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At least 559 records · Page 31

Composition-Dependent Photoluminescence Properties and Anti-Counterfeiting Applications of A 2 AgX 3 (A = Rb, Cs; X = Cl, Br, I)

Copper(I) halides are emerging as attractive alternatives to lead halide perovskites for optical and electronic applications. However, blue-emitting all-inorganic copper(I) halides suffer from poor stability and lack of tunability of their photoluminescence (PL) properties. In this work, the preparation of silver(I) halides A 2 AgX 3 (A = Rb, Cs; X = Cl, Br, I) through solid-state synthesis is reported. In contrast to the Cu(I) analogs, A 2 AgX 3 are broad-band emitters sensitive to A and X site substitutions. First-principle calculations show that defect-bound excitons are responsible for the observed main PL peaks in Rb 2 AgX 3 and that self-trapped excitons (STEs) contribute to a minor PL peak in Rb 2 AgBr 3 . This is in sharp contrast to Rb 2 CuX 3 , in which the PL is dominated by the emission by STEs. Moreover, the replacement of Cu(I) with Ag(I) in A 2 AgX 3 significantly improves photostability and stability in the air under ambient conditions, which enables their consideration for practical applications. Thus, luminescent inks based on A 2 AgX 3 are prepared and successfully used in anti-counterfeiting applications. The excellent light emission properties, significantly improved stability, simple preparation method, and tunable light emission properties demonstrated by A 2 AgX 3 suggest that silver(I) halides may be attractive alternatives to toxic lead halide perovskites and unstable copper(I) halides for optical applications.

36 MATERIALS SCIENCE↗

Ion irradiation induced crystalline disorder accelerates interfacial phonon conversion and reduces thermal boundary resistance

Traditional understanding of the thermal boundary resistance (TBR) across solid-solid interfaces posits that the vibrational densities of states overlap between materials dictates interfacial energy transport, with phonon scattering occurring at the interface. Using atomistic simulations, we show a mechanism for control of TBR; point defects near an interface can lead to both short- and midrange disorder, accelerating the conversion of vibrational energy between bulk and interfacial modes, ultimately reducing the TBR. In conclusion, we experimentally demonstrate this reduction through ion irradiation of gallium nitride and subsequently measuring the TBR across Al/GaN interfaces.

Pfeifer, Thomas W.↗

Crystal Growth of II-VI Semiconducting Alloys by Directional Solidification

This research study is investigating the effects of a microgravity environment during the crystal growth of selected II-VI semiconducting alloys on their compositional, metallurgical, electrical and optical properties. The on-going work includes both Bridgman-Stockbarger and solvent growth methods, as well as growth in a magnetic field. The materials investigated are II-VI, Hg(1-x)Zn(x)Te, and Hg(1-x)Zn(x)Se, where x is between 0 and 1 inclusive, with particular emphasis on x-values appropriate for infrared detection and imaging in the 5 to 30 micron wavelength region. Wide separation between the liquidus and solidus of the phase diagrams with consequent segregation during solidification and problems associated with the high volatility of one of the components (Hg), make the preparation of homogeneous, high-quality, bulk crystals of the alloys an extremely difficult nearly an impossible task in a gravitational environment. The three-fold objectives of the on-going investigation are as follows: (1) To determine the relative contributions of gravitationally-driven fluid flows to the compositional redistribution observed during the unidirectional crystal growth of selected semiconducting solid solution alloys having large separation between the liquidus and solidus of the constitutional phase diagram; (2) To ascertain the potential role of irregular fluid flows and hydrostatic pressure effects in generation of extended crystal defects and second-phase inclusions in the crystals; and, (3) To obtain a limited amount of "high quality" materials needed for bulk crystal property characterizations and for the fabrication of various device structures needed to establish ultimate material performance limits. The flight portion of the study was to be accomplished by performing growth experiments using the Crystal Growth Furnace (CGF) manifested to fly on various Spacelab missions.

