Effect of friction stir processing on the kinetics of superplastic deformation in an Al-Mg-Zr alloy

The effect of friction stir processing on the superplastic behavior of extruded Al-4Mg-1Zr was examined at 350 °C to 600 °C and at initial strain rates of 1×10⁻³ to 1 s⁻¹. A combination of a fine grain size of 1.5 μm and high-angle grain boundaries in the friction stir-processed (FSP) alloy led to considerably enhanced superplastic ductility, much-reduced flow stress, and a shift to a higher optimum strain rate and lower optimum temperature. The as-extruded alloy exhibited the highest superplastic ductility of 1015 pct at 580 °C and an initial strain rate of 1×10⁻²s⁻¹, whereas a maximum elongation of 1280 pct was obtained at 525 °C and an initial strain rate of 1×10⁻¹s⁻¹ for the FSP alloy. The FSP alloy exhibited enhanced superplastic deformation kinetics compared to that predicted by the constitutive relationship for superplasticity in fine-grained aluminum alloys. A possible origin for enhanced superplastic deformation kinetics in the FSP condition is proposed.     

Nitridation kinetics of niobium in the temperature range of 873 to 1273 K

The kinetics of Nb (Cb) nitridation and ε-NbN growth obey a parabolic relationship and their temperature dependence can be expressed ask _p = 5.19 × 10⁻⁷ exp (−125,500/RT) and (k _{p ξ} = 1.15 × 10⁻⁴ exp (−61,500/RT), respectively, with the activation energies in joules/mole. The nitrogen diffusion coefficient in niobium, obtained from microhardness traverses, is given byD = 1.02 × 10⁻⁵ exp (−77,000/RT). A diffusion model accounting for the partition of nitrogen between ε-NbN and Nb is proposed. The total nitrogen uptake calculated from the model is compared to that obtained experimentally.     

Thermal dependence of austempering transformation kinetics of compacted graphite cast iron

The evolution of the relative fraction of high-carbon austenite with austempering time and temperature was analyzed in a compacted graphite (CG) cast iron (average composition, in wt pct: 3.40C, 2.8Si, 0.8Mn, 0.04Cu, 0.01P, and 0.02S) at five different austempering temperatures between 573 and 673 K. Samples were characterized by Mössbauer spectroscopy, hardness measurements, and optical microscopy. During the first stage of transformation, the kinetics parameters were determined using the Johnson-Mehl’s equation, and their dependence with temperature in the range from 573 to 673 K indicates that the transformation is governed by nucleation and growth processes. The balance between growth-rate kinetics and nucleation kinetics causes the kinetics parameter (k) to have a maximum at ≈623 K of 3.9×10^?3(s^?1). The evolution of the C content in the high-carbon austenite was found to be controlled by the volume diffusion of carbon atoms from the ferrite/austenite interface into austenite, with a dependence of t ^0.40±0.05 on the austempering time (t).     

Plastic deformation kinetics of fine-grained alumina

The plastic deformation kinetics of a commercial fine-grained alumina with ∼300 ppm MgO and grain sizes from 1.4 to 2.9 μm were determined in tension at 1475 °C to 1600 °C and strain rates from 10⁻⁵ to 10⁻³ s⁻¹, employing stress relaxation (SR) as the principal test mode. The constants in the Weertman-Dorn (W-D) equation were determined and had the following values: A=2.9±0.5×10⁹, n=2.2±0.1, p=1.9±0.1, Q=492±3 kJ/mole, and threshold stress σ ₀=0. These constants are in accord with grain boundary sliding (GBS) accommodated by dislocation glide and climb with Al³⁺ ion lattice diffusion as the rate-controlling mechanism.     

