Hydrogen Effects in Prestrained Transformation Induced Plasticity Steel

Thermal desorption analysis (TDA) was performed on laboratory heat-treated transformation induced plasticity (TRIP) steel with 14.5?pct retained austenite (RA), ultimate tensile strength (UTS) of 880?MPa, and elongation to failure of 33?pct. Samples were tensile prestrained 5?pct at 253?K (?C20?°C), 296?K (23?°C), and 375?K (102?°C) to generate different amounts of deformation-induced martensite, 10.5, 5.5, and 0.5?pct, respectively, prior to cathodically charging to a hydrogen content of 1 to 2 ppm. TDA was performed on charged samples to determine the location and strength of hydrogen trapping sites. TDA results suggest that dislocations were the main trapping sites in prestrained TRIP steel. The TDA peak intensity increased with prestrain, suggesting that the quantity of hydrogen trap sites increased with deformation. Tensile tests were performed on the four hydrogen-charged TRIP steel conditions. As confirmed with transmission electron microscope images, samples with more homogeneous dislocation distributions (i.e., prestrained at 375?K (102?°C)) exhibited greater resistance to hydrogen embrittlement than samples that included a high dislocation density adjacent to the formations of strain-induced martensite (i.e., samples prestrained at 253?K (?C20?°C) and 296?K (23?°C)).     

Hardening mechanisms in a dynamic strain aging alloy,HASTELLOY X,during isothermal and thermomechanical cyclic deformation

Isothermal cyclic deformation tests were conducted on HASTELLOY X with a total strain range of ±0.3 pct at several temperatures and strain rates. Cyclic hardening exhibited a broad peak between about 200 °C and 700 °C, with a maximum near 500 °C of about 80 pct increase in stress amplitude, Δσ/2, at failure. The present work examines the mechanisms contributing to this marked cyclic hardening. Cr₂₃C₆ precipitation on dislocations contributed to hardening, but only with sufficient time above about 500 °C. The substantial hardening rate at lower temperatures or shorter times was attributed to solute drag. The contribution of solute drag was evidenced in tests at both 400 °C and 600 °C by a continually decreasing strain rate sensitivity of the AcrJ2. Solute drag alone produced very considerable cyclic hardening. The increase in AcrJ2 after 1000 cycles at 427 °C was 75 pct of the maximum observed at higher temperatures where carbides did precipitate. Additionally, thermomechanical tests were conducted between various temperature limits, but with the same ±0.3 pct mechanical strain range. Hardening was bounded by isothermal behavior at the temperature limits of the thermomechanical cycles, except for tests between 400 °C and 600 °C which exhibited extreme hardening. However, microstructural examination did not suggest a cause. Specimens subjected to thermomechanical cycles appeared similar to those isothermally cycled at the maximum temperature of the thermomechanical cycle, including those from the 400 °C to 600 °C tests.     

On the effect of plastic deformation on the coarsening of ϑ-phase precipitation in an Al-Cu alloy

In the present investigation, the focus is on dynamic coarsening of the equilibrium ϑ phase in an Al-4wt pct Cu alloy. For this purpose, specimens containing a uniform ϑ particle distribution have been produced and deformed in compression at two different temperatures (200 °C and 250 °C) and strain rates in the ranges of 200 °C to 250 °C and 10⁻⁵ to 10⁻² s⁻¹, respectively. The particle size distribution measurements performed in a scanning microscope in back-scattered mode demonstrated a double peak behavior depending on temperature: at the lowest test temperature, the dynamic coarsening is enhanced at the highest strain rate, while at 250 °C, the coarsening seems to be affected by crushing of small and medium size particles during straining.     

