomplished by dendritic growth of hexagonal C14 Laves phase, peritectic solidification of cubic C15 Laves phase, and formation of cubic B2 phase in the interdendritic regions. The B2 phase decomposes in the solid state into a complex multivariate platelike structure containing Zr-Ni–rich intermetallics. The observed sequence C14/C15 upon solidification agrees with predictions using effective compositions and thermodynamic assessments of the ternary systems, Ni-Cr-Zr and Cr-Ti-Zr. Experimentally, the closeness of the compositions of the C14 and C15 phases required the use of compositional mapping with an energy dispersive detector capable of processing a very high X-ray flux to locate regions in the microstructure for quantitative composition measurement and transmission electron microscope examination.     

<Emphasis Type="Italic">In-Situ</Emphasis> Observation on the Diversified Morphology and Growth Behavior of Al<Subscript>3</Subscript>Ni Phase at the Liquid Al/Solid Ni Interface

The morphology and growth behavior of Al₃Ni in the liquid Al/solid Ni interface were observed through synchrotron radiation. The formation time and mechanism of Al₃Ni are connected with saturation of the molten layer. In unsaturated conditions, the growth of columnar Al₃Ni formed during solidification governed by the melting of small grains accompanied by the growth of adjacent large grains and coalescence of grains near the tips. Conversely, the scallop-type Al₃Ni formed in holding showed annexation of adjacent small grains with its morphology changing from scallop to hemisphere.     

Stray Grain Formation in Welds of Single-Crystal Ni-Base Superalloy CMSX-4

Autogenous welds on the single-crystal (SX) alloy CMSX-4 were prepared over a wide range of welding parameters and processes to investigate the formation and behavior of stray grains (SGs). The quantity and location of SGs in the welds were analyzed by orientation imaging microscopy (OIM). Heat- and fluid-flow modeling was conducted to understand the influence of welding parameters on the local solidification conditions and resultant SG formation tendency. The results indicate that constitutional supercooling and SG formation are generally reduced in low-power, high-travel-speed welds. Because of the complex effect of travel speed on temperature gradient and solidification velocity, the worst conditions for SG formation in alloy CMSX-4 for the conditions examined here occur at intermediate travel speeds of ~6 mm/s. These findings were corroborated with heat-transfer/fluid-flow modeling simulations that were coupled with SG predictions. These calculations also indicate that SG formation will be greatest where different regions of dendrite growth intersect, due to the so-called off-axis heat flow. For a given set of welding conditions, the amount of SGs will also vary with substrate orientation. This effect is attributed to differences in the number and location of dendrite growth intersection regions within the melt pool that occur with changes in substrate orientation.     

Effects of Zr on the eutectoid decomposition behavior of Nb<Subscript>3</Subscript>Si into (Nb)/Nb<Subscript>5</Subscript>Si<Subscript>3</Subscript>

The effect of Zr on the formation of Nb/Nb₅Si₃ lamellar microstructure by eutectoid decomposition reaction of Nb₃Si is investigated. It has been shown that the kinetics of the eutectoid decomposition of high-temperature Nb₃Si phase into Nb and Nb₅Si₃ phases are sluggish in the binary Nb-Si system and that they are enhanced by Zr additions. The time-temperature-transformation (TTT) diagram for the decomposition is experimentally determined and the acceleration of the reaction by small Zr addition of 1.5 at. pct is confirmed by comparison with the reported TTT curves of binary and ternary alloys containing Ti. The role of the ternary element on the decomposition kinetics is discussed in terms of crystallographic orientation relationships (ORs) and Zr distribution in the parent Nb₃Si phase during solidification. This article is based on a presentation made in the symposium entitled “Beyond Nickel-Base Superalloys,” which took place March 14–18, 2004, at the TMS Spring meeting in Charlotte, NC, under the auspices of the SMD-Corrosion and Environmental Effects Committee, the SMD-High Temperature Alloys Committee, the SMD-Mechanical Behavior of Materials Committee, and the SMD-Refractory Metals Committee.     

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO Slags

The crystallization kinetics of CaO-SiO₂-Al₂O₃-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent (n), rate coefficient (K), and effective activation energy of crystallization (E _A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.