Effects of temperature and strain rate on tensile properties and activation energy for dynamic strain aging in alloy 625

Alloy 625 ammonia cracker tubes were service exposed for 60,000 hours at 873 K. These were then subjected to a solution-annealing treatment at 1473 K for 0.5 hours. The effects of temperature and strain rate on the tensile properties of the solution-annealed alloy were examined in the temperature range of 300 to 1023 K, employing the strain rates in the range of 3×10⁻⁵ s⁻¹ to 3×10⁻³ s⁻¹. At intermediate temperatures (523 to 923 K), various manifestations of dynamic strain aging (DSA) such as serrated flow, peaks, and plateaus in the variations of yield strength (YS) and ultimate tensile strength (UTS) and work-hardening rate with temperature were observed. The activation energy for serrated flow (Q) was determined by employing various methodologies for T<823 K, where a normal Portevien-Le Chatelier effect (PLE) was observed. The value of Q was found to be independent of the method employed. The average Q value of 98 kJ/mol was found to be in agreement with that for Mo migration in a Ni matrix. At elevated temperatures (T≥823 K), type-C serrations and an inverse PLE was noticed. The decrease in uniform elongation beyond 873 K for 3×10⁻⁵ s⁻¹ and 3×10⁻³ s⁻¹ and beyond 923 K for 3×10⁻⁴ s⁻¹ strain rates seen in this alloy has been ascribed to reduction in ductility due to precipitation of carbides and δ phase on the grain boundaries.     

Effect of strain rate on the fracture behavior at 1366 K of the bcc iron base oxide dispersion strengthened alloy MA 956

The tensile behavior of the oxide dispersion strengthened iron-base alloy MA 956 was investigated as a function of strain-rate ranging from 3.3×10⁻² to 8.3×10⁻⁸ s⁻¹ at 1366 K. All tests were conducted in the longitudinal direction on specimens machined from bar stock. Because of the microstructure of this alloy, all specimens were either single crystals or bicrystals with the boundary parallel to the gage length. Testing revealed that the strength was rather insensitive to strain-rate, the tensile ductility decreased with decreasing strain-rate, and for strain-rates ≤8.3×10⁻⁵ s⁻¹, the alloy fractured in brittle manner. Evidence of transgranular cracking perpendicular to the applied stress was observed at all strain-rates; failure at strain-rates ≤8.3×10⁻⁵ s⁻¹ was due to cracks which grow by the joining together of cavities ahead of the running crack. This alloy appears to possess a critical stress intensity factor for rapid crack growth.     

Fracture behavior of a B2 Ni-30Al-20Fe-0.05Zr intermetallic alloy in the temperature range 300 to 1300 K

Tensile tests were conducted on a Ni-30 (at. pct) Al-20Fe-0.05Zr intermetallic alloy in the temperature range 300 to 1300 K under initial strain rates varying between 10⁻⁶ and 10⁻³ s⁻¹. The alloy did not exhibit any room-temperature ductility and failed at an average stress of about 710 MPa. The brittle-to-ductile transition temperature (BDTT), which was higher than those for Ni-50Al and Ni-50Al-0.05Zr, was relatively insensitive to strain rate and varied between about 960 K at a nominal strain rate of 1.4×10⁻⁵s⁻¹ to about 990 K at a strain rate of 1.4× 10⁻³s⁻¹. Detailed observations of the fracture surfaces revealed that cleavage failure had originated at a pre-existing defect in all instances, where the fracture stress, σ _f , correlated extremely well with the square root of the average defect size, 2c, in accordance with linear elastic fracture mechanics. The average value of the critical stress intensity factor estimated from the σ _f − 2c data varied between 4 to 7 MPa m^1/2. A comparison of the fracture map for this intermetallic alloy with those for face-centered cubic (fcc) and refractory body-centered cubic (bcc) metals, alkali halides, refractory oxides, and covalent-bonded ceramics indicated that the low-temperature brittleness of the alloy is, in part, due to mixed atomic bonding.     

