Investigation of the Effects of Ni, Fe, and Mn on the Formation of Complex Intermetallic Compounds in Al-Si-Cu-Mg-Ni Alloys

The aim of this work is to partially substitute Fe and Mn for Ni in the 3HA piston alloy and to study the consequences through microstructural evaluation and the thermal analysis technique. Three types of near-eutectic alloys containing (2.6 wt pct Ni-0.2 wt pct Fe-0.1 wt pct Mn), (1.8 wt pct Ni-0.75 wt pct Fe-0.3 wt pct Mn), and (1 wt pct Ni-1.15 wt pct Fe-0.6 wt pct Mn) were produced, and their solidification was studied at the cooling rate of 0.9 K/s (°C/s) using the computer-aided thermal analysis technique. Optical microscopy and scanning electron microscopy were used to study the microstructure of the samples, and energy dispersive X-ray (EDX) analysis was used to identify the composition of the phases. Also, the quantity of the phases was measured using the image analysis technique. The results show that Ni mainly participates as Al₃Ni, Al₉FeNi, and Al₃CuNi phases in the high Ni-containing alloy (2.6 wt pct Ni). In addition, substitution of Ni by Fe and Mn makes Al₉FeNi the only Ni-rich phase, and Al₁₂(Fe,Mn)₃Si₂ appears as an important Fe-rich intermetallic compound in the alloys with the higher Fe and Mn contents.     

Effect of Cr Additions on Toughness,Strength, and Oxidation Resistance of an Nb-4Si-20Ti-6Hf Alloy at Room and/or High Temperatures

The mechanical properties and oxidation resistance of Nb-4Si-20Ti-6Hf-yCr alloys (where y = 6, 10, 14 at. pct) with an Nb_SS-dominant Nb_SS/Nb₃Si/Nb₅Si₃ microstructure at room and/or high temperatures were primarily studied. It was found that at room temperature, fracture toughness was decreased by Cr additions, the fracture mode of the Nb_SS phase was intergranularly cleavage, and the silicides (Nb₃Si and Nb₅Si₃) fractured in a brittle manner. It is interesting that strength as a function of Cr content is dependent on temperature. Up to 1423 K (1150 °C), the strength was improved by Cr additions, whereas above that temperature, the strength decreased. As the Cr content increased from 6 to 14 at. pct, for example, the yield strength σ _0.2 increased from 198 to 258 MPa at 1423 K (1150 °C) but decreased from 109 to 83 MPa at 1623K (1350 °C). Cr additions cannot improve the oxidation resistance of this Nb_SS-dominant microstructure considerably; the weight gain at 100 hours of air exposure at 1523 K (1250 °C) was 255 mg/cm² at a nominal Cr content of 6 at. pct and 220 mg/cm² at a Cr content of 14 at. pct.     

Alumina Solubility and Diffusion Coefficient of the Dissolved Alumina Species in Low-Temperature Fluoride Electrolytes

The solubility of alumina was measured by rotating an alumina cylinder (~500 rpm) in a high-purity melt for ~3 to 6 hours, crushing and sampling the frozen melt, and determining the oxygen content in a Leco analyzer. The alumina solubilities determined were as follows: (1) 3.2 ± 0.3 wt pct in NaF-AlF₃ eutectic at 1023 K (750 °C); (2) 3.0 ± 0.3 wt pct in NaF-AlF₃-CaF₂ (5 wt pct) at 1023 K (750 °C); and (3) 5.2 ± 0.5 wt pct in a KF-AlF₃ eutectic at 1003 K (730 °C). The alumina solubility in the KF-AlF₃ eutectic was 2 wt pct more than in the sodium analogue, offering the possibility of operating a low-temperature aluminum smelting cell without the need for an alumina slurry. The diffusion coefficient of the dissolved alumina species was determined in the NaF-AlF₃ eutectic at 1023 K (750 °C) using the rotating disc method and applying the Levich equation. Through a limited range of rotation rates, the system seemed to be mass-transfer controlled, and the diffusion coefficient was estimated to be in the range 1.8 to 2.2 × 10⁻⁶ cm² s⁻¹. This value is about five times lower than the values encountered at traditional aluminum smelting temperatures (~1233 K (960 °C)) and would result in relatively low mass transfer coefficients.     

