The microstructure of metastable phases in Ag-Cu alloys generated by continuous laser melt quenching

A scanning high power CW CO₂ laser with an average power density of 13.4 MW cm^-2 was used to produce metastable phases in three Ag-Cu alloys; Cu 25 at pct Ag, Cu 50 at pct Ag, and Cu 75 at pct Ag. Scanning, at traverse rates of 10 to 115 cm s^-1, was performed in an inert atmosphere to prevent oxidation. Inspection of the trails by scanning electron microscopy showed the microstructure to be either cellular dendritic or featureless. X-ray examination of the trails verified the presence of extended metastable solid solutions. After etching, the transverse section showed alternating light and dark bands perpendicular to the local growth direction. Through the use of energy dispersive X-ray analysis, it was shown that there was a significant increase in the Ag concentration in the light bands.     

Discussion of “effects of tensile stress on microstructural change of eutectoid Zn-AI alloy”

In a recent contribution,[1] Zhu and Orozco presented a phase transformation of the ternary alloy Zn-20.2 wt pct Al-1.8 wt pct Cu, studied under tensile stress by using X-ray diffraction and scanning electron microscopy techniques. The authors report the existence of three phases in the alloy at room temperature after furnace cooling,α,ε, and a newη _′ ^T instead of the zinc-rich solid solutionη, as appears in the phase diagrams. The reported parameters for this hcp metastable phase are^[1,2] a = 0.2663 andc = 0.4873 nm; these values are close to the parameters of pure zinc,^[3] witha = 0.2664 nm andc = 0.4946 nm. The difference betweenη _′ ^T and zinc in thea parameter is around 0.03 pct, and it is 1.47 pet for thec parameter. When zinc is saturated with aluminum in the Zn-AI alloys, thea parameter shrinks^[3] to 0.2660 nm. It is possible to see that the value ofa of theη _′ ^T phase lies in-between the values of pure zinc and zinc-aluminum solid solution. The solubility of Al and Cu in Zn^[4] at 100 °C is 0.3 wt pct Cu and 0.06 wt pct Al. The covalent radius of Cu (0.117 nm) is smaller than the covalent radius of Al (0.118 nm) and Zn (0.125 nm), so the introduction of Cu in the zinc structure can result in a reduction of thec parameter. These values suggest that the metastable phaseη _′ ^T could be the hcp zincrich solid solution with low aluminum and copper contents. The article of Zhu and Goodwin,^[5] cited by Zhu and Orozco in their Reference 14, is related not to the eutectoid alloy, as they argue, but to an alloy with 27 wt pct Al, and no reports about the transformation ofε intoT′ were found. The presence of the metastable e phase (CuZn₄, sometimes called CuZn₅) at room temperature and its transformation to the stable phaseT′ (rhombohedral intermetallic phase, Al₄Cu₃Zn) have been observed by other authors.^[6,7] Y.H. ZHU and E. OROZCO:Metall Mater. Trans. A, 1995, vol. 26A, pp. 2611-15.     

Diffusion paths and structures in multiphase Cu−Ni−Zn couples at 775°C

Multiphase diffusion was investigated in the Cu−Ni−Zn system at 775°C for the development of diffusion structures involving two interfaces. Selected series of diffusion couples characterized by a common γ (cubic) terminal alloy joined to a set of α (fcc) alloys developed an intermediate β (bcc) phase with two interfaces, α/β and β/γ. The α/β interface showed transitions from planar to nonplanar and back to planar morphology, as the copper concentration of the α terminal alloy was decreased from 100 to about 30 at. pct. Planar β/γ interfaces were observed for all but two of the couples. The compositions on either side of planar α/β interfaces were consistent with those based on equilibrium tielines, while the compositions at nonplanar α/β interfaces differed from those of equilibrium. Selected series of couples assembled with γ and β alloys were also investigated for the development of interface instability at the β/γ interface. The diffusion paths of γ/β couples were consistent with those of γ/α couples.     