Diffusion of managenese and silicon in liquid iron over the whole range of composition

The measurement of the diffusivities of manganese and silicon in molten binary ferroalloys over the whole range of composition was undertaken to clarify existing but conflicting data at lower concentrations, to present new data at higher concentrations and to indirectly confirm the behavior of both systems observed in thermodynamic studies. The experiments were carried out under argon atmosphere in a Tammann furnace. The diffusion couples were held in 5 mm ID alumina tubes (98 pct Al₂O₃). Electron probe microanalysis of the samples led to a diffusion-penetration curve for the system under consideration. Results obtained over the whole range of composition showed a slight negative deviation for the Fe−Mn system and a very large positive deviation for the Fe−Si system. At lower concentrations (0 to 4 pct Mn), the temperature dependence of managanese diffusivity for the Fe−Mn binary alloy in the temperature range 1550° to 1700°C is as follows:D _Fe−Mn=1.8×10⁻³ exp (−13,000/RT) cm²/sec The concentration dependence of manganese diffusivity for the same system at 1600°C may be expressed asD _Fe−Mn={5.48−0.0137 (%Mn)+0.000276 (%Mn)²}×10⁻⁵ cm²/sec The temperature dependence of silicon diffusivity for the Fe−Si binary system in the temperature range 1550° to 1725°C at various concentrations is as follows:D _Fe−Si=2.8×10⁻³ exp (−11,900/RT) cm²/sec at 20 pct SiD _Fe−Si=2.1×10⁻³ exp (−13,200/RT) cm²/sec at 12.5 pct SiD _Fe−Si=5.1×10⁻⁴ exp (−9,150/RT) cm²/sec at 2.2 pct Si FELIPE P. CALDERON, formerly Graduate Student. University of Tokyo, Tokyo, Japan. This paper is based on a portion of a thesis submitted by FELIPE P. CALDERON in partial fulfillment of the requirements for the degree of Doctor of Engineering at University of Tokyo.     

High-strain-rate superplastic behavior of equal-channel angular-pressed 5083 Al-0.2 wt pct Sc

Tensile tests were carried out at temperatures of 673 to 773 K and strain rates of 1×10⁻³ to 1 s⁻¹ on an ultrafine-grained (UFG) 5083 Al alloy containing 0.2 wt pct Sc fabricated by equal-channel angular pressing, in order to examine its high-strain-rate superplastic characteristics. The mechanical data for the alloy at 723 and 773 K exhibited a sigmoidal behavior in a double logarithmic plot of the maximum true stress vs true strain rate. The strain-rate sensitivity was 0.25 to 0.3 in the low-( <5×10⁻³ s⁻¹) and high- ( >5×10⁻² s⁻¹) strain-rate regions, and ∼0.5 in the intermediate-strain-rate region (5×10⁻³ s⁻¹< <5 × 10⁻² s⁻¹). The maximum elongation to failure of ∼740 pct was obtained at 1×10⁻² s⁻¹ and 773 K. By contrast, no sigmoidal behavior was observed at 673 K. Instead, the strain-rate sensitivity of 0.3 was measured in both intermediate-and low-strain-rate regions, but it was about 0.25 in the high-strain-rate region. High-strain-rate superplasticity (HSRS) in the intermediate-strain-rate region at 723 and 773 K was dominated by grain-boundary sliding (GBS) associated with continuous recrystallization and preservation of fine recrystallized grains by second-phase particles. However, the activation energy for HSRS of the present alloy was lower than that predicted for any standard high-temperature deformation mechanism. The low activation energy was likely the result of the not-fully equilibrated microstructure due to the prior severe plastic deformation (SPD). For 673 K, the mechanical data and the microstructural examination revealed that viscous glide was a dominant deformation mechanism in the intermediate- and low-strain-rate regions. Deformation in the high-strain-rate region at all testing temperatures was attributed to dislocation breakaway from solute atmospheres.     