A Study of the Effect of Nanosized Particles on Transient Liquid Phase Diffusion Bonding Al6061 Metal–Matrix Composite (MMC) Using Ni/Al2O3 Nanocomposite Interlayer

Transient liquid phase (TLP) diffusion bonding of Al-6061 containing 15 vol pct alumina particles was carried out at 873 K (600 °C) using electrodeposited nanocomposite coatings as the interlayer. Joint formation was attributed to the solid-state diffusion of Ni into the Al-6061 alloy followed by eutectic formation and isothermal solidification of the joint region. An examination of the joint region using an electron probe microanalyzer (EPMA), transmission electron microscopy (TEM), wavelength-dispersive spectroscopy (WDS), and X-ray diffraction (XRD) showed the formation of intermetallic phases such as Al₃Ni, Al₉FeNi, and Ni₃Si within the joint zone. The result indicated that the incorporation of 50 nm Al₂O₃ dispersions into the interlayer can be used to improve the joint significantly.     

Thermal-Treated Pitches as Binders for TiB2/C Composite Cathodes

The effect of thermal treatment on the microstructure and properties of pitches and thermal-treated, pitch-based TiB₂/C composite cathodes were investigated. Thermal treatments were performed at 473 K, 523 K, 573 K, 623 K, and 673 K (200 °C, 250 °C, 300 °C, 350 °C, and 400 °C), respectively. The results show that the aromaticity of the treated pitches increases with an increasing thermal treatment temperature, and subsequently, the coking value and quinoline-insoluble (QI) content increase from 60.62 wt pct to 79.09 wt. pct and from 8.97 wt pct to 32.54 wt pct when the treatment temperature increases from 473 K to 623 K (200 °C to 350 °C). The volume fraction of coalesced mesophase in semicoke decreases with an increasing thermal treatment temperature, and after 673 K (400 °C) is reached, the coalesced mesophase is almost invisible. The bulk density and compressive strength of modified pitch-based cathodes increase with an increasing thermal treatment temperature from 2.24 g cm⁻³ to 2.39 g cm⁻³ and from 24.21 MPa to 54.85 MPa, whereas open porosity decreases from 34.62 pct to 27.06 pct. Both electrical resistivity and electrolysis expansion ratio first decrease and then increase with an increasing thermal treatment temperature, and the lowest values (45.63 μΩ m and 0.65 pct) are achieved at 573 K (300 °C). Compared with those of the parent pitch-based cathode, the properties of the modified pitch-based cathodes had improved significantly. The mechanisms of the improvements are discussed in the text.     

Effects of Different Boron Compounds on the Corrosion Resistance of Andalusite-Based Low-Cement Castables in Contact with Molten Al Alloy

Interfacial reactions between Al alloy and andalusite low-cement castables (LCCs) containing 5 wt pct B₂O₃, B₄C, and BN were analyzed at 1123 K and 1433 K (850 °C and 1160 °C) using the Alcoa cup test. The results showed that the addition of boron-containing materials led to the formation of aluminoborate (9Al₂O₃.2B₂O₃) and glassy phase containing boron in the prefiring temperature (1373 K [1100 °C]), which consequently improved the corrosion resistance of the refractories. The high heat of formation of the aluminoborate phase (which increased its stability to reactions with molten Al alloy) and the low solubility of boron in molten Al were the major factors that contributed to the improvement in the corrosion resistance of B-doped samples.     

Brazing Inconel 625 Using Two Ni/(Fe)-Based Amorphous Filler Foils

For MBF-51 filler, the brazed joint consists of interfacial grain boundary borides, coarse Nb₆Ni₁₆Si₇, and Ni/Cr-rich matrix. In contrast, the VZ-2106 brazed joint is composed of interfacial Nb₆Ni₁₆Si₇ precipitates as well as grain boundary borides, coarse Nb₆Ni₁₆Si₇, and Ni/Cr/Fe-rich matrix. The maximum tensile strength of 443?MPa is obtained from the MBF-51 brazed specimen. The tensile strengths of VZ-2106 brazed joints are approximately 300?MPa. Both amorphous filler foils demonstrate potential in brazing IN-625 substrate.     

