Spark Plasma Sintering of Nanocrystalline Cu and Cu-10?Wt?Pct Pb Alloy

For the first time, we report here that high purity nanocrystalline Cu and Cu-10 wt pct Pb alloys can be densified with more than 90 pct theoretical density at a low temperature of 623 K (350 °C) using spark plasma sintering (SPS) in argon atmosphere at a pressure of 100 MPa. Scanning electron microscopy (SEM) analysis indicates that molten Pb particles travel through Cu grain boundaries, delineating a “flowlike” pattern in the microstructure. An extensive transmission electron microscopy (TEM) analysis of the ultrafine scale microstructure reveals partial wetting of Cu by liquid Pb as well as entrapment of Pb particles within the Cu matrix. The sintering kinetics and microstructural evolution are discussed in reference to the intrinsic characteristics of SPS as well as phase equilibria in the Cu-Pb system. An important result is that high hardness of around 2 GPa is measured in the Cu-10 wt pct Pb nanostructured alloy, SPS at 573 K to 623 K (300 °C to 350 °C).     

Dissolution and Interface Reactions between Palladium and Tin(Sn)-Based Solders: Part II. 63Sn-37Pb Alloy

The interface microstructures and dissolution behavior were studied, which occur between 99.9 pct Pd substrates and molten 95.5Sn-3.9Ag-0.6Cu (wt pct, Sn-Ag-Cu) solder. The solder bath temperatures were 513 K to 623 K (240 °C to 350 °C). The immersion times were 5 to 240 seconds. The IMC layer composition exhibited the (Pd, Cu)Sn₄ (Cu, 0 to 2 at. pct) and (Pd, Sn) solid-solution phases for all test conditions. The phases PdSn and PdSn₂ were observed only for the 623 K (350 °C), 60 seconds test conditions. The metastable phase, Pd₁₁Sn₉, occurred consistently for the 623 K (350 °C), 240 seconds conditions. Palladium-tin needles appeared in the Sn-Ag-Cu solder, but only at temperatures of 563 K (290 °C ) or higher, and had a (Pd, Cu)Sn₄ stoichiometry. Palladium dissolution increased monotonically with both solder bath temperature and exposure time. The rate kinetics of dissolution were represented by the expression At ⁿ exp(∆H/RT), where the time exponent (n) was 0.52 ± 0.10 and the apparent activation energy (∆H) was 44 ± 9 kJ/mol. The IMC layer thickness increased between 513 K and 563 K (240 °C and 290 °C) to approximately 3 to 5 μm, but then was less than 3 μm at 593 K and 623 K (320 °C and 350 °C). The thickness values exhibited no significant time dependence. As a protective finish in electronics assembly applications, Pd would be relatively slow to dissolve into molten Sn-Ag-Cu solder. The Pd-Sn IMC layer would remain sufficiently thin and adherent to a residual Pd layer so as to pose a minimal reliability concern for Sn-Ag-Cu solder interconnections.     

Superplasticity in a thermomechanically processed High-Mg,Al-Mg alloy

Superplastic elongations in excess of 400 pct have been observed in tension testing at 573 K (300 °C) and strain rate έ= 2 × 10^-3 s^-1 for a thermomechanically processed Al-10.2 pct Mg-0.52 pct Mn alloy. The thermomechanical processing consists of solution treatment and hot working, followed by extensive warm rolling at 573 K (300 °C), a temperature below the solvus for Mg in the alloy. This processing results in a fine subgrain structure in conjunction with refined and homogeneously distributed β(Al₈Mg₅) and MnAl₆ precipitates. This structure does not statically recrystallize when annealed at 573 K (300 °C) but appears to recrystallize continuously during deformation at such a temperature and the resulting fine grain structure deforms with minimal cavitation. At temperatures above the Mg-solvus,e.g., 673 K (400 °C), recrystallization and growth occur readily resulting in rela tively coarser structures which deform superplastically but with extensive grain boundary sliding and cavitation. Formerly in Materials Group, Mechanical Engineering, Naval Postgraduate School Formerly Graduate Student in Mechanical Engineering, Naval Postgraduate School     

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.     

