Alloy design and coarsening phenomenon of L12 precipitates in high-temperature Al-2 At. Pct (Ti,V,Zr) systems

Aging works of two melt-spun Al-2 at pct (Ti,V,Zr) alloys showed that metastable L1₂ Al₃(Ti,V,Zr) precipitates were dominant and did not transform to stable D0₂₃ ones: the average radius was 3 to 4 nm and the interparticle spacing was 10 to 30 nm at 698 K up to 400 hours. Coarsening kinetics was found to be very sluggish and was coincident with the low lattice mismatch. Due to the low coarsening rate and the high thermal stability of the precipitated phase, rapidly so-lidified Al-Ti-V-Zr systems show promise as base of high-strength Al alloys for high-temperature applications. Formerly with the Department of Materials Science andEngineering, Korea Advanced Institute of Science and Technology, Taejon, Korea     

Substructure strengthening in dispersion-strengthened nickel alloys

Pure nickel, 80 pct Ni-20 pct Cr, 98 pct Ni-2 pct ThO₂, and 78 pct Ni-20 pct Cr-2 pct ThO₂ were studied in a wide range of thermomechanical conditions to identify strengthening mechanisms in the dispersion-strengthened materials. An X-ray line profile technique was used to determine the distribution of lattice strain, the crystallite domain size and the incidence of twins and stacking faults. Transmission electron microscopy was carried out, and tensile tests were done at room temperature and at an elevated temperature. It was found that cold deformation of Ni?ThO₂ did not produce lattice strains as large as was the case with pure nickel and Ni?Cr. However, deformation of Ni?Cr?ThO₂ did generate high lattice strains, due it is thought to the influence of chromium on cross-slip. The materials containing high lattice strains recrystallized more readily on annealing or testing at high temperature. It was concluded that room temperature strength was related to domain size without regard to composition in the series investigated. Strengthening by particle-dislocation interaction was not thought to be applicable when the domain size was small compared to the interparticle spacing, or at elevated temperatures. High temperature strength was determined primarily by the presence of a polygonized dislocation substructure which was stabilized by the thoria dispersion.     

Dispersion strengthening austenitic stainless steels by nitriding

The internal nitridation of thin sections of austenitic Fe−Cr−Ni−Ti alloys containing up to 2 pct Ti was studied over the temperature range 1600° to 2210°F in order to develop a method of strengthening the alloys through the introduction of a dispersoid of stable titanium nitrides. The interparticle spacing (IPS) of the nitrides was found to increase linearly with depth from the external surface; the effects of various parameters on the rate of change of IPS vs depth are presented. The mechanical properties of these alloys at room and elevated temperatures were markedly improved by internally nitriding. Useful mechanical properties were obtained up to 2200°F, with typical properties at 2000°F of 10 to 20 ksi 0.2 pct offset yield strength and 15 to 25 ksi ultimate tensile strength, but section thickness was limited to about 10 mils because of the increase in IPS with depth and the long nitriding times needed for thicker material. In order to produce a small interparticle spacing in a heavier section, internally nitrided 5 mil strip was consolidated by hot roll bonding and evaluated at a 60 mil thickness by tensile and rupture testing at 2000°F. It is demonstrated that the approach taken in this work offers a feasible technique for making a high temperature alloy having useful engineering properties.     

Effect of Aluminum Content on the Microstructure and Mechanical Properties of Hypereutectoid Steels

Hypereutectoid steels with 0, 0.69, 1.29, and 1.95 wt pct aluminum were prepared. The samples were hot rolled at 1100 °C followed by cooling in air. The microstructure of the as-rolled samples was characterized using field emission–scanning electron microscopy (FE-SEM). The electron backscattered diffraction (EBSD) technique was used to identify the grain boundary phases. The steels have a pearlitic microstructure with different amounts of grain boundary cementite. A continuous grain boundary cementite network is present in the 0 wt pct Al steel. Grain boundary cementite formation is completely suppressed in the 1.29 wt pct Al steel. Phase diagram calculations show that aluminum increases the eutectoid temperature. However, the interlamellar spacing and pearlite colony size decrease with increase in aluminum content. Dilatometry measurements show that aluminum addition increases the undercooling below the eutectoid temperature. The yield strength increases with the decrease in interlamellar spacing and colony size. Very high ultimate tensile strengths (1200 to 1400 MPa) and improved elongations to failure (7 to 9 pct) are achieved in the as-rolled condition.     