Studies on Direct Laser Cladding of SiC Dispersed AISI 316L Stainless Steel

In the present study, attempts have been made to develop SiC dispersed (5 and 20 wt pct) AISI 316L stainless steel matrix composite by direct laser cladding with a high power diode laser. Direct laser cladding has been carried out by melting the powder blends of AISI 316L stainless steel and SiC (5 and 20 wt pct) and, subsequently, depositing it on mild steel (0.15 pct C steel) in a layer by layer fashion to develop a coupon of 100 mm² × 10 mm dimension. A continuous, defect-free (microcracks and micro- or macroporosities), and homogeneous microstructure is formed, which consists of a dispersion of partially dissolved SiC (leading to formation of very low fraction of Cr₃C₂ and Fe₂Si) in grain-refined austenite. The microhardness of the clad layer increases from 155 VHN to 250 to 340 VHN (for 5 wt pct SiC dispersed) and 450 to 825 VHN (for 20 wt pct SiC dispersed) as compared to 155 VHN of commercially available AISI 316L stainless steel. The corrosion rate in 3.56 wt pct NaCl solution is significantly reduced in 5 wt pct SiC dispersed steel; however, 20 wt pct SiC dispersed steel showed a similar behavior as the commercially available AISI 316L stainless steel. The processing zone for the development of a defect-free microstructure with improved properties has been established.     

Interface microchemistry of silicon nitride/nickel-chromium,alloy joints

Silicon nitride ceramics were joined by diffusion bonding with a Ni−Cr alloy foil. The reactions between the alloy foil and the silicon nitride were examined using optical (OM) or scanning electron microscopy (SEM) and electron probe microanalysis and related to published thermodynamic phase diagram, and diffusion data. Joints were produced using Cr-precoated or uncoated Si₃N₄ ceramics and Ni-20 pct Cr foils either at 1423 K by applying 100 MPa for 1 hour in an Ar atmosphere or at 1473 K in vacuum. All joints formed were bonded by bridging layers of alloyed CrN, whose thickness and Cr content were affected by the joining conditions. Bonding both in Ar, and vacuum produced volume diffusion-controlled concentration gradients of Cr and Si in the Ni−Cr foil. Similarly, N₂ diffusion from the ceramic into the metal foils produced grain boundary precipitation of Cr₂N. For samples bonded in vacuum, a two-phase zone was additionally formed between the CrN bridging, layers and the metal foils consisting of a Ni₅Si₂ matrix that was molten at the bonding temperature and undissolved islands of foil material. The interfacial microchemistries are discussed with reference to the mechanical properties and hightemperature stability of the joints. MICHAEL G. NICHOLAS, formerly Visiting Scientist, Institute for Advanced Materials, is Section Manager AEA Technology, Harwell Laboratory, Oxon, United Kingdom.     

Effects of Fe Addition on the Snoek-Type Damping Behavior of Surface-Oxidation-Treated Ti-Mo Alloys

Effects of Fe addition on the oxygen diffusion and the Snoek-type relaxation damping behavior of the Ti-15 wt pct Mo alloy were investigated in this study. After surface oxidation treatment, the Ti-15 wt pct Mo-1 wt pct Fe alloy exhibits a higher damping capacity compared to the Ti-15 wt pct Mo alloy. The dual-phase zone and the oxygen-enriched β-phase zone in the surface-oxidation-treated Ti-Mo alloys were determined by electron backscattered diffraction (EBSD) and hardness measurements. Based on the oxygen distributions in both alloys obtained through a diffusion model, the relative damping capacity of different zones contributing to the beam sample damping was estimated to be proportional to the thickness of the oxygen dissolved zones. On the other hand, the substitutional solute of Fe in the Ti-Mo-Fe alloy is considered to affect the oxygen distribution by lengthening the oxygen diffusion zone and increasing the oxygen concentration in this zone. As a result, the addition of Fe in Ti-Mo alloy improves the damping capacity of the surface-oxidation-treated alloys.     