Formation of Delta Ferrite in 9 Wt Pct Cr Steel Investigated by <Emphasis Type="Italic">In-Situ</Emphasis> X-Ray Diffraction Using Synchrotron Radiation

In-situ X-ray diffraction (XRD) measurements using high energy synchrotron radiation were performed to monitor in real time the formation of delta ferrite in a martensitic 9 wt pct chromium steel under simulated weld thermal cycles. Volume fractions of martensite, austenite, and delta ferrite were measured as a function of temperature at a 10 K/s heating rate to 1573 K (1300 °C) and subsequent cooling. At the peak temperature, the delta ferrite concentration rose to 19 pct, of which 17 pct transformed back to austenite on subsequent cooling.     

Transition of dominant diffusion process during superplastic deformation in AZ61 magnesium alloys

The superplastic behavior of the AZ61 magnesium alloy sheet, processed by one-step hot extrusion and possessing medium grain sizes of ∼12 μm, has been investigated over the temperature range of 523 to 673 K. The highest superplastic elongation of 920 pct was obtained at 623 K and a deformation rate of 1×10⁻⁴ s⁻¹. In the lower and higher strain rate regimes, with apparent m values of ∼0.45 and ∼0.25, respectively, grain-boundary sliding (GBS) and dislocation creep appeared to dominate the deformation, consistent with the scanning electron microscopy (SEM) examination. The SEM examination also revealed that individual GBS started to operate from the very initial deformation stage in the strain rate range with m∼0.45, which was attributed to the relatively high fraction (88 pct) of high-angle boundaries. The analyses of the superplastic data over 523 to 673 K and 5×10⁻⁵ to 1×10⁻³ s⁻¹ revealed a true stress exponent of ∼2, and the activation energy was close to that for grain-boundary and lattice diffusion of magnesium at 523 to 573 K and 573 to 673 K, respectively. The transition temperature of activation energy is ∼573 K, which is attributed to the change in the dominant diffusion process from grain-boundary diffusion to lattice diffusion. It is demonstrated that the effective diffusion coefficient is a valid parameter to characterize the superplastic behavior and the dominant diffusion process.     

Mechanical Properties and Corrosion–Abrasion Wear Behavior of Low-Alloy MnSiCrB Cast Steels Containing Cu

Two medium carbon low-alloy MnSiCrB cast steels containing different Cu contents (0.01 wt pct and 0.62 wt pct) were designed, and the effect of Cu on the mechanical properties and corrosion–abrasion wear behavior of the cast steels was studied. The results showed that the low-alloy MnSiCrB cast steels obtained excellent hardenability by a cheap alloying scheme. The microstructure of the MnSiCrB cast steels after water quenching from 1123 K (850 °C) consists of lath martensite and retained austenite. After tempering at 503 K (230 °C), carbides precipitated, and the hardness of the cast steels reached 51 to 52 HRC. The addition of Cu was detrimental to the ductility and impact toughness but was beneficial to the wear resistance in a corrosion–abrasion wear test. The MnSiCrB cast steel with Cu by the simple alloying scheme and heat treatment has the advantages of being high performance, low cost, and environmentally friendly. It is a potential, advanced wear-resistant cast steel for corrosion–abrasion wear conditions.     

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.     

Influence of Copper Addition and Temperature on the Kinetics of Austempering in Ductile Iron

Austempered ductile iron (ADI) is a material that exhibits excellent mechanical properties because of its special microstructure, combining ferrite and austenite supersaturated with carbon. Two ADI alloys, Fe-3.5 pct C-2.5 pct Si and Fe-3.6 pct C-2.7 pct Si-0.7 pct Cu, austempered for various times at 623 K (350 °C) and 673 K (400 °C) followed by water quenching, were investigated. The first ferrite needles nucleate mainly at the graphite/austenite interface. The austenite and ferrite weight fractions increase with the austempering time until stabilization is reached. The increase in the lattice parameter of the austenite during austempering corresponds to an increase of carbon content in the austenite. The increase in the ferrite weight fraction is associated with a decrease in microhardness. As the austempering temperature increases, the ferrite weight fraction decreases, the high carbon austenite weight fraction increases, but the carbon content in the latter decreases. Copper addition increases the high carbon austenite weight fraction. The results are discussed based on the phases composing the Fe-2Si-C system.     