Lehoczky, Sandor L.↗

Friction Stir Welding of SiC/Aluminum Metal Matrix Composites

Friction Stir Welding (FSW) is a new solid state process for joining metals by plasticizing and consolidating materials around the bond line using thermal energy producing from frictional forces. A feasibility study for FSW of Metal Matrix Composites (MMC) was investigated using aluminum 6092 alloy reinforced with 17% SiC particulates. FSW process consists of a special rotating pin tool that is positioned to plunge into the MMC surface at the bond line. As the tool rotates and move forward along the bond line, the material at the bond line is heated up and forced to flow around the rotating tip to consolidate on the tip's backside to form a solid state joint. FSW has the potential for producing sound welds with MMC because the processing temperature occurs well below the melting point of the metal matrix; thereby eliminating the reinforcement-to-matrix solidification defects, reducing the undesirable chemical reactions and porosity problems.

Lee, Jonathan A.↗

High frequency atomic tunneling yields ultralow and glass-like thermal conductivity in chalcogenide single crystals

Crystalline solids exhibiting glass-like thermal conductivity have attracted substantial attention both for fundamental interest and applications such as thermoelectrics. In most crystals, the competition of phonon scattering by anharmonic interactions and crystalline imperfections leads to a non-monotonic trend of thermal conductivity with temperature. Defect-free crystals that exhibit the glassy trend of low thermal conductivity with a monotonic increase with temperature are desirable because they are intrinsically thermally insulating while retaining useful properties of perfect crystals. However, this behavior is rare, and its microscopic origin remains unclear. Here, we report the observation of ultralow and glass-like thermal conductivity in a hexagonal perovskite chalcogenide single crystal, BaTiS 3 , despite its highly symmetric and simple primitive cell. Elastic and inelastic scattering measurements reveal the quantum mechanical origin of this unusual trend. A two-level atomic tunneling system exists in a shallow double-well potential of the Ti atom and is of sufficiently high frequency to scatter heat-carrying phonons up to room temperature. While atomic tunneling has been invoked to explain the low-temperature thermal conductivity of solids for decades, our study establishes the presence of sub-THz frequency tunneling systems even in high-quality, electrically insulating single crystals, leading to anomalous transport properties well above cryogenic temperatures.

36 MATERIALS SCIENCE↗

Impact of chemical ordering on thermodynamic properties of point defects and Xe substitutional in U-10Mo

The accurate knowledge of defect energetics is critical to understanding the aging and irradiation behavior of U-10Mo nuclear fuel, which is selected as the fuel type for conversion of the United States High-Performance Research Reactors (HPRRs). Furthermore, using hybrid molecular dynamics and Monte Carlo (MDMC) simulation, we studied the impact of chemical ordering on the formation energies of vacancies, interstitials, and the solution energy of the Xe substitutionals. Instead of forming a random solid solution (RSS), substantial short-range-order (SRO) develops in U-10Mo, particularly at low temperatures. Mo atoms are found to repel each other and prefer U-rich local atomic environments within the 1st nearest neighbor (1NN) cutoff. Compared to the case of a RSS, the state with equilibrated Mo ordering shifts the distributions of vacancy and interstitial formation energies due to the dependence of defect energies on the local atomic environment, without a clear effect on Xe solution energy. In the operation temperature range (100–250 °C) of U-Mo fuels, neglecting SRO can lead to an inaccurate estimate of thermal equilibrium point defect concentrations by over an order of magnitude and incorrectly predict the preference among different types of dumbbells, highlighting the critical importance of accounting for the impact of chemical ordering for accurate atomistic calculations of defect properties.

Molecular dynamics and Monte Carlo (MDMC)↗

Thermodynamic and Kinetic Barriers Limiting Solid-State Reactions Resolved through In Situ Synchrotron Studies of Lithium Halide Salts