Recrystallization and grain growth phenomena in a particle-reinforced aluminum composite

Recrystallization and grain growth in a 2219/TiC/15p composite were investigated as functions of the amount of deformation and deformation temperature. Both cold and hot deformed samples were annealed at the normal solution treatment temperature of 535 °C. It was shown that large recrystallized grain diameters, relative to the interparticle spacing, could be produced in a narrow range of deformation for samples cold-worked and those hot-worked below 450 °C. For cold-worked samples, between 4 to 6 pct deformation, the recrystallized grain diameters varied from 530 to 66 μm as the amount of deformation increased. Subsequent grain growth was not observed in these recrystallized materials and noncompact grain shapes were observed. For deformations greater than 15 pct, recrystallized grain diameters less than the interparticle spacing were observed and subsequent grain growth produced a pinned grain diameter of 27 μm. The pinned grain diameter agreed well with an empirical model based on three dimensional (3-D) Monte Carlo simulations of grain growth and particle pinning in a two-phase material. Tensile properties were determined as a function of grain size, and it was shown that grain size had a weak influence on yield strength. A maximum in the yield strength was observed at a grain size larger than the normal grain growth and particle-pinned diameter.     

Effects of chromium and copper additions on precipitation in Al−Zn−Mg alloys

The effects of chromium and copper additions on precipitation in several Al?Zn?Mg alloys have been investigated. Results show that chromium additions heterogenize precipitation in aged Al?Zn?Mg alloys by creating special nucleation sites. Multirowed bands of incoherent precipitates appeared in the grain boundaries and subboundaries in an Al-5 pct Zn-2 pct Mg-0.1 pct Cr alloy. It is believed that fine nuclei associated with the existence of chromium-rich regions are formed during solidification and are retained after solution heat treatment. These nuclei would lead to the formation of incoherent precipitates during quenching and aging. Chromium is, therefore, considered to causehigh temperature nucleation. Copper additions to Al?Zn?Mg alloys accelerate precipitation at lower aging temperatures and increase the density of G. P. zones nucleated at relatively lower temperatures (20 to 90°C). In this way copper considerably strengthens Al?Zn?Mg alloys. Copper, in contrast to chromium, causes increased low-temperature nucleation of G. P. zones.     

The influence of interparticle spacing on cyclic deformation and fatigue crack propagation in an aluminum-4 Pct copper alloy

A high purity Al-4 pct Cu alloy has been overaged for two different times at 400°C giving interparticle spacings (λ) of about 0.53 and 1.37 μm. Cyclic plasticity of the alloy with the smaller interparticle spacing can be explained in terms of plastic deformation behavior controlled by the structure whereas that for the alloy with the larger interparticle spacing is controlled by the matrix. The fatigue lives of the weaker alloy (λ = 1.37 μm) may be accurately predicted using the models of Coffin-Manson and Tomkins, however, these models are not applicable to the stronger alloy (λ = 0.53 μm). It was found that the crack tip opening displacement at the threshold stress intensity range (ΔK_th) was equivalent to the interparticle spacing. ΔK_th is related to the cyclic yield stress, σ_cy and the interparticle spacing in the following manner: ΔK_th ≈ (2 Eλσ_cy)^1/2, whereE is the modulus of elasticity. In the present case, the term λσ_cy is constant, giving the impression that ΔK_th is independent of the mechanical properties and microstructure. At very low growth rates, however, the fatigue crack growth is independent of these parameters and also the method of cyclic deformation. A transition to higher crack growth rates occurs when the plastic zone size reaches approximately one-seventh of the specimen thickness, allowing a nonplanar crack front to be developed. The value of the stress intensity range (ΔK_T) at this transition was found to be dependent upon the interparticle spacing according to the relation: ΔK_Tλ = 9.6 Pa-m^3/2. Formerly Lecturer and Research Associate, Department of Mechanical Engineering, University of Waterloo     