Age-Induced Precipitating and Strengthening Behaviors in a Cu–Ni–Al Alloy

Microstructural response and variations in strength and electrical conductivity of a Cu−20 at. pct Ni–6.7 at. pct Al alloy during isothermal aging at temperatures from 723 K to 1023 K (450 °C to 750 °C) were investigated to discuss the age-induced precipitation behavior and strengthening mechanism. At all aging temperatures, fine spherical γ′-Ni₃Al particles were found to nucleate coherently with parent Cu grains by continuous precipitation and then grew gradually by Ostwald ripening. Domains with a high density of twins developed at grain boundaries during aging below 873 K (600 °C) followed by cellular components composed of fiber-shaped γ′-Ni₃Al and Cu solid solution phases at the domain boundaries later. Both the domains and cellular components were suppressed at aging above 923 K (650 °C). The age-induced strengthening principally resulted from fine dispersion of γ′-Ni₃Al coherent particles in the grains. The precipitation strengthening by the fine γ′-Ni₃Al coherent particles exhibited a maximum at an aging temperature of 873 K (600 °C), resulting in excellent mechanical properties such as a high hardness of 340 ± 7 HV and an ultimate tensile strength of 980 ± 14 MPa, which are comparable to those of other commercial age-hardened Cu–Be, Cu–Ni–Si, and Cu–Ti alloys.

     

Influence of peak pressure and temperature on the structure/property response of shock- loaded Ta and Ta-10W

The deformation behavior and substructure evolution of unalloyed-Ta and Ta-10W under quasistatic conditions have been compared to their respective responses when shock prestrained to 20 GPa at 25 °C as well as to unalloyed-Ta shocked to 7 GPa at 25 °C, 200 °C, and 400 °C. The reload yield behavior of shock-prestrained Ta and Ta-10W did not exhibit enhanced shock hardening when compared to their respective quasistatic stress-strain response at an equivalent strain level. In addition, the reload yield behavior of Ta shock prestrained to 7 GPa at 200 °C or 400 °C was found to exhibit increased hardening compared to the shock prestraining at 25 °C. The quasistatic substructure evolution and shock-hardening responses of Ta and Ta-10W were investigatedvia transmission electron microscopy (TEM). The dislocation substructures in both materials and at each strain rate condition and temperature were similar and consisted primarily of long, straight, ( α/2) 〈111〉 type screw dislocations. The propensity for long, straight screw dislocations, irrespective of the loading condition, supports the theory of strong Peierls stress control on defect generation and defect storage. The substructure evolution and mechanical behavior of Ta and Ta-10W are discussed in terms of defect storage mechanisms and compared to the mechanisms operative in face-centered cubic (fcc) metals. This article is based on a presentation made in the symposium “Dynamic Behavior of Materials,” presented at the 1994 Fall Meeting of TMS/ASM in Rosemont, Illinois, October 3-5, 1994, under the auspices of the TMS-SMD Mechanical Metallurgy Committee and the ASM-MSD Flow and Fracture Committee.     

Secondary precipitation and allotropic transformation of Cobalt-Rich Co-Ti-C alloys using transmission electron microscopy

The effect of heat-treatment and deformation on microstructural features and related mechanical properties of the cobalt phase of the hard metal compound Co-TiC has been investigated. Two quasibinary alloys, Co-l.25Ti-l.25C at. pct and Co-2.5 Ti-2.5C at. pct, were prepared, solution treated, quenched and annealed at selected temperatures in the range 500 to 1000 °C. The microstructures were characterized by optical microscopy, X-ray diffraction and high voltage electron microscopy and the mechanical properties were characterized by Vickers hardness measurements. The annealed Co-Ti-C alloys exhibit a two-phase matrix structure containing the equilibrium phase HCP-Co and some retained fcc-Co. The fcc-Co phase is stabilized at lower temperatures by titanium and carbon atoms in solid solution, by fine dispersions of coherent TiC particles, and by a refinement of the grain structure to grain diameters in the range of about 5μm. In addition, the matrix is dispersed with titanium carbide particles in a variety of morphologies, the distribution of which depends upon annealing conditions. These are nucleated homogeneously at low temperatures (600 °C) and heterogeneously at higher temperatures. These heterogeneous nucleation sites include grain boundaries, stacking faults, dislocations, and retained martensite grains. The matrix transformation and the precipitation processes are closely interrelated, and both affect the mechanical properties of the compound. The strongest hardening effects are achieved by the homogeneous distribution of coherent TiC particles and by TiC nucleated on stacking faults. Deformation prior to annealing causes a considerable refinement of the annealed structures which, in consequence, mainly consists of the fcc-Co phase. The nucleation and growth processes of TiC are also affected by this deformation and less pronounced hardening effects are obtained. Formerly with the Department of Materials Science and Engineering, Stanford University, Stanford, CA94305     