Although halide salts such as LiCl and LiBr are routinely used as a source of Li ions during ion exchange reactions, a detailed understanding of the processes controlling the rates of these reactions is presently lacking. Recently, it has been discovered that the rate limiting barriers for ion exchange are commonly associated with these salts rather than the ceramic target of ion exchange, making it important to quantitatively understand of salt processes. Here it is demonstrated that in situ synchrotron studies of ion exchange reactions can be used to precisely quantify the thermodynamic activation energies associated with these solid state reactions in a manner that can be directly compared with predictions from density functional theory (DFT). While the temperature dependence of the LiCl reaction rate is found to be set by a barrier associated with ion hopping, it was discovered that for LiBr it is also affected by the defect formation energy – an energy found to be substantially lower than predicted by DFT. Furthermore, it is shown that when reaction rates for different relative amounts of reactants are varied, it is possible to identify the rate-limiting reagent and to elucidate an overall scaling relationship that controls the concentration-dependence of the reaction rate. Also, it is demonstrated that global fits across doped and undoped salts can be used to probe both intrinsic and extrinsic vacancy concentrations. This improved understanding of ion exchange mechanisms can be used to accelerate ion exchange reaction rates by orders of magnitude. In conclusion, the techniques demonstrated here can be broadly applied to probe the kinetics and thermodynamics of solid state reactions.

36 MATERIALS SCIENCE↗

Optical and electronic functionality arising from controlled defect formation in nanoscale complex oxide lateral epitaxy

Epitaxial crystallization of complex oxides provides the means to create materials with precisely selected composition, strain, and orientation, thereby controlling their functionalities. Extending this control to nanoscale three-dimensional geometries can be accomplished via a three-dimensional analog of oxide solid-phase epitaxy, lateral epitaxial crystallization. The orientation of crystals within laterally crystallized SrTiO 3 systematically changes from the orientation of the SrTiO 3 substrate. This evolution occurs as a function of lateral crystallization distance, with a rate of approximately 50° μm -1 . The mechanism of the rotation is consistent with a steady-state stress of tens of megapascal over a 100–nanometer scale region near the moving amorphous/crystalline interface arising from the amorphous-crystalline density difference. Second harmonic generation and piezoelectric force microscopy reveal that the laterally crystallized SrTiO 3 is noncentrosymmetric and develops a switchable piezoelectric response at room temperature, illustrating the potential to use lateral crystallization to control the functionality of complex oxides.

36 MATERIALS SCIENCE↗

All-optical reconfiguration of single silicon-vacancy centers in diamond for non-volatile memories

Strain engineering is vital for tuning the optical and spin properties of solid-state color centers, enhancing spin coherence and compensating emission wavelength shift. Here, we develop an all-optical approach to directly modify the local strain of color centers at the nanoscale by migrating the nearby defect. High-power pulsed optical irradiation triggers defect migration, which subsequently leads to the redistribution of the local crystal lattice of the host material. This redistribution alters the strain experienced by nearby color centers. Using silicon-vacancy centers in diamond, we validate this method and demonstrate a ground state splitting enhancement of up to 1.8 THz. Unlike conventional methods, our approach requires no external fields or nanostructure modifications, enabling non-volatile strain control and optical memory functionality across wide temperature ranges. Its local, permanent nature offers a scalable path for enhancing spin coherence in large-scale quantum systems and has potential applications in photonic machine learning.

Nanoscale devices↗

Using Inorganic Crystals To Grow Protein Crystals

Solid materials serve as nucleating agents. Protein crystals induced by heterogeneous nucleation and in some cases by epitaxy to grow at lower supersaturations than needed for spontaneous nucleation. Heterogeneous nucleation makes possible to grow large, defect-free single crystals of protein more readily. Such protein crystals benefits research in biochemistry and pharmacology.

Shlichta, Paul J.↗

Growth experiment of narrow band-gap semiconductor PbSnTe single crystals in space (M-1)