Structural Characterization of Sputter-Deposited 304 Stainless Steel+10 wt pct Al Coatings

An SS304?+?10?wt pct Al (with a nominal composition of Fe-18Cr-8Ni-10Al by wt pct and corresponding to Fe-17Cr-6Ni-17Al by at. pct) coating was deposited on a 304-type austenitic stainless steel (Fe-18Cr-8Ni by wt pct) substrate by the magnetron sputter-deposition technique using two targets: 304-type stainless steel (SS304) and Al. The as-deposited coatings were characterized by X-ray diffraction, transmission electron microscopy, and three-dimensional (3-D) atom probe techniques. The coating consists of columnar grains with ?? ferrite with the body-centered cubic (bcc) (A2) structure and precipitates with a B2 structure. It also has a deposition-induced layered structure with two alternative layers (of 3.2 nm wavelength): one rich in Fe and Cr, and the other enriched with Al and Ni. The layer with high Ni and Al contents has a B2 structure. Direct confirmation of the presence of B2 phase in the coating was obtained by electron diffraction and 3-D atom probe techniques.     

Nitrogen solubility and aluminum nitride precipitation in liquid iron,Fe-Cr,Fe-Cr-Ni,and Fe-Cr-Ni-Mo alloys

The nitrogen solubility and aluminum nitride formation in liquid Fe-Al, Fe-Cr-Al, Fe-18 pct Cr-8 pct Ni-Al and Fe-18 pct Cr-8 pct Ni-Mo-Al alloys were measured by the Sieverts' method. The temperature range extended from 1823 to 2073 K, and the aluminum contents from 1.01 to 3.85 wt pct Al. Increasing aluminum content increases the nitrogen solubility. The effect of molybdenum additions was determined for 2, 4 and 8 wt pct Mo levels. The first and second order effects of chromium, nickel, molybdenum and aluminum on the activity coefficient of nitrogen in iron were determined. The first and second order effects of chromium, nickel and molybdenum on the activity coefficient of aluminum also were determined. The nitride precipitates were identified as stoichiometric aluminum nitride, AIN, by X-ray diffraction analysis. The lattice spacing was in good agreement with the ASTM standard patterns for AIN in both higher and lower Al content solutions. The solubility product of AIN increases with increasing aluminum concentration and with temperature in liquid iron and the iron alloys studied. However, the magnitudes of the solubility products of AIN in those alloys are different because of the effects of chromium and nickel additions. Additions of molybdenum show little effect on the solubility product of AIN. The standard free energy of formation of AIN in liquid iron is: δG? = -245,990 + 107.59 \T J/g-molAIN, based on the standard state of the infinitely dilute solution in liquid iron for aluminum and nitrogen, referred to a hypothetical one wt pct solution, and on the pure compound for A1N.     

Room-temperature mechanical behavior of cryomilled al alloys

Room-temperature mechanical properties of cryomilled Al-7.5 pct Mg and Al 5083 alloys are discussed in the context of a duplex microstructure, which arises during processing. After consolidation via hot isostatic pressing (“hipping”), coarse-grained regions are formed in former interparticle void volumes, and these regions become elongated during extrusion. Comparison of tensile and compression testing results on both “as-hipped” and extruded materials shows that tension-compression asymmetry is the result of these coarse-grained regions and not necessarily a fundamental property of ultrafine grained Al. The strength of the extruded materials is consistent with the Hall-Petch model of strengthening by grain size refinement, but the hipped material deviates from this trend, with a lower strength despite finer average grain size. This can also be attributed to the presence of coarse-grained regions, which substract from the strength in a predictable manner and also enhance the ability of the cryomilled material to work harden.     