Thermal properties and interfacial reaction between the Sn-9Zn-<Emphasis Type="Italic">x</Emphasis>Ag lead-free solders and Cu substrate

The thermal properties and interfacial reaction between the Sn-9Zn-xAg lead-free solders and Cu substrate, such as solidus and liquidus temperatures, heat of fusion, intermetallic compounds, and adhesion strength, have been investigated. Two endothermic peaks appear in the DSC curve when the Ag content in the Sn-9Zn-xAg solder alloy is above 1.5 wt pct. The solidus temperatures of the Sn-9Zn-xAg solder alloys are around 197 °C, but the liquidus temperatures decrease from 225.3 °C to 221.7 °C and 223.6 °C with increasing the Ag content in the solder alloy from 1.5 to 2.5 and 3.5 wt pct, respectively. Three intermetallic compounds, namely, Cu₆Sn₅, Cu₅Zn₈, and Ag₃Sn are observed at the Sn-9Zn-xAg/Cu interface. The Cu₅Zn₈ is formed close to the Cu substrate, Ag₃Sn is adjacent to it, and Cu₆Sn₅ is nearest the Sn-9Zn-1.5Ag solder alloys. A bi-structural Cu₆Sn₅ layer with hexagonal η-Cu₆Sn₅ and monoclinic η′-Cu₆Sn₅ is found at the Sn-9Zn-1.5Ag/Cu interface due to Ag dissolution. A maximum adhesion strength of 10.7±0.8 MPa is obtained at the Sn-9Zn-2.5Ag/Cu interface as soldered at 250 °C for 30 seconds.     

Temperature dependence of yield stress in fe-1.67 at. pct Cu and fe-0.5 at. pct Au

A supersaturated solid solution of 1.67 at. pct Cu in Fe has a lower temperature dependence of the yield stress (prestrained 0.2 pct at 368°K) than pure iron over the temperature range 77° to 298°K. No change in temperature dependence is observed on aging to form copper clusters (1 hr at 475°C) but after precipitation of ε the temperature dependence is the same as in pure iron. The activation volume at 77°K is unaffected by treatment in the alloy and the amount of deformation. The value is essentially the same as in iron. It was suggested that copper clusters present after aging 1 hr as well as dissolved copper assist formation of double kinks at 77°K reducing the stress required to surmount the Peierls barrier. Addition of 0.5 at. pct Au also reduced the temperature dependence of iron. Formerly Graduate Student, Department of Materials Science and Materials Research Center, The Technological Institute, Northwestern University, Evanston, Ill.     