An experiment on crystal growth of Pb(1-x)Sn(x)Te in microgravity is planned. This material is an alloy of the compound semiconductors PbTe and SnTe. It is a promising material for infrared diode lasers and detectors in the wavelength region between 6 and 30 micron. Since the electrical properties of Pb(1-x)Sn(x)Te depend greatly on the Pb/Sn ratio and crystalline defects as well as impurity concentration, homogeneous, defect-free, high-quality crystals are anticipated. Although many growth methods, such as the pulling method, the Bridgman method, the vapor growth method, etc., have been applied to the growth of Pb(1-x)Sn(x)Te, large, homogeneous, low-defect-density crystals have not yet been grown on Earth. The unsuccessful results were caused by buoyancy-driven convection in the fluids induced by the specific gravity difference between heated and cooled fluids on Earth. A crystal is grown by cooling the melt from one end of the ampoule. In crystal growth from the melt, about 30 percent of the SnTe in the melt is rejected at the solid-liquid interface during solidification. On Earth, the rejected SnTe is completely mixed with the remaining melt by convection in the melt. Therefore, SnTe concentration in the melt, and accordingly in the crystal, increases as the crystal grows. In the microgravity environment, buoyancy-driven convection is suppressed because the specific gravity difference is negligible. In that case, the rejected SnTe remains at the solid-liquid interface and its concentration increases only at the interface. If the growth rate is higher than the PbTe-SnTe interdiffusion rate, the amount of SnTe which diffuses from the interface into the melt increases as SnTe piles up at the interface, and finally it balances the amount of rejected SnTe during solidification, resulting in steady-state SnTe transportation at the interface. By using this principle, compositionally homogeneous crystals can be grown. Furthermore, low-defect-density crystals will be grown in microgravity, because convection causes crystalline defects by mising hot and cold fluids and generating temperature fluctuations in them.

Yamada, Tomoaki↗

Microstructure and mechanical properties of friction stir welded Haynes 282

Advanced ultrasupercritical (A-USC) steam plants are designed to operate at high temperatures and pressures due to the necessity for higher operational efficiency. The extreme operating conditions of A-USC requires the deployment of precipitation strengthened Ni-base alloys that exhibit elevated temperature strength and good fabricability. Fusion welding of precipitation strengthened nickel alloys lead to solidification cracking in fusion zone and/or liquation cracking in heat affected zone. Therefore, an alternative non-melting welding technique is a necessity to efficiently join nickel alloys. In the current study, friction stir welding, a solid state joining technique was implemented on a precipitation strengthened nickel-based superalloy, Haynes 282. Detailed microstructural and mechanical properties characterization was carried out. The processed region exhibited wrought, fine-grained microstructure, absence of weld defects such as voids and cracks and absence of elemental segregation. Both hardness and cross-weld tensile tests demonstrated that the weld region was stronger than the base material. And the cross-weld tensile samples failed in the base material. Based on joint efficiency analysis, friction stir welded Haynes 282 outperformed fusion welds.

36 MATERIALS SCIENCE↗

Tool Measures Depths of Defects on a Case Tang Joint

A special-purpose tool has been developed for measuring the depths of defects on an O-ring seal surface. The surface lies in a specially shaped ringlike fitting, called a capture feature tang, located on an end of a cylindrical segment of a case that contains a solid-fuel booster rocket motor for launching a space shuttle. The capture feature tang is a part of a tang-and-clevis, O-ring joint between the case segment and a similar, adjacent cylindrical case segment. When the segments are joined, the tang makes an interference fit with the clevis and squeezes the O-ring at the side of the gap.

Ream, M. Bryan↗

A combined ensemble-volume average homogenization method for lattice structures with defects under dynamic and static loading

In the study of lattices structures, both experiments and numerical simulations are often conducted with small samples. Using combined ensemble and volume averaging, this work introduces a method to extract a macroscopic constitutive response of a lattice material from numerical simulations performed in periodic domains. The domain size needed to obtain statistically accurate results is investigated. Similar to molecular dynamics, the concept of the virial stress is introduced after homogenized equations are derived using the ensemble averaging method. Under static conditions, the virial stress is shown to agree with the volume averaged solid stress. Using the homogenization method, constitutive relations for this stress can be obtained from systems with uniform strains. Application of such obtained constitutive relations to more general cases results in an error proportional to the square of the ratio between the lattice length scale and the macroscopic length scale. Taking advantage of this property, numerical simulations are performed in systems with a uniform gradient of the average velocity. The volume average method is then used to accelerate convergence when studying lattices with defects. To avoid the artificial numerical time scale from the size of a representative volume element divided by the wave speed, a numerical scheme is developed to enforce a spatially uniform velocity gradient within the computational domain while allowing fluctuations of the velocity or displacement to develop naturally. To account for probability distribution of lattice defects, the stress is calculated as the ensemble-volume averaged value. For dynamic systems, energy dissipation properties are also studied.