The growth and morphology of directionally solidified nickel base γ/γ′- σ superalloys

A series of Ni-Nb-Al-Cr(γ/γ′- σ) alloys in the composition ranges Nb 19.3 to 23.2 wt pct, Al 2.5 to 5.2 wt pct and Cr 0 to 7.05 wt pct have been directionally solidified under high thermal gradient (G) at both steady state and under conditions of abruptly or gradually changing growth rate(ft). The critical ratio of G andR, (g/r)*, to achieve two-phase plane frontin- situ composite growth increases as chromium and niobium (Cb) concentration deviates from the trough or surface of two-fold saturation. Interlamellar spacing of composites tend to decrease with increasing chromium content. Structures produced at steady state growth in whichG/R < (G/R)* are consistent with previous work and can be related to the location of the alloy composition with respect to the line of two-fold saturation. For alloys, which at lowG/R exhibited σ dendrites, any perturbation in growth velocity (atG/R > (G/R)*) precipitated a single phase σ (Ni₃Nb) band. For alloys which at lowG/R exhibited γ dendrites a similar effect was achieved only when growth rate was reduced abruptly by more than an order of magnitude. Interlamellar spacing of two alloys (approximately Ni-20 wt pct Nb-2.5 wt pct Al-6 wt pct Cr) was studied and for abrupt reductions in growth rate in which bands were not produced, it was observed to decay slowly to the new steady state value over distances which are inconsistent with the assumption of simple niobium diffusion control. A gradual increase in growth velocity for one of these alloys resulted in extremely slow adjustment of interlamellar spacing occurring over a period greater than one hour. An abrupt increase in growth velocity for all alloys caused immediate adjustment of interlamellar spacing to the new steady state value.     

Effect of Cold Rolling on as–ECAP Interstitial Free Steel

Ti-stabilized interstitial free steel subjected to eight passes, route B_C room temperature equal channel angular pressing (ECAP) additionally was cold rolled (CR) up to 95 pct thickness reduction. Electron back-scattering diffraction and transmission electron microscopy characterized microstructural refinement and microtexture evolution, whereas the mechanical properties were assessed by uniaxial tensile tests. After 95 pct CR, the average high-angle grain boundary spacing reduces to 0.14 μm, whereas the high-angle boundary fraction increases to ~81 pct. The ECAP negative simple shear texture components rotate by ~15 deg around the transverse direction toward the rolling direction for up to 50 pct CR, with typical rolling textures observed at 95 pct CR. The decrease in boundary spacing produces a ~500 MPa gain in 0.2 pct proof stress, a ~600 MPa increase in ultimate tensile strength (UTS), and a ~4 pct loss in total elongation after 95 pct CR. Similar rates of decrease in work hardening correspond to comparable rates of cross and/or multiple slip events irrespective of the processing regime and substructural refinement. The fracture mode of the tensile samples changes from ductile to brittle type between ECAP and 95 pct CR and is attributed to the reduced work hardening capacity of the latter. The modified Hall–Petch equation shows that the convergence of high-angle boundary spacing values with their low-angle counterparts results in an increased contribution via boundary strengthening to the 0.2 pct proof stress and UTS.     