Intrinsic kinetics of the reaction between zinc sulfide and water vapor

The reaction between zinc sulfide and water vapor is a component reaction in a new reaction scheme recently developed to transform zinc sulfide to zinc oxide through the use of lime and water vapor. The intrinsic kinetics of this reaction for ultrafinely ground (<1 μm) ZnS particles was determined by carrying out measurements in the absence of heat- and mass-transfer effects. The reaction products were identified to be ZnO and H₂S. The kinetics of the reaction can be represented by and 3.94<C _H2_O <9.84 mol/m³ withn=1.28 andk ₁=45.3 exp(−14600/T) m³·mol⁻¹·s⁻¹, whereX _B is the fractional conversion. DAESOO KIM, formerly Granduate Student at the University of Utah     

High temperature deformation of a commercial aluminum alloy

A study of high temperature deformation of a commercial aluminum alloy has been undertaken through tensile tests at strain rates ranging from 5.6×10⁻⁵ s⁻¹ to 5.6×10⁻² s⁻¹ and load relaxation testing in the temperature range 473 to 873 K. Experiments have established that maximum ductility is reached at about 623 K and at maximum strain rates. Maximum fracture ductility corresponds to minimum uniform elongation. The deformation and fracture mechanisms operating in the temperature range 473 to 573 K seem to differ from those between 623 K and 823 K; different strain rate sensitivities are also observed. Dynamic recovery is the dominant softening mechanism in high temperature plastic deformation—that is, a thermally activated process whose kinetics can be suitably described by an empirical power relation.     

Kinetics of reduction of hematite with hydrogen gas at modest temperatures

The kinetics of hydrogen reduction of thin, dense strips of hematite were investigated in the range 245 °C to 482 °C. Pure hydrogen gas at 1 atm was used as the reducing agent. Because of the relative thinness (only 136 /μm thick) of the specimens used, the pore-diffusion of gases offered no significant resistance to the reduction process. The interfacial-reaction-rate constantk _s ^* , which has been corrected for film-mass-transfer effects, is found to be given by logk _s ^* = −1.032 (±0.138) -[7860 (±200)]/2.303r where k _s ^* is in g · atom O · cm⁻² · s⁻¹ · atm⁻¹. The activation energy for the reduction process is found to be 65,325 (±1650) J · mol⁻¹; the rate-controlling step appears to be the Fe₃O₄ → Fe conversion step.     

Rate of interfacial reaction between liquid iron oxide and CO-CO2

The interfacial reaction rate between liquid iron oxide and CO-CO₂ was determined using a thermogravimetric technique. The measured rates were controlled by the chemical reactions at the gas-slag interface. The apparent first-order rate constant, for the oxidation of liquid iron oxide by CO₂, decreased sharply with the equilibrium CO₂/CO ratio. The rate of reduction of liquid iron oxide by CO showed a slight increase with the oxidation state of the melt. At 1773 K, the apparent first-order rate constants are given by k=4.0×10⁻⁵(CO₂/CO)^−0.8 and k=4.0 × 10⁻⁵(CO₂/CO)^0.18 mol cm⁻² s⁻¹ atm⁻¹ for the oxidation and reduction, respectively. The addition of basic oxides, such as BaO and CaO, resulted in an increased reaction rate, while the addition of acidic oxide, such as SiO₂, decreased the rate. The results are consistent with the dissociation or formation of the CO₂ molecule, involving the transfer of two charges, being the rate controlling mechanism of the reactions. This article is based on a presentation made in the “Geoffrey Belton Memorial Symposium,” held in January 2000, in Sydney, Australia, under the joint sponsorship of ISS and TMS.     

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.     