36 MATERIALS SCIENCE↗

The importance of properties in modeling

Casting and welding of superalloys, stainless steel and titanium alloys are processes which can be improved through modeling of heat flow, fluid flow, residual stress development, and microstructural evolution. These simulations require inputs of thermophysical data, some of which involves the partially or totally liquid state. In particular, these processes involve melting, flow in the liquid, and solidification. Modeling of such processes can lead to an improved understanding of defects such as shrinkage, inclusions, cracks, incomplete filling (or penetration), macrosegregation, improper grain structure, and deviations from dimensional specifications. Effective modeling can shorten process development time and improve quality. An approach to these problems is to develop efficient models; validate through correlations with thermal, distortion, and microstructural data; run parametric studies; extract knowledge based rules; and apply to adaptive closed loop control systems. With the appropriate pre- and post-processing, such analyses can be made 'user friendly'. This would include graphical user interfaces as well as realistic images and color maps. In such form, these models can be used for sensitivity analyses, which are useful in defining appropriate sensors and in the development of control strategies. Such modeling can be done at several levels, e.g., the MARO level, modeling large scale phenomena such as heat and fluid flow or material deformation; the MICRO level, modeling the development of dendrites, grains or precipitates; or at the NANO level, modeling point defects, dislocations, stacking faults, etc. There are many computational issues associated with these simulations, e.g. computational efficiency and accuracy. In addition, there are many materials issues, not the least of which is the availability of accurate high temperature thermophysical data for complex alloys. This would include latent heat of fusion, temperature dependent heat capacity and thermal conductivity (for liquid and solid), viscosity, surface tension, thermal expansion, mechanical properties, etc. Preliminary data is frequently gathered from the literature; however, this is often not available for modern alloys. If additional data are required, measurements can be used; however, these are costly, time consuming and can be erroneous due to a lack of testing standards or impure materials. Microstructural predictors can be extracted from thermal information, e.g. cooling rate and thermal gradient; the prediction of microstructure is dependent on solidus and liquidus temperature, mushy zone permeability, the solidification curve, volume changes, phase transformations, alloying effects (such as surface tension or viscosity), mold/metal reactions, metal/environment reactions, etc. Defect maps may be needed to predict the onset of shrinkage, hot cracking or 'freckling'. Constants may be needed for stress relaxation, dendrite coarsening, vaporization, etc. Visualization was used as a tool to better comprehend complex data sets associated with the analysis of directional solidification (including crystal growth) and welding. Examples include not only isotherms, but also cooling rate, growth rate and thermal gradient. The latter two are not single valued scalars, but rather time and space dependent vector fields. Efficient models were developed for both casting and welding to predict heat flow and the relationship to dendrite and grain growth. These codes include many of the non-linear effects, e.g. radiation, which dominate these processes. The home-built FDM code(s) were designed to be useful not only to the scientist, but also to the process engineer. Special output can be requested to compare directly to experimental data. Visualization procedures were developed to visualize critical results, e.g. fusion zone width at the surface opposite that where the arc is applied ('penetration'). Both elaborate and simplified distortion analyses were carried out. It is clear that extensive mechanical property data are critical in order to accurately predict residual stress patterns. A scheme is currently being developed to integrate these modeling tools into a set of control algorithms; however, the success of this approach is critically dependent on the availability of accurate high temperature thermophysical data.