Influence of the Processing Temperature on the Microstructure, Texture, and Hardness of the 7075 Aluminum Alloy Fabricated by Accumulative Roll Bonding

The 7075 alloy is an Al-Zn-Mg-Cu wrought age-hardenable aluminum alloy widely used in the aeronautical industry. The alloy was accumulative roll bonded at 300 °C (573 K), 350 °C (623 K), and 400 °C (673 K), and the microstructure, texture, and hardness were investigated. Cell/(sub)grain size in the nanostructured range, typical β-fiber rolling texture, and homogeneous hardness through thickness were determined in all cases. Misorientation was different at each processing temperature. At 400 °C, the presence of elements in solid solution and the partial dissolution of the hardening precipitates lead to a poorly misoriented microstructure with a high dislocation density and a homogeneous β-fiber texture of low intensity, typical of intermediate degrees of rolling. At 350 °C and 300 °C, highly misoriented microstructures with smaller dislocation density and intense heterogeneous β-fiber rolling texture are observed, especially at 350 °C, wherein the degree of dynamic recovery (DRV) is higher. Hardness of the accumulative roll bonded samples is smaller than that of the starting material due to particle coarsening, and it is affected by solid solution and/or by fine precipitates produced by reprecipitation of the elements in solid solution.     

Solid Solution Strengthening for Mg-3.0 Mass?Pct (2.71 At.?Pct)Al and Mg-0.06 Mass?Pct (0.036 At.?Pct)Ca Alloys

Tensile tests were carried out at 123 K to 373 K (–150 °C to 100 °C) on pure Mg, Mg-3.0 mass pct (2.71 at. pct) Al alloy, and Mg-0.06 mass pct (0.036 at. pct) Ca alloy. Little decrease occurred in the yield stress of the pure Mg and the Mg-Ca alloy with increasing temperature from 223 K to 373 K (–50 °C to 100 °C). For the Mg-Al alloy, however, its yield stress decreased with increasing temperature from 223 K to 373 K (–50 °C to 100 °C). Analyses based on the existing solid-solution strengthening theories, focusing on the athermal component of stress, revealed that the dominant strengthening mechanism is the shear modulus effect for the Mg-Ca alloy and the chemical interaction for the Mg-Al alloy. It is suggested that the shear modulus effect is dominant at a low concentration and the chemical interaction is dominant at a high concentration for Mg alloys.     

Selective Oxidation and Reactive Wetting of 1.0 Pct Si-0.5 Pct Al and 1.5 Pct Si TRIP-Assisted Steels

Heat treatments were performed using an isothermal bainitic transformation (IBT) temperature compatible with continuous hot-dip galvanizing on two high Al–low Si transformation induced plasticity (TRIP)-assisted steels. Both steels had 0.2 wt pct C and 1.5 wt pct Mn; one had 1.5 wt pct Al and the other had 1 wt pct Al and 0.5 wt pct Si. Two different intercritical annealing (IA) temperatures were used, resulting in intercritical microstructures of 50 pct ferrite (α)-50 pct austenite (γ) and 65 pct α-35 pct γ. Using the IBT temperature of 465 °C, five IBT times were tested: 4, 30, 60, 90, and 120 seconds. Increasing the IBT time resulted in a decrease in the ultimate tensile strength (UTS) and an increase in the uniform elongation, yield strength, and yield point elongation. The uniform elongation was higher when using the 50 pct α-50 pct γ IA temperature when compared to the 65 pct α-35 pct γ IA temperature. The best combinations of strength and ductility and their corresponding heat treatments were as follows: a tensile strength of 895 MPa and uniform elongation of 0.26 for the 1.5 pct Al TRIP steel at the 50 pct γ IA temperature and 90-second IBT time; a tensile strength of 880 MPa and uniform elongation of 0.27 for the 1.5 pct Al TRIP steel at the 50 pct γ IA temperature and 120-second IBT time; and a tensile strength of 1009 MPa and uniform elongation of 0.22 for the 1 pct Al-0.5 pct Si TRIP steel at the 50 pct γ IA temperature and 120-second IBT time.     