The as-quenched form of the omega phase in Zr-Nb alloys

The as-quenched Ω phase was examined in the Zr-Nb system using high resolution dark field electron microscopy and selected area diffraction. The morphology of the Ω phase was shown to be based upon (111) tl(0001) rows of particles 10 to 15Å in diameter with an interparticle spacing of 15 to 25Å. The row morphology is in agreement with previous observations on a Zr-Ti alloy. In the Zr-8 wt pct Nb alloy, clusters made up of many rows were observed and, as the solute content increased up to 15 wt pct Nb, the clusters became smaller and the length of the individual rows decreased. Sharp ω reflections and {111} planes of intensity in reciprocal space were observed in the 8 wt pct Nb alloy. As the niobium content increased, the ω reflections broadened and became more diffuse, while the thickness of the {111} planes of intensity increased. It was suggested that the sharp ω reflections result from scattering by the clusters while the {111} planes of intensity result from scattering by isolated rows of particles. Comparison of the ω morphology with the diffraction effects showed good agreement with these suggestions. In alloys with 15 wt pct and higher Nb content, the 0001 and 0002 broadened ω reflections were observed to be displaced toward each other alongω phase. It was suggested that these displacements are related to the mechanism of the transformation, which is thought to involve instability of the bcc structure relative to atomic displacement waves. The electron diffraction patterns were in agreement with predictions concerning this mechanism.     

Microstructural evolution of submicron sized ferrite in bimodal structural ultrafine grained ferrite/cementite steels by annealing below austenized temperature

The microstructural evolution of submicron sized ferrite in bimodal structural ultrafine grained ferrite/cementite steels with 0.15 pct carbon content and 0.45 pct carbon content upon annealing below the austenized temperature was investigated. The average grain sizes of the ferrites with a normal density and with a high density of cementite particles were plotted, respectively, as a function of the annealed temperature and time, and exhibited different coarsening behaviors. The average grain sizes of the ferrites with a normal density of cementite particles gradually coarsened by increasing the annealing temperature or time, while those with a high density of cementite particles hardly changed at first, and then coarsened after reaching a certain annealing condition. The coarsening of the ferrite grain size in the steel with 0.15 pct carbon content occurred much more readily than that in the steel with 0.45 pct carbon content upon annealing. The spacing and the critical spacing of cementite particle were measured and hypothetically calculated, respectively. The size and the distribution of cementite particles was one of the critical factors affecting the microstructural evolution in this type of cementite particle spherodized steels. Most of the coarsening of the ferrite grain size occurred after the cementite particle spacing reached the required critical value.     

The influence of stacking fault energy on the mechanical behavior of Cu and Cu-Al alloys: Deformation twinning, work hardening, and dynamic recovery

The role of stacking fault energy (SFE) in deformation twinning and work hardening was systematically studied in Cu (SFE ∼78 ergs/cm²) and a series of Cu-Al solid-solution alloys (0.2, 2, 4, and 6 wt pct Al with SFE ∼75, 25, 13, and 6 ergs/cm², respectively). The materials were deformed under quasi-static compression and at strain rates of ∼1000/s in a Split-Hopkinson pressure bar (SHPB). The quasi-static flow curves of annealed 0.2 and 2 wt pct Al alloys were found to be representative of solid-solution strengthening and well described by the Hall-Petch relation. The quasi-static flow curves of annealed 4 and 6 wt pct Al alloys showed additional strengthening at strains greater than 0.10. This additional strengthening was attributed to deformation twins and the presence of twins was confirmed by optical microscopy. The strengthening contribution of deformation twins was incorporated in a modified Hall-Petch equation (using intertwin spacing as the “effective” grain size), and the calculated strength was in agreement with the observed quasi-static flow stresses. While the work-hardening rate of the low SFE Cu-Al alloys was found to be independent of the strain rate, the work-hardening rate of Cu and the high SFE Cu-Al alloys (low Al content) increased with increasing strain rate. The different trends in the dependence of work-hardening rate on strain rate was attributed to the difference in the ease of cross-slip (and, hence, the ease of dynamic recovery) in Cu and Cu-Al alloys.     

Solid/Liquid Interfacial Energy of Mg-Al Alloys

The variation of solid–liquid interfacial energy (σ) for Mg–Al binary alloys was investigated as a function of Al content (3, 6, and 9 wt pct) based on the microstructure analysis of directional solidified Mg alloys. Primary dendrite arm spacing was measured from the directionally solidified alloys and used in Kurz and Fisher’s and Trivedi’s relations to calculate the value of σ. The calculated results reveal that the increasing Al content in Mg can significantly decrease the interfacial energy, which indicates a possible high adsorption tendency of Al at the solid/liquid interface.     