Giamei, A. F.↗

Correlation between microstructure and residual stress formation in friction stir welded armor steels characterized by neutron diffraction

Friction stir welding (FSW) is a solid-state joining process that minimizes the heat-affected zone (HAZ) compared with fusion-based arc welding, making it well suited for joining martensitic armor steels where hardness and ballistic resistance are critical. This study investigates residual stress formation in three defect-free FSW butt-joint configurations relevant to armored-vehicle fabrication: similar rolled homogeneous armor (RHA–RHA, Case 1), similar high-hardness armor (HHA–HHA, Case 2), and dissimilar HHA–RHA (Case 3) joints produced under temperature-controlled conditions (770 °C). Neutron diffraction was employed to quantify the magnitude and spatial distribution of residual stresses in the longitudinal, transverse, and normal directions and to correlate them with weld microstructure and hardness. Tensile residual stresses were concentrated in the softened HAZ, reaching approximately 300 MPa for Case 2 and 400 MPa for Case 1 (≈50–70 % of the base-metal yield strength; ∼581 MPa for RHA and ∼566 MPa for HHA), while compressive residual stresses dominated the stir zone. The spatial extent of tensile stresses scaled with the width of the softened HAZ, which was largest in the dissimilar HHA–RHA joint and smallest in the HHA–HHA joint. Full-width-at-half-maximum (FWHM) analysis revealed low microstrain in overtempered HAZ regions and high microstrain in the stir zone associated with severe plastic deformation and fresh martensite formation. This work demonstrates that residual stress evolution in FSW of martensitic armor steels is governed not primarily by peak temperature or thermal contraction, as inferred from fusion-welding analogies, but by the competition between transformation-induced volumetric expansion and tempering-induced stress relaxation. The relative dominance of these mechanisms is shown to depend on alloy hardenability and local thermal history, leading to more extensive HAZ softening and broader tensile stress regions in the lower-hardenability RHA steel. These findings establish a transferable mechanistic framework for optimizing solid-state joining strategies in high-strength steels and other transformation-hardening alloys beyond armor applications.

Friction stir welding↗

Development of Corrosion- and Erosion-Resistant Coatings for Advanced Ultra-Supercritical Materials

This final report summarized the research efforts and major findings of the Phase I Project “Development of Corrosion- and Erosion-Resistant Coatings for Advanced Ultra-Supercritical Materials”, for the period of October 1, 2019 – Sept. 30, 2021. This project is a collaborative endeavor between Tennessee Tech University, Purdue University, Oak Ridge National Laboratory, Siemens Corporation, and Eastern Plating, LLC, aiming at improving the durability and lifetime of high-pressure (HP) steam turbine blades in advanced ultra-supercritical (A-USC) coal-fired power plants through the development of corrosion/erosion-resistant coatings manufactured via a low-cost electrolytic codeposition process. While Tribaloy alloy T-400C was identified by the U.S. A-USC Materials Consortium as a promising coating composition, further composition optimization is needed to enhance its corrosion and erosion resistance for protecting the A-USC Ni-base turbine components. An integrated computational and experimental approach was employed to optimize coating composition/microstructure and processing parameters. In order to identify candidate coating compositions that could offer balanced properties, thermodynamic calculations were performed to explore the γ+Laves composition space in the Co-Ni-Cr-Mo-Si system with different alloying additions at 600-800 °C. Guided by the calculation results, experimental assessment of selected alloys led to the development of a new generation of Tribaloy compositions with the optimal levels of Cr, Mo and Si, reactive element (e.g., 0.4-0.6 wt.% Y) and other alloying additions. The low-cost and non-line-of-sight electro-codeposition process was employed to deposit a Ni(Co)-CrMoSiY composite coating on commercial Haynes 282 (H282) Ni-base alloy. A diffusion treatment was subsequently applied to convert the composite to the Tribaloy-type coating. Both the codeposition parameters and heat treatment conditions were varied to achieve the desired coating composition, microstructure and phase constituents. In addition, since additive manufacturing (AM) may be an alternative cost-saving option for potential A-USC turbine repair, laser direct deposition was explored to fabricate the H282 alloy with minimal defects. The electro-codeposited Tribaloy coating was also applied to the AM H282 substrate to demonstrate the viability of the coating process in improving the surface finish of AM alloys. Both high-temperature oxidation performance and solid particle erosion (SPE) resistance of model alloys and electro-codeposited coatings were evaluated. About 25 model alloys with various Cr/Mo ratios and reactive element levels, as well as partial substitution of Mo with Nb were evaluated with regard to their oxidation resistance in both air and pure steam at 760-800°C. Compositions based on Ni(Co)-20Cr-18Mo-2.6Si-0.6Y (wt.%) showed significantly improved oxidation resistance over the baseline T400-C. Based on the alloy development results, three generations of new Tribaloy coatings (Gen-1, Gen-2, and Gen-3) with various Mo/Cr contents and Y levels were prepared via electro-codeposition and their microstructure/performance were evaluated. Outstanding air and steam oxidation resistance was achieved for the Gen-2 and Gen-3 coatings. Furthermore, while the SPE resistance of the coatings depended on many factors such as temperature, environment, erodent, velocity and impact angle, the coated samples exhibited similar or better SPE resistance compared to the H282 substrate when magnetite was used as erodent (which is a realistic erodent in A-USC steam turbines). The new Tribaloy coatings also had good long-term compatibility with the H282 alloy substrate. The two large-sized rotating barrels were designed, constructed, and employed to coat dummy HP blades. Uniform coating thickness and microstructure were achieved at various blade locations. Also, a preliminary techno-economic analysis of the proposed coating process was conducted to quantify the cost-effectiveness and to assess the commercial viability of the corrosion- and erosion-resistant coatings. It is estimated that a cost reduction of ~30% could be achieved with the electro-codeposition coating process over the state-of-the-art high velocity oxygen fuel (HVOF) thermal spray. Compared to the leading Tribaloy coating technologies such as HVOF and plasma transfer alloying, electro-codeposition based process has advantages such as low-cost process equipment, uniform deposition even for complex shapes, low levels of contaminants/porosities, reduction of powder waste, and potentially better surface finish and longer turbine service life. The Phase 1 study has demonstrated that it is feasible to develop an electro-codeposited Tribaloy coating with balanced corrosion and erosion properties, even though additional research efforts such as further coating process scale-up and longer-term performance evaluation under realistic A-USC conditions are clearly needed.