The effect of small deformation on abnormal grain growth in bulk Cu

The effect of small deformation below the level (about 8 pct) required for primary recrystallization on abnormal grain growth (secondary recrystallization) has been investigated in bulk polycrystalline Cu. The starting microstructure, without any texture and with a nearly uniform grain size of 168 μm, has been obtained by compressing a cylindrical Cu specimen and recrystallizing at 800 °C. The fully recrystallized specimen shows distinct abnormal grain growth (AGG) after heat treatment at 800 °C for 12 hours. Most of the grain boundaries are faceted when observed under transmission electron microscopy (TEM), and most of the faceted segments are expected to be singular. A singular grain boundary free of defects will migrate by two-dimensional nucleation of new layers, with its velocity varying nonlinearly with the driving force arising from the grain-size difference. Such a growth mechanism is analogous to the well known process for the growth of crystals with singular surfaces from liquid or vapor. The grains slightly larger than the average size will hardly grow, because the driving force for their growth is not sufficient for nucleation of new crystal layers at the boundaries. Those grains larger than a certain critical size will, however, grow at ever-increasing rates with their increasing size, because of the sufficient driving force for two-dimensional nucleation. Such a selective accelerated growth of large grains results in overall AGG behavior. The specimen deformed to 2 pct shows AGG after heat treatment for only 5 minutes at 800 °C, and after 1 hour, large impinged grains are obtained. The grain boundaries show many extrinsic dislocations even after the heat treatments. As proposed earlier by Gleiter, Balluffi, Smith, and their colleagues, the extrinsic grain-boundary dislocations increase the grain-boundary mobilities even at low driving forces, and, hence, even those grains slightly larger than the average size can rapidly grow at the early stages of the heat treatment, in agreement with the observation. In the specimens deformed to 4 to 8 pct, below the level for primary recrystallization, all grains grow steadily without producing distinct AGG. With high densities of extrinsic dislocations at the grain boundaries even after long heat treatments, all grains can readily grow, resulting in overall growth patterns resembling the normal growth. When deformed to 20 and 50 pct, primary recrystallization occurs, and the subsequent AGG behavior depends on the grain size obtained at the completion of the primary recrystallization. Similar small-deformation effects are observed with heat treatment at 600 °C.     

Study of 6061-Al2O3p composites produced by reciprocating extrusion

A reciprocating extrusion process was developed to consolidate 6061-Al₂O_3p composites from mixed powders. The 6061 alloy powder was first dehydrated in a vacuum chamber at 450 °C and then mixed with 12.5 μm Al₂O₃ powder in various volume fractions: 0, 5, 10, 20, and 30 pct. The mixed powders were hot pressed at 300 °C under a pressure of 300 MPa and finally extruded reciprocatingly 14 times at 460 °C. The results show that the composites were fully densified, with no sign of pores or oxide layers observable in the optical microscope. The Al₂O₃ particles were distributed uniformly in the matrix. As compared with 6061 alloys, the composites demonstrated a smaller precipitation hardening and elongation, but exhibited a higher Young’s modulus and a larger work hardening capacity. The degradation of precipitation hardening was due to the loss of Mg, which reacts with Al₂O₃ to form MgAl₂O₄. The large work-hardening capacity is attributable to the incompatibility between Al₂O₃ and the matrix, which possibly generates more dislocations to harden the matrix. The composites had much higher friction coefficients and greater wear resistances than the 6061 alloy against steel disc surface. The friction coefficient of the 6061-30 vol pct Al₂O_3p composite was double that of the 6061 alloy and the wear resistance was 100-fold. As compared with similar composites reported previously, these composites possessed much higher elongation at the same strength level. A 30 vol pct Al₂O_3p still displayed an elongation of 9.8 pct in the T6 condition. All of these improvements are attributed to the merits, including full densification of the bulk, uniform dispersion of the Al₂O₃ particles in the matrix, and strong binding between the Al₂O₃ particles and the matrix resulting from reciprocating extrusion.     