Determination of Solid Fraction from Cooling Curve

A new method to determine directly the solid fraction using the cooling curve was proposed for solidification of undercooled melts. Then, to construct three different baselines, a sudden function ξ _α (x) is introduced. In terms of the ξ _α (x) function, accordingly, the solid fractions during solidification of Ni-3.3 wt pct B, Al-7 wt pct Si, Al-14 wt pct Cu, and Fe-4.56 wt pct Ni alloys were predicted. The predictions of the primary, the regular lamellar eutectic, the anomalous eutectic, and the peritectic phases from cooling curves of the solidified samples coincide with the results of measurement or the available methods.     

Transient liquid-phase bonding in the Ni-Al-B system

Transient liquid-phase (TLP) bonding experiments were performed using a Ni-10.3 at. pct Al alloy and a Ni-10 at. pct B filler material, and the results were compared to simulations performed using the finite-difference diffusion code, DICTRA. For the simulations, a thermodynamic assessment of the Ni-Al-B system was used to define the phase diagram and the thermodynamic factors of the diffusion coefficients. Composition-dependent diffusion mobilities were assessed for the ternary system. Predicted liquid widths as functions of time were in good agreement with the experiments. The calculated and experimental Al composition profiles agree in the matrix but not in the liquid. The simulations qualitatively predicted the observed precipitation and later dissolution of the intermetallic τ phase (Ni₂₀Al₃B₆) in the base material. This research demonstrated the potential for modeling the formation of spurious phases during TLP bonding of practical superalloy systems.     

Electrolytic Deposition and Diffusion of Lithium onto Magnesium-9 Wt Pct Yttrium Bulk Alloy in Low-Temperature Molten Salt of Lithium Chloride and Potassium Chloride

The electrolytic deposition and diffusion of lithium onto bulk magnesium-9 wt pct yttrium alloy cathode in molten salt of 47 wt pct lithium chloride and 53 wt pct potassium chloride at 693 K were investigated. Results show that magnesium-yttrium-lithium ternary alloys are formed on the surface of the cathodes, and a penetration depth of 642 μm is acquired after 2 hours of electrolysis at the cathodic current density of 0.06 A·cm⁻². The diffusion of lithium results in a great amount of precipitates in the lithium containing layer. These precipitates are the compound of Mg₄₁Y₅, which arrange along the grain boundaries and hinder the diffusion of lithium, and solid solution of yttrium in magnesium. The grain boundaries and the twins of the magnesium-9 wt pct yttrium substrate also have negative effects on the diffusion of lithium.     

Effect of Bonding Temperature on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

An investigation was carried out on the solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200-μm thickness as an intermediate material prepared in vacuum in the temperature range from 973 K to 1073 K (700 °C to 800 °C) in steps of 298 K (25 °C) using uniaxial compressive pressure of 3 MPa and 60 minutes as bonding time. Scanning electron microscopy images, in backscattered electron mode, had revealed existence of layerwise Ti-Ni-based intermetallics such as either Ni₃Ti or both Ni₃Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) diffusion zone was free from intermetallic phases for all joints processed. Chemical composition of the reaction layers was determined in atomic percentage by energy dispersive spectroscopy and confirmed by X-ray diffraction study. Room-temperature properties of the bonded joints were characterized using microhardness evaluation and tensile testing. The maximum hardness value of ~800 HV was observed at TiA/Ni interface for the bond processed at 1073 K (800 °C). The hardness value at Ni/SS interface for all the bonds was found to be ~330 HV. Maximum tensile strength of ~206 MPa along with ~2.9 pct ductility was obtained for the joint processed at 1023 K (750 °C). It was observed from the activation study that the diffusion rate at TiA/Ni interface is lesser than that at the Ni/SS interface. From microhardness profile, fractured surfaces and fracture path, it was demonstrated that failure of the joints was initiated and propagated apparently at the TiA/Ni interface near Ni₃Ti intermetallic phase.     