Dynamic-coarsening behavior of an α/β titanium alloy

The dynamic-coarsening behavior of Ti-6Al-4V with an equiaxed α microstructure was established via isothermal hot-compression testing of cylindrical samples cut from an ultra-fine-grain-size (UFG) billet. Compression experiments were conducted at 900 and 955 °C, strain rates between 10⁻⁴ and 1 s⁻¹, and imposed true strains between 0 and 1.4. Following deformation, quantitative metallography revealed marked coarsening of the primary α particles at low strain rates (10⁻⁴ and 10⁻³ s⁻¹). The dynamic-coarsening rate followed rⁿ vs time kinetics, in which n was between 2 and 3, or behavior between those of bulk-diffusion and interface-reaction controlled. An examination of the temperature and strain-rate dependence of theoretical coarsening rates, however, strongly suggested that bulk diffusion (with n=3) was more important. The dynamic-coarsening behavior was also interpreted in the context of the observed plastic-flow behavior. At low strain rates, high values of the strain-rate sensitivity (m>0.5) and the overall shape of log stress-log strain rate plots indicated that the majority of the imposed strain was accommodated by grain-boundary sliding (gbs) and only a small amount via dislocation glide/climb processes. In addition, an analysis of the flow hardening that accompanied dynamic coarsening indicated that the flow stress varied approximately linearly with the α particle size, thus providing support for models based on gbs accommodation by dislocation activity in grain-mantle regions.     

Deformation behavior of a Ni−30Al−20Fe−0.05Zr intermetallic alloy in the temperature range 300 to 1300 K

The deformation behavior of an extruded Ni-30 (at. pct) Al−20Fe−0.05Zr intermetallic alloy was studied in the temperature range of 300 to 1300 K under initial tensile strain rates varying between about 10⁻⁶ and 2×10⁻³ s⁻¹ and in constant load compression creep between 1073 and 1300 K. The deformation microstructures of the fractured specimens were characterized by transmission electron microscopy (TEM). Three deformation regimes were observed: Region I consisted of an athermal regime of low tensile ductility (less than 0.3 pct) occurring between 400 and 673 K, where the substructure consisted of slip bands in a few grains. Exponential creep was dominant in region II between 673 and 1073 K, where the substructure changed from a mixture of dislocation tangles, loops, and dipoles at 673 K to a microstructure consisting of subgrains and dislocation tangles at 973 K. The tensile ductility was generally about 2.0 to 2.5 pct below 980 K in this region. A significant improvement in tensile ductility was observed in region III, which occurred between 1073 and 1300 K. An analysis of the data suggests that viscous glide creep with a stress exponent,n, of about 3 and high-temperature dislocation climb withn≈4.5 where the two dominant creep mechanisms in this region depending on stress and temperature. The average activation energy for deformation in this region was about 310±30 kJ mol⁻¹ for both processes. In this case, a transition from viscous glide creep to dislocation climb occurred when σ/E<1.7×10⁻⁴, where σ is the applied stress andE is the Young’s modulus.     

Coarsening of Al<Subscript>3</Subscript>Sc precipitates in an Al-0.28 wt pct Sc alloy

The Ostwald ripening of Al₃Sc precipitates in an Al-0.28 wt pct Sc alloy during aging at 673, 698, and 723 K has been examined by measuring the average size of precipitates by transmission electron microscopy (TEM) and the reduction in Sc concentration in the Al matrix with aging time, t, by electrical resistivity. The coarsening kinetics of Al₃Sc precipitates obey the t ^1/3 time law, as predicted by the Lifshitz-Slyozov-Wagner (LSW) theory. The kinetics of the reduction of Sc concentration with t are consistent with the predicted t ^−1/3 time law. Application of the LSW theory has enabled independent calculation of the Al/Al₃Sc interface energy, γ, and volume diffusion coefficient, D, of Sc in Al during coarsening of precipitates. The Gibbs-Thompson equation has been used to give a value of γ using coarsening data obtained from TEM and electrical resistivity measurements. The value of γ estimated from the LSW theory is 218 mJ m⁻², which is nearly identical to 230 mJ m⁻² from the Gibbs-Thompson equation. The pre-exponential factor and activation energy for diffusion of Sc in Al are determined to be (7.2±6.0)×10⁻⁴ m² s⁻¹ and 176±9 kJ mol⁻¹, respectively. The values are in agreement with those for diffusion of Sc in Al obtained from tracer diffusion measurements.     