Microstructure and mechanical properties of sputter-deposited Cu1−x Ta x alloys

The microstructures and mechanical properties of a family of sputter-deposited Cu_1−x Ta _x (0<x<0.18) alloys have been investigated. The as-deposited microstructures for all film compositions consisted of a polycrystalline, face-centered-cubic (fcc) Cu matrix, with varying levels of Ta in solid solution, plus a very high density of discrete, 1 to 3 nm, fcc Ta particles. Decreased deposition temperature (−120 °C vs 100 °C) increased the level of Ta in solid solution. After annealing (900 °C for 1 hour) the as-deposited 6 at. pct Ta films, the Cu matrix grains remained submicron and the Ta particles remained fcc with no apparent particle coarsening. Additionally, the fcc Ta particles were found before and after annealing to be oriented identically with the Cu matrix and aligned on {111} and {100} habit planes. Annealing 17 at. pct Ta films at 900 °C for 1 hour resulted in the formation of body-centered-cubic (bcc) Ta particles (>50-nm diameter) in addition to the much smaller fcc Ta particles. Annealing the low and high Ta composition films at 900 °C for as long as 100 hours produced no observed change in either the Cu matrix grain size or the size and distribution of the fcc and bcc Ta particles. Microhardness and nanoindentation mechanical property evaluations of bulk hot-pressed materials indicated that the high strengths of the composites were unchanged, even after annealing for 100 hours at 900 °C.     

Influence of Cu additions on the morphology of GeSi precipitates in an Al-Ge-Si alloy

Combined additions of Ge and Si to Al are known to produce higher precipitation hardening than that which occurs in the constituent binaries, when the total amounts of alloying atoms are the same for all the alloys investigated. In the resultant Al-Ge-Si alloys, the diamond cubic precipitates contain both Ge and Si and are designated as GeSi. During artificial aging at 160 °C, the GeSi precipitates are commonly present in three forms, i.e., equiaxed, 〈100〉_Al lath, and triangular plate. The equiaxed form is the dominant one of the three. This article examines the influence of varying amounts (i.e., 2 to 4 wt pct) of Cu additions on the morphology of GeSi precipitates formed in an Al-2.6 wt pct Ge-1.04 wt pct Si alloy during artificial aging at 160 °C. It is shown that Cu additions have the remarkable effect of maximizing the nucleation frequency of the 〈100〉_Al lath form and simultaneously suppressing the nucleation of the equiaxed and the plate forms of the GeSi precipitates. Increasing Cu additions also increase the homogeneity and cause refinement of the 〈100〉_Al laths. These results are discussed in light of (1) the critical requirement of vacancies for the nucleation and growth of GeSi precipitates having an atomic volume larger than Al and (2) the crystallographic nature of the negative dilation strains that develop locally in the Cu-rich regions of the Al matrix. It is further shown that, in the alloys containing increased levels (i.e., exceeding about 2.5 wt pct) of Cu, the precipitation of ϑ′ (metastable ϑ-Al₂Cu) phase occurs, and that the nucleation of Cu-rich ϑ′ precipitates occurs upon the 〈100〉_Al laths of GeSi. The latter effect is discussed in terms of the attainment of both the nucleation site and the necessary solute supersaturation at the 〈100〉_Al GeSi/α-Al interfaces.     

Investigation of Precipitation Behavior in Age-Hardenable Cu-Ti Alloys by an Extraction-Based Approach

We investigated the precipitation processes in Cu-4 mol pct Ti alloy specimens aged at 723 K (450 °C), by means of X-ray diffraction and chemical analyses of the precipitates extracted from the parent alloy specimens. Aging-induced precipitate particles of a spinodally decomposed disorder, α′; those of a metastable order, β′-Cu₄Ti; and those of a stable order, β-Cu₄Ti, were continuously formed in the aged specimens. The extraction of the precipitate particles from the aged specimens by submergence in a nitric solution allowed for not only the structural analyses of the constituent precipitate phases but also the quantitative evaluation of their chemical compositions and volume fractions. Early during the aging process, the supersaturated Cu solid solution decomposes spinodally in a continuous manner, and an unstable disorder, α′, appears. Then, fine needle-shaped β′-Cu₄Ti particles, which have a Ti content of approximately 37.5 mol pct, form in the Cu matrix. During prolonged aging, coarse cellular components composed of the terminal Cu solid solution and stable β-Cu₄Ti particles which have a Ti content of 20.5 mol pct nucleate and grow, primarily in the grain boundaries, at the expense of the metastable β′-Cu₄Ti particles. The volume fraction of the β′-Cu₄Ti particles in the alloy reaches a maximum of approximately 1.7 pct after aging for 24 hours, while that of the β-Cu₄Ti particles increases steadily to more than 18 pct after 480 hours. The volume fraction of the fine β′-Cu₄Ti particles in the alloy specimens remained constant throughout the age-hardening, indicating that the hardening is primarily owing to the fine dispersion of the β′-Cu₄Ti particles and not because of the large volume fraction of coarse β-Cu₄Ti particles.     