Electrochemical Removal of AlCl3 from LiCl-KCl Melts

In order to remove impurity AlCl₃ from LiCl-KCl melts before Li electrolysis, the Al³⁺ reduction potential on a tungsten electrode and the relation between Al³⁺ reduction peak current and AlCl₃ concentration in LiCl-KCl-AlCl₃ melts were determined by cyclic voltammetry (CV). Constant potential electrolysis at –1.6 V vs Cl₂/Cl^– on both solid Fe and liquid Zn cathodes was performed to remove AlCl₃ impurity from the LiCl-KCl-AlCl₃ melts. The removal rate of Al³⁺ from the melts was analyzed by both electrochemical methods and inductively coupled plasma–atomic emission spectrometry (ICP-AES) analysis. The results showed that 96.11 wt pct of Al were removed on a Fe cathode and 99.90 wt pct on a Zn cathode through 10 hours electrolysis, respectively. While stirring the melts by argon gas, 99.21 wt pct of Al³⁺ was separated from the melts by 4 hours of electrolysis at 723 K (450 °C), which effectively expedited the Al³⁺ electrochemical reduction rate and shortened the electrolysis time.     

Thermodynamics of Arsenic in FeOx-CaO-SiO<Subscript>2</Subscript> Slags

The distribution of arsenic between calcium ferrite slag and liquid silver (wt pct As in slag/ wt pct As in liquid silver) with 22 wt pct CaO and between iron silicate slag with 24 wt pct SiO₂ and calcium iron silicate slags was measured at 1573 K (1300 °C) under a controlled CO-CO₂-Ar atmosphere. For the calcium ferrite slags, a broad range of oxygen partial pressure (10^–11 to 0.21 atm) was covered, whereas for the silicate slags, the oxygen partial pressure was varied from 10^–9 to 3.1 × 10^–7 atm. The measured relations between the distribution ratio of As and the oxygen partial pressure indicates that the oxidation state of arsenic in these slags is predominantly As³⁺ or AsO_1.5. The measured distribution ratio of arsenic between the calcium ferrite slag and the liquid silver was about an order of magnitude higher than that of the iron silicate slag. In addition, an increasing concentration of SiO₂ in the calcium-ferrite-based melts resulted in decreases in the distribution of arsenic into the slag. Through the use of measured equilibrium data on the arsenic content of the metal and slag in conjunction with the composition dependent on the activity of arsenic in the metal, the activity of AsO_1.5 in the slags was deduced. These activity data on AsO_1.5 show a negative deviation from the ideal behavior in these slags.     

Phase Constituents and Microstructure of Interaction Layer Formed in U-Mo Alloys <Emphasis Type="Italic">vs</Emphasis> Al Diffusion Couples Annealed at 873 K (600 °C)

U-Mo dispersion and monolithic fuels are being developed to fulfill the requirements for research reactors, under the Reduced Enrichment for Research and Test Reactors program. In dispersion fuels, particles of U-Mo alloys are embedded in the Al-alloy matrix, while in monolithic fuels, U-Mo monoliths are roll bonded to the Al-alloy matrix. In this study, interdiffusion and microstructural development in the solid-to-solid diffusion couples, namely, U-15.7 at. pct Mo (7 wt pct Mo) vs pure Al, U-21.6 at. pct Mo (10 wt pct Mo) vs pure Al, and U-25.3 at. pct Mo (12 wt pct Mo) vs pure Al, annealed at 873 K (600 °C) for 24 hours, were examined in detail. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA) were employed to examine the development of a very fine multiphase interaction layer with an approximately constant average composition of 80 at. pct Al. Extensive TEM was carried out to identify the constituent phases across the interaction layer based on selected area electron diffraction and convergent beam electron diffraction (CBED). The cubic-UAl₃, orthorhombic-UAl₄, hexagonal-U₆Mo₄Al₄₃, and cubic-UMo₂Al₂₀ phases were identified within the interaction layer that included two- and three-phase layers. Residual stress from large differences in molar volume, evidenced by vertical cracks within the interaction layer, high Al mobility, Mo supersaturation, and partitioning toward equilibrium in the interdiffusion zone were employed to describe the complex microstructure and phase constituents observed. A mechanism by compositional modification of the Al alloy is explored to mitigate the development of the U₆Mo₄Al₄₃ phase, which exhibits poor irradiation behavior that includes void formation and swelling.