20 FOSSIL-FUELED POWER PLANTS↗

Use of rotation to suppress thermosolutal convection in directionally solidified binary alloys

Effects of rotation on onset of convection during plane-front directional solidification of Pb-Sn and the pseudobinary system mercury cadmium telluride (Hg(1-x)Cd(x)Te), and on dendritic solidification of Pb-Sn have been studied by means of linear stability analysis. Incorporating Coriolis and centrifugal accelerations into the momentum equation of Coriell et al., we find that under realistic processing conditions, a large degree of stabilization can be achieved using modest rotation rates for both Pb-Sn and mercury cadmium telluride. At a growth velocity of 5 micron/sec and nominal liquid-side temperature gradient of 200 K/cm in Pb-Sn, rotation at 500 rpm results in a hundredfold increase in the critical Sn concentration. Large increases in the maximum allowable growth velocity at fixed melt composition are also attainable with modest rotation rates. The effect is amplified under conditions of reduced gravitational acceleration. For Hg(1-x)Cd(x)Te, we have also studied the nonrotating case. The key differences are due to the existence of a composition range for Hg(1-x)Cd(x)Te in which the melt density has a local maximum as a function of temperature. When the melt solidifies by cooling from below, the liquid density may initially increase with distance above the interface, before ultimately decreasing as the melt temperature increases above the value at which the local density maximum occurs. In contrast to the Pb-Sn case where density depends monotonically on temperature and composition, for Hg(1-x)Cd(x)Te there exists a critical value of the growth velocity above which plane-front solidification is unstable for all bulk CdTe mole fractions. Again, rotation leads to significant inhibition of onset. We identify the predicted stabilization with the Taylor-Proudman mechanism by which rotation inhibits thermal convection in a single-component fluid heated from below. In a binary liquid undergoing solidification, rotation inhibits the onset of buoyancy-driven convection, and has no effect on the short-wavelength morphological instability. At large growth velocities, the plane-front interface between liquid and solid becomes unstable with respect to a morphological instability and solidification occurs dendritically, with a mushy zone of dendrites and interdendritic fluid separating the solid from the melt. For the Pb-Sn system, rotation substantially suppresses the onset of convection in the mushy zone and in the overlying liquid, holding open the promise that rotation can suppress freckling and other macrosegregation defects.

Pearlstein, Arne J.↗