The effects of deformation and pre-heat-treatment on abnormal grain growth in RENÉ 88 superalloy

When an extruded strain-free RENé 88 Ni-base superalloy about 1 to 2 μm in grain diameter is heattreated at 1150°C, abnormal grain growth (AGG) begins after 50 hours. When heat-treated at 1200 °C, AGG occurs at 15 minutes. Some of the grain boundaries are faceted with hill-and-valley structures when observed in transmission electron microscopy (TEM), and the occurrence of AGG is consistent with the boundary step and dislocation mechanism for the migration of singular boundaries with faceted shapes, as observed and proposed in other pure metals and alloys. The dissolution of abundant γ′ precipitates (with a solvus temperature of 1107 °C), which are coherent with the matrix and hence strongly pin the grain boundaries, does not cause AGG during early stages of heat-treatment at 1150 °C. Small deformations drastically alter the AGG behavior. When deformed to 4 pct, AGG begins after heat-treating for 10 minutes at 1150 °C, compared to the apparent incubation time of 50 hours for an undeformed specimen, and very large abnormal grains are produced. With increasing deformation to 6 and 9.2 pct, the abnormal grain size decreases. These results are qualitatively similar to those observed in Cu. This deformation effect on AGG is attributed to the absorption of lattice dislocations in the grain boundaries, which produces nonequilibrium structures that, in turn, can apparently cause rapid boundary migration. When heat-treated at 1200 °C, the largest abnormal grains are found in the specimens deformed to 2 pct. When the initial grain size is increased to about 14 μm by heattreating the extruded alloy at 1150 °C for 30 minutes, similar low deformation effects on AGG are observed. When these specimens are deformed to 10, 13, and 15.2 pct, primary recrystallization occurs during the heat-treatment at 1150 °C, and large abnormal grains are again produced because of the small recrystallized grain size. Therefore, there are two peaks in the grain size vs deformation curve after heat-treating at 1150 °C for 1 hour. A pre-heat-treatment of this alloy at 1050 °C below the solvus temperature of the γ′ phase greatly reduces the size of the abnormal grains obtained in the specimen deformed to 4 pct after the heat-treatment at 1150 °C, probably because some recovery of the dislocations takes place at grain boundaries during the pre-heat-treatment. The deformation effect on AGG observed in this alloy is qualitatively similar to that previously observed in Cu and appears to be consistent with the boundary step and dislocation mechanism for AGG. An erratum to this article is available at .     

Strength of initially virgin martensites at - 196 °C after aging and tempering

The compressive strength at -196°C of martensites in Fe-0.26 pct C-24 pct Ni, Fe-0.4 pct C-21 pct Ni, and Fe-0.4 pct C-18 pct Ni-3 pct Mo alloys, all with subzero M temperatures, has been determined in the virgin condition and after one hour at temperatures from -80 to +400 °C. The effects of ausforming (20 pct reduction in area of the austenite by swaging at room temperature prior to the martensitic transformation) were also investigated. For the unausformed martensites, aging at temperatures up to 0 °C results in relatively small increases in strength. Above 0 °C, the age hardening increment increases rapidly, reaching a maximum at 100 °C. Above 100 °C, the strength decreases continuously with increasing tempering temperature except for the molybdenum-containing alloy, which exhibits secondary hardening on tempering at 400 °C. For the ausformed martensites, the response to aging at subzero temperatures is greater than for unausformed material. Strength again passes through a maximum on aging at 100 °C. However, on tempering just above 100 °C, the ausformed materials show a slower rate of softening than the unausformed martensites. The strengthening produced by the ausforming treatment is largest for the Fe-0.4 pct C-18 pct Ni-3 pct Mo alloy, but there is no evidence of carbide precipitation in the deformed austenite to a°Count for this effect of molybdenum.     