On the decomposition of β phase in some rapidly quenched titanium-eutectoid alloys

The decomposition of the β phase in rapidly quenched Ti-2.8 at. pct Co, Ti-5.4 at. pct Ni, Ti-4.5 at. pct, and 5.5 at. pct Cu alloys has been investigated by electron microscopy. During rapid quenching, two compctitive phase transformations, namely martensitic and eutectoid transformation, have occurred, and the region of eutectoid transformation is extended due to the high cooling rates involved. The β phase decomposed into nonlamellar eutectoid product (bainite) having a globular morphology in Ti-2.8 pct Co and Ti-4.5 pct Cu (hypoeutectoid) alloys. In the near-eutectoid Ti-5.5 pct Cu alloy, the decomposition occurred by a lamellar (pearlite) type, whereas in Ti-5.4 pct Ni (hypereutectoid), both morphologies were observed. The interfaces between the proeutectoid α and the intermetallic compound in the nonlamellar type as well as between the proeutectoid α and the pearlite were often found to be partially coherent. These findings are in agreement with the Lee and Aaronson model proposed recently for the evolution of bainite and pearlite structures during the solid-state transformations of some titanium-eutectoid alloys. The evolution of the Ti₂Cu phase during rapid quenching involved the formation of a metastable phase closely related to an “ω-type” phase before the equilibrium phase formed. Further, the lamellar intermetallic compound Ti₂Cu was found to evolve by a sympathetic nucleation process. Evidence is established for the sympathetic nucleation of the proeutectoid a crystals formed during rapid quenching.     

Transformation squence in a Cu-Al-Ni shape memory alloy at elevated temperatures

Precipitation sequences in a Cu-14 pct Al-4 pct Ni (wt pct) shape memory alloy were studied by means of transmission electron diffraction and microscopy as well as X-ray microanalysis techniques. On aging thin foil specimens up to 550 °C in the electron microscope, an as-quenched sample having a mixture of 2H-type and D0₃-type metastable structures transformed to the stable simple cubic γ₂ phase at or above 450 °C. The remaining matrix either showed precipitates of the fcc α-phase on prolonged annealing at 500 to 550 °C for a longer period, or transformed to martensite on cooling below theM _s temperature (~150 °C).     

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.     

Effects of Cu content and preaging on precipitation characteristics in aluminum alloy 6022

Effects of Cu content and preaging treatments on precipitation sequence and artificial aging response in aluminum alloy 6022 were investigated using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and hardness tests. It was found that Cu induces the formation of Q and its precursor metastable phases and has a beneficial effect on the kinetics of artificial aging. For the alloy with 0.07 wt pct Cu, the precipitation sequence is GP zones → needlelike β″ → rodlike β′ + lathlike Q′ → β + Si. On the other hand, the precipitation sequence in the alloy with 0.91 wt pct Cu is GP zones → needlelike β′ → lathlike Q′→Q+Si. For the artificial aging condition of 20 minutes at 175 °C, which is the typical automotive paint bake condition, suitable preaging treatments were found to significantly reduce the detrimental effect of the natural aging on artificial aging response.     

The compctition between the alpha and omega phases in aged Ti-Nb alloys

The compctition between the stable α phase and metastable ω phase to precipitate in a metastableβ phase matrix was investigated in the present study. Four binary Ti-Ni alloys with compositions between 20 and 35 at. pct Nb were air cooled to room temperature from 1000 °C and then aged at temperatures between 300 and 500 °C. For aging temperatures of 400 °C and lower it was found that the quench before aging enabled ω phase precipitates to grow to the exclusion of α precipitates. When specimens were directly aged at 400 °C only α precipitates were observed. Precipitates which could not be identified using SAD were observed in specimens of the 30 and 35 at. pct Nb alloys. All precipitation reactions became more sluggish as the niobium content of an alloy was increased. The results reported here form the second part of a study of the stable and metastable equilibria of the Ti-Nb alloy system. Formerly a Graduate Student in the Materials Science Program at the University of Wisconsin-Madison     