Nitrogen solubility and aluminum nitride precipitation in liquid iron, Fe-Cr, Fe-Cr-Ni, and Fe-Cr-Ni-Mo alloys

The nitrogen solubility and aluminum nitride formation in liquid Fe-Al, Fe-Cr-Al, Fe-18 pct Cr-8 pct Ni-Al and Fe-18 pct Cr-8 pct Ni-Mo-Al alloys were measured by the Sieverts' method. The temperature range extended from 1823 to 2073 K, and the aluminum contents from 1.01 to 3.85 wt pct Al. Increasing aluminum content increases the nitrogen solubility. The effect of molybdenum additions was determined for 2, 4 and 8 wt pct Mo levels. The first and second order effects of chromium, nickel, molybdenum and aluminum on the activity coefficient of nitrogen in iron were determined. The first and second order effects of chromium, nickel and molybdenum on the activity coefficient of aluminum also were determined. The nitride precipitates were identified as stoichiometric aluminum nitride, AIN, by X-ray diffraction analysis. The lattice spacing was in good agreement with the ASTM standard patterns for AIN in both higher and lower Al content solutions. The solubility product of AIN increases with increasing aluminum concentration and with temperature in liquid iron and the iron alloys studied. However, the magnitudes of the solubility products of AIN in those alloys are different because of the effects of chromium and nickel additions. Additions of molybdenum show little effect on the solubility product of AIN. The standard free energy of formation of AIN in liquid iron is: δG‡ = -245,990 + 107.59 \T J/g-molAIN, based on the standard state of the infinitely dilute solution in liquid iron for aluminum and nitrogen, referred to a hypothetical one wt pct solution, and on the pure compound for A1N.     

Numerical Simulation of Laser Surface Remelting on Unstructured Grids

A three dimensional, transient numerical simulation of laser surface remelting of eutectic Al?CCu 33 wt pct is presented in this paper. This work involves solution of conduction based energy equation with phase change using the Finite Volume Method on unstructured grids. Coordinate system is fixed to the laser and is moving with the laser scanning velocity. Model adopts ??Fixed Grid Enthalpy Method??, in which fluid fraction in the cell is continuously calculated. Model uses Implicit Euler discretisation in time, while the diffusion term are discretised using Jasak??s over relaxed approach. Microstructure formed in the remelted zone are predicted once the steady state molten pool is evolved. The resolidified interlamellar spacing in the remelted zone and the molten pool dimensions at the steady state are compared with the experimental data available in literature, which are found to be in good agreement over a range of scanning speed.     

The Effect of Calcium Oxide Addition on the Removal of Metal Impurities from Metallurgical-Grade Silicon by Acid Leaching

The removal of metal impurities from metallurgical grade silicon (MG-Si) by acid leaching has been investigated with the addition of CaO. Prior to adding CaO, Fe is the main impurity in the MG-Si sample, and the 2nd-phase precipitates in silicon are Si-Fe-based alloys, such as Si-Fe, Si-Fe-Ti, Si-Fe-Al, Si-Fe-Mn, and Si-Fe-Ni. The phases of Si-Fe and Si-Fe-Ti are not appreciably soluble in HCl. After the introduction of CaO, Ca becomes the dominant impurity, and the 2nd-phase precipitates become Si-Fe-based alloys, such as Si-Ca, Si-Ca-(Fe, Ti, Ni, Al), and Si-Ca-Fe-Al. These are effectively leached with HCl. Therefore, the HCl leaching effect on the removal of metal impurities has been improved. The optimum content of Ca in the MG-Si samples after adding CaO is in the range of 1?pct to 4?pct, the contents of Fe, Al, Ti, and Ni have been decreased to a minimum of less than 5?ppmw (ppm by weight) each, and the acid leaching results do not show a dependence on Ca content at this range.