Laves phase precipitation in Fe-Ta alloys

Development of an iron-base alloy hardened by particles of an intermetallic compound rather than a carbide is a desirable goal because of the greater thermal stability of such a dispersion. As a first step in the development of iron-base alloys hardened with the Laves phase, structural studies of binary Fe-Ta alloys have been undertaken. The structures of two phase Fe-Ta alloys have been studied by means of optical and transmission electron microscopy, X-ray diffraction, electron beam microprobe analysis, and scanning electron microscopy. The hardness change as a function of time at 600°, 700°, and 800°C has been determined for binary alloys with 1 at. pct Ta and 2 at. pct Ta in iron. Also, the uniaxial tensile strengths of solution treated, quenched, and aged samples have been determined. These studies suggest that the compound, Fe₂Ta, is isomorphous with the structure type, MgZn₂, (C14) and has a range of compositional homogeneity. The latter results correspond with the predictions of the Engel-Brewer correlation. Also, it has been found that precipitation occurs at grain boundaries, dislocations, and randomly throughout the matrix. Particles which form at dislocations have a (100)α habit plane; whereas a (110)α habit plane has been reported by others^1,3 for the hexagonal Laves phase in α iron. Hypereutectoid composition alloys quenched from the ö phase field have a completely retained § structure. Isothermal decomposition at 600°, 700°, and 800°C of alloys with the retained § structure results in a sizable hardness increase in 2 at. pct Ta alloys but only a modest increase in 1 at. pct Ta alloys. Brittle fracture of aged tensile specimens tested at room temperature reveals that the ductile-brittle transition temperature in tension is above room temperature.     

Dissolution and melting of secondary Al2Cu phase particles in an AlCu alloy

When up-quenching an Al-4.2 wt pct Cu alloy which has been equilibrated at 450 °C to a temperature at or above the eutectic temperature of 547 °C, liquid drops are found to form. Inside the matrix grains they have a globular shape, while they have a lenticular shape with a low dihedral angle when formed on grain boundaries. It is demonstrated metallographically that drops are formed by the melting of the Al₂Cu phase particles together with the surroundingα matrix to form a liquid of chemical composition around the eutectic composition. On prolonged annealing, the drops are dissolved in theα matrix. The kinetics of this dissolution reaction of the drops, as well as the dissolution of Al₂Cu phase particles at a temperature below 547 °C, is studied in some detail and compared with a simple mathematical model. Also, the thermodynamics of the melting and dissolution reactions are discussed by means of a free-energy diagram.     

Precipitation and Recrystallization in Some Vanadium and Vanadium-Niobium Microalloyed Steels

Static precipitation and recrystallization following hot compression of austenite and the interactions between the two processes have been studied in a set of aluminum-killed HSLA steels containing 0.1 pct carbon, [0.016 - 0.026] pct nitrogen and 0.1 or 0.2 pct vanadium. Two steels containing both vanadium (0.1 and 0.2 pct) and niobium (0.03 pct) were included for purposes of comparison. The compression and the static tests were all carried out isothermally at temperatures between 800 and 900 °C. The course of recrystallization was followed by measurements of the rate of softening and by optical metallography of specimens quenched from the test temperature after different times. Precipitation was studied by measurements of the rate of hardening, by transmission electron microscopy of thin foils, carbon and aluminum extraction replicas, and by X-ray dispersion and energy-loss spectroscopy from individual precipitates. The temperature of the nose of theC-curve for precipitation in vanadium steels is much lower than that in niobium steels, as is the temperature, T_R, below which no recrystallization occurs in short times. Precipitation occurs both at austenite grain boundaries and in the grains (matrix precipitation). The former starts early and the precipitates grow rapidly to an approximately constant size; the matrix precipitates grow more slowly and are responsible for the observed hardening of the austenite. The relevance of various models proposed for the retardation and arrest of recrystallization of austenite are discussed. In the steels containing vanadium and niobium the precipitates contain both heavy elements: (V,Nb) (C,N). The Nb/V ratio in the matrix precipitates is different than in the parent austenite. The grain-boundary precipitates, however, contain the same Nb/V ratio as the parent austenite. The rate of hardening exhibits a reverseC-curve behavior, being more rapid than in the corresponding vanadium steels at higher temperatures and about the same at lower temperatures. Formerly Research Associate at MIT     