Tensile and Thermal Properties in Compacted Graphite Irons at Elevated Temperatures

Tensile and thermal properties of compacted graphite irons (CGIs), prepared with various molybdenum additions and solidification rates, have been investigated for temperatures between room temperature and 873 K (600 °C). A slower solidification rate resulted in larger and fewer graphite particles as well as in an increase of intercellular cementite, or carbides. Molybdenum is a carbide stabilizing element; i.e., increasing additions of molybdenum increased the amount of carbides. Young’s modulus decreased with increasing temperature, and a lower solidification rate increased this parameter slightly. Both increasing content of carbide and increasing nodularity increased the Young’s modulus. Strength parameters such as yield strength and ultimate tensile strength (R _m ) were affected in similar ways by temperature and solidification rate. The strength values were generally quite temperature independent for temperatures below 573 K (300 °C) but decreased rapidly for higher temperatures. Increasing nodularity increased the strength, while increasing content of carbide had little influence on the values. The thermal conductivity decreased with increasing content of carbide and increasing nodularity. The thermal conductivity generally showed a maximum value at 573 K (300 °C). A contradictory linear relationship was found between yield strength and thermal conductivity.     

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.     

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.     

Superplastic behavior of thermomechanically treated P/M 7091 aluminum alloy

The superplastic behavior of thermomechanically treated P/M 7091 aluminum alloy was assessed in the temperature range of 573 to 773 K. The thermomechanical treatment (TMT) comprised of three steps of solution treatment, overaging, and warm rolling. There are large η-phase (MgZn₂) precipitate particles of average size of 1.30 μm in the overaged condition. The warm-rolled alloy undergoes continuous recrystallization at the test temperatures of 573 and 623 K, exhibiting a maximum tensile elongation of 450 pct at 573 K and a strain rate of 8 × 10⁻⁵ s⁻¹. The precipitate particles play a major role in the process of continuous recrystallization. For a given volume fraction of precipitate particles and constant amount of warm rolling (in the course of TMT), an optimum precipitate particle size is expected to maximize the rate of continuous recrystallization and render the finest recrystallized grain size. The warm-rolled alloy undergoes static recrystallization at temperatures above 673 K. The grain growth accompanying the deformation at these test temperatures limits the tensile ductility to a lower value. Irrespective of the test temperature and strain rate, the specimens undergo extensive cavitation when deformed at elevated temperatures.     

The Mechanism of High Strength-Ductility Steel Produced by a Novel Quenching-Partitioning-Tempering Process and the Mechanical Stability of Retained Austenite at Elevated Temperatures

The designed steel of Fe-0.25C-1.5Mn-1.2Si-1.5Ni-0.05Nb (wt pct) treated by a novel quenching-partitioning-tempering (Q-P-T) process demonstrates an excellent product of strength and elongation (PSE) at deformed temperatures from 298 K to 573 K (25 °C to 300 °C) and shows a maximum value of PSE (over 27,000 MPa pct) at 473 K (200 °C). The results fitted by the exponent decay law indicate that the retained austenite fraction with strain at a deformed temperature of 473 K (200 °C) decreases slower than that at 298 K (25 °C); namely, the transformation induced plasticity (TRIP) effect occurs in a larger strain range at 473 K (200 °C) than at 298 K (25 °C), showing better mechanical stability. The work-hardening exponent curves of Q-P-T steel further indicate that the largest plateau before necking appears at the deformed temperature of 473 K (200 °C), showing the maximum TRIP effect, which is due to the mechanical stability of considerable retained austenite. The microstructural characterization reveals that the high strength of Q-P-T steels results from dislocation-type martensite laths and dispersively distributed fcc NbC or hcp ε-carbides in martensite matrix, while excellent ductility is attributed to the TRIP effect produced by considerable retained austenite.     