Plastic deformation of austenitic iron at intermediate strain rates

The plastic deformation of austenitic iron, represented by a zone-refined iron, an electrolytic iron, an Fe−0.05 C alloy, and an Fe−5.2 Mn alloy, has been documented for the temperature range 950 to 1350°C (1740 to 2460°F) and the strain-rate range 2.8 × 10⁻⁵ to 2.3 × 10⁻² s⁻¹. The intrusion of recrystallization during deformation restricts the documentation to initial periods of strain usually less than 0.10. The general problem of retaining grain structures representative of polycrystals in specimens annealed at temperatures above 0.95T _m is recognized, and a basis for its solution is presented. Chemical composion appears to influence the plastic-flow behavior of austenitic iron primarily through its effect on the grain structure. Thus, the large-grained zone-refined iron is relatively weak, and the difference in behavior between the Fe−0.05 C alloy and the Fe−5.2 Mn alloy is small. Formerly Associate Scientist, U.S. Steel Corporation.     

Internal displacement reactions in multicomponent oxides. Part I. Line compounds with narrow homogeneity range

As a model of an internal displacement reaction involving a ternary oxide “line” compound, the following reaction was studied at 1273 K as a function of time, t: Both polycrystalline and single-crystal materials were used as the starting NiTiO₃ oxide. During the reaction, the Ni in the oxide compound is displaced by Fe and it precipitates as a γ-(Ni-Fe) alloy. The reaction preserves the starting ilmenite structure. The product oxide has a constant Ti concentration across the reaction zone, with variation in the concentration of Fe and Ni, consistent with ilmenite composition. In the case of single-crystal NiTiO₃ as the starting oxide, the γ alloy has a “layered” structure and the layer separation is suggestive of Liesegang-type precipitation. In the case of polycrystalline NiTiO₃ as the starting oxide, the alloy precipitates mainly along grain boundaries, with some particles inside the grains. A concentration gradient exists in the alloy across the reaction zone and the composition is >95 at. pct Ni at the reaction front. The parabolic rate constant for the reaction is k _p =1.3 × 10⁻¹² m² s⁻¹ and is nearly the same for both single-crystal and polycrystalline oxides.     

Superplastic behavior and microstructure evolution in a commercial Al-Mg-Sc alloy subjected to intense plastic straining

A commercial Al-6 pct Mg-0.3 pct Sc-0.3 pct Mn alloy subjected to equal-channel angular extrusion (ECAE) at 325 °C to a total strain of about 16 resulted in an average grain size of about 1 μm. Superplastic properties and microstructural evolution of the alloy were studied in tension at strain rates ranging from 1.4 × 10⁻⁵ to 1.4 s⁻¹ in the temperature interval 250 °C to 500 °C. It was shown that this alloy exhibited superior superplastic properties in the wide temperature range 250 °C to 500 °C at strain rates higher than 10⁻² s⁻¹. The highest elongation to failure of 2000 pct was attained at a temperature of 450 °C and an initial strain rate of 5.6 × 10⁻² s⁻¹ with the corresponding strain rate sensitivity coefficient of 0.46. An increase in temperature from 250 °C to 500 °C resulted in a shift of the optimal strain rate for superplasticity, at which highest ductility appeared, to higher strain rates. Superior superplastic properties of the commercial Al-Mg-Sc alloy are attributed to high stability of ultrafine grain structure under static annealing and superplastic deformation at T ≤ 450 °C. Two different fracture mechanisms were revealed. At temperatures higher than 300 °C or strain rates less than 10⁻¹ s⁻¹, failure took place in a brittle manner almost without necking, and cavitation played a major role in the failure. In contrast, at low temperatures or high strain rates, fracture occurred in a ductile manner by localized necking. The results suggest that the development of ultrafine-grained structure in the commercial Al-Mg-Sc alloy enables superplastic deformation at high strain rates and low temperatures, making the process of superplastic forming commercially attractive for the fabrication of high-volume components.