Effect of Pd, Cu, and Ni additions on the kinetics of NiCl2 reduction by hydrogen

Differnetial thermal analysis (DTA) and thermal gravimetric analysis (TGA), at a heating rate of 10 °C/min, revealed a complete reduction of NiCl₂ by hydrogen in a temperature interval of 375 °C to 450 °C. However, addition of 0.1 mass pct of Pd, Cu, or Ni to the sample caused the reduction to occur at considerably lower temperatures, in the rather narrow range of 315 °C to 370 °C. The activation energy of NiCl₂ reduction by hydrogen (between 300 °C and 550 °C) without additives is 54 kJ/mol, and with Pd and Cu or Ni added, under isothermal conditions (from 260 °C to 380 °C), is 33 and 50 kJ/mol, respectively. These values confirm a positive effect of additives on the reduction kinetics. The positive effect of Pd is a consequence of the dissociation and spillover of hydrogen, whereas in the case of Cu and Ni(HCOO)₂, it is manifested in a decrease in bonds energy in the nickel lattice because of good Cu solubility, and in the formation of artificial nickel nuclei that intensify the reduction, respectively. Scanning electron microscopy (SEM) analysis of nickel powders obtained under isothermal conditions shows relatively rounded spherical particles (0.321 to 0.780 μm in size) of powder samples with additives, and particles of irregular shape (2.085 μm mean size) of the sample without additives. This illustrates the positive effect of Pd, Cu, or Ni added in the reduction process, in decreasing the size of nickel particles and in the production of a more uniform particle shape.     

Dislocation structures in single-crystal tungsten and tungsten alloys

Deformation of tungsten single crystals as a function of strain, temperature, and alloying was studied by transmission electron microscopy. Single crystals oriented for (?101)[lll] slip were grown by electron beam zone refining. Compression specimens of tungsten, W-l and 3 pct Re and W-l and 3 pct Ta were deformed to 2 pct strain at 150°, 300°, and 590°K (0.04, 0.08, and 0.16T _m). Specimens were also strained to 0.5 and 5.0 pct strain at 300°K. Transmission microscopy revealed that the dislocation substructures in single-crystal tungsten are similar to substructures in other refractory metals when compared on a homologous temperature basis. At temperatures greater than 0.1T _m, the substructure is characterized primarily by edge dipoles. At temperatures less than 0.1T _m, long screw dislocations lying parallel to the primary [111] slip direction characterize the substructure. Rhenium additions to tungsten promote formation of edge dipoles at temperatures of 300° and 150°K and increase dislocation density at all three temperatures. In addition, dislocations consistent with (1?12)[?111] slip were observed in the W-Re single crystals after deformation at 150°K. Tantalum additions had a lesser effect on the dislocation substructure compared to rhenium additions. The W-l and 3 pct Ta alloys exhibited higher dislocation densities than unalloyed tungsten after similar strains and, at 150°K, W-3 pct Ta contained a few dislocations consistent with (1?12)[?111] slip. It is concluded that the reduction in ductile-brittle transition temperature of poly crystalline tungsten containing dilute rhenium additions, 1 to 5 pct, can be attributed to an increase in dislocation mobility at temperatures less than 0.1 T_m.