Mechanical and Thermal Properties of Pulsed Electric Current Sintered (PECS) Cu-Diamond Compacts

In this work, dispersion strengthening of copper by diamonds is explored. In particular, the influence of 50- and 250-nm diamonds at contents of 3 and 6 vol. pct on the mechanical and thermal properties of pulsed electric current sintered (PECS) Cu composites is studied. The composite powders were prepared by mechanical alloying in argon atmosphere using a high-energy vibratory ball mill. The PECS compacts prepared had high density (>97 pct of T.D.) with quite evenly distributed diamonds. The effectiveness of dispersoids in increasing the microhardness was more pronounced at a smaller particle size and larger volume fraction, explained by Hall–Petch and Orowan strengthening models. The microhardness of Cu with 6 and 3 vol. pct nanodiamonds and pure sm-Cu (submicron-sized Cu) was 1.77, 1.46, and 1.02 GPa, respectively. In annealing experiments at 623 K to 873 K (350 °C to 600 °C), the composites with 6 vol. pct dispersoids retained their hardness better than those with less dispersoids or sm-Cu. The coefficient of thermal expansion was lowered when diamonds were added, being the lowest at about 14 × 10^?6 K^?1 between 473 K and 573 K (200 °C and 300 °C). Good bonding between the copper and diamond was qualitatively demonstrated by nanoindentation. In conclusion, high-quality Cu-diamond composites can be produced by PECS with improved strength and better thermal stability than for sm-Cu.     

A New Paradigm for Designing High-Fracture-Energy Steels

The steels used for structural and other applications ideally should have both high strength and high toughness. Most high-strength steels contain substantial carbon content that gives poor weldability and toughness. A theoretical study is presented that was inspired by the early work of Weertman on the effect that single or clusters of solute atoms with slightly different atom sizes have on dislocation configurations in metals. This is of particular interest for metals with high Peierls stress. Misfit centers that are coherent and coplanar in body-centered cubic (bcc) metals can provide sufficient twisting of nearby screw dislocations to reduce the Peierls stress locally and to give improved dislocation mobility and hence better toughness at low temperatures. Therefore, the theory predicts that such nanoscale misfit centers in low-carbon steels can give both precipitation hardening and improved ductility and fracture toughness. To explore the validity of this theory, we measured the Charpy impact fracture energy as a function of temperature for a series of low-carbon Cu-precipitation-strengthened steels. Results show that an addition of 0.94 to 1.49 wt pct Cu and other accompanying elements results in steels with high Charpy impact energies down to cryogenic temperatures (198 K [–75 °C]) with no distinct ductile-to-brittle transition. The addition of 0.1 wt pct Ti results in an additional increase in impact toughness, with Charpy impact fracture energies ranging from 358 J (machine limit) at 248 K (–25 °C) to almost 200 J at 198 K (–75 °C). Extending this concept of using coherent and coplanar misfit centers to decrease the Peierls stress locally to other than bcc iron-based systems suggests an intriguing possibility of developing ductile hexagonal close-packed alloys and intermetallics.     

Low Temperature Sensitization on the Orthogonal Surfaces of Prior Deformed AISI 304LN and Aged at 673 K to 873 K (400 °C to 600 °C)

This study investigates the sensitization behavior of AISI 304LN deformed previously by cold rolling (CR) to 5 pct to 25 pct reduction in thickness and aged at 673 K to 873 K (400 °C to 600 °C). The emphasis was on revealing the degree of sensitization (DOS) resulting from low-temperature sensitization (LTS) on the orthogonal surfaces and correlation thereof with the changes in various metallurgical properties caused by cold rolling. It was found that the DOS differs among the orthogonal surfaces such as the rolling surface (RS), transverse surface (TS), and cross transverse surface (CTS). RS showed lower DOS compared with CTS and TS. The differences in the DOS were attributed to the combined effect of deformation-induced martensite (DIM), grain size, and slip band formation. A deformation of 5 pct was critical to the susceptibility of AISI 304LN to intergranular (IGC) and transgranular corrosion (TGC). The sensitization kinetics was slow or saturated leading to desensitization beyond 5pct deformations at 773 K (500 °C) and 873 K (600 °C). It was, however, uniformly accelerated over 5 to 25 pct deformation when aged at 673 K (400 °C).