Microstructure and phase relations for Ti-Mo-Al alloys

The influence of aluminum additions to a Ti-7 at. pet Mo alloy on the phase equilibria was investigated. The microstructures of the alloys, Ti-7 pct Mo-7 pct Al and Ti-7 pct Mo-16 pct Al, were determined by light and electron microscopy. It was found that with increasing aluminum concentration the formation of the metastable w phase was suppressed. In the Ti-7 pct Mo-16 pct Al alloy the β phase decomposed upon quenching by precipitating coherent, ordered particles having a B2 type of crystal structure (β₂). At low temperatures the equilibrium phases for this alloy were β + α+ β ₂, whereas at high temperature (850° to 950°C) the Ti₃Al phase was in two-phase equilibrium with the β phase. The four-phase equilibrium which exists at a temperature of about 550°C involves the reaction β + Ti₃Al ⇌ α + β₂. G. LUETJERING, formerly Staff Member Materials Research Center, Allied Chemical Corp., Morristown, N. J.,     

Microstructure and its development in Cu-Al-Ni alloys

The microstructure of as-cast Cu-AI-Ni alloys, based on copper containing 9 to 10 wt pct Al and up to 5 wt pct Ni, has been examined. The development of the microstructure on continuous cooling has also been investigated. For alloys with 9.2 to 9.3 wt pct Al, and less than 1 wt pct Ni, the as-cast microstructure consists of proeutectoid α solid solution, α + γ₂ eutectoid, and martensitic β. If the nickel content is more than 2.5 wt pct, the α + γ₂ eutectoid is replaced by α + β ₂ ^′ eutectoid, and no martensitic β is observed in the as-cast alloys. The morphologies of the β ₂ ^′ and γ₂ eutectoid phases are similar; both have the Kurdjumov-Sachs (K-S) orientation relationship with the a phase. Two eutectoid reactions, involving β to α + γ₂ and β to α + β′₂, have been observed in an alloy containing 9.7 wt pct Al and 2.7 wt pct Ni. When both eutectoid reactions occur, the Nishiyama-Wassermann (N-W) orientation relationship exists between γ₂ or β ₂ ^′ and the α phase. During continuous cooling, proeutectoid α solid solution is the first phase to precipitate from the high-temperature β phase. The β to α + β ₂ ^′ eutectoid reaction starts at higher temperatures than the β to α + γ₂ reaction. Tempering of the as-cast alloys results in the elimination of the martensitic β. Y.S. SUN formerly Research Associate with the Manchester Materials Science Centre.     

Microstructure and corrosion behavior of as-cast and heat-treated Al-4.5 Wt pct Cu-2.0 wt pct Mn alloys

The microstructure and corrosion behavior of as-cast and heat-treated Al-4.5 pct Cu-2.0 pct Mn alloy specimens solidified at various cooling rates were investigated. The equilibrium phases Al₆Mn and θ-Al₂Cu, which are observed in the conventionally solidified alloy in the as-cast condition, were not detected in rapidly solidified (melt-spun) material. Instead, the ternary compound Al₂₀Cu₂Mn₃ was present in addition to the α phase, which was present in all cases. The morphological and kinetic nature of corrosion was investigated metallographically and through potentiostatic techniques in 3.5 wt pct NaCl aqueous solution. Corrosion of the as-cast material was described by two anodic reactions: corrosion of the intermetallic phases and pitting of the α-Al solid solution. The corrosion rate increased with cooling rate from that for the furnace-cooled alloy to that for the copper mold-cast alloy and, subsequently, decreased in the rapidly solidified alloy. In the heat-treated material, corrosion could be described by two anodic reactions: corrosion of Al₂₀Cu₂Mn₃ precipitate particles and pitting of the α-Al matrix. S.M. Skolianos, formerly Graduate Student, Department of Metallurgy, University of Connecticut     

The vanadium-platinum constitution diagram

The system V-Pt was investigated over the entire composition range by metallography, X-ray diffraction and electron microprobe studies. There are at least four equilibrium intermediate phases in this system and they are stable to progressively higher temperatures with increasing vanadium concentration. The phases which have been observed are: γ^′, cubic, Cu₃Au type; θ, tetragonal, TiAl₃ type; δ, orthorhombic, MoPt₂ type; ζ, orthorhombic, AuCd type; and β, cubic, Cr₃Si type (A15). The gg^′ phase is possibly metastable. A very stable ribbon-like growth of ζ phase in the fcc platinum terminal solid solution has been observed in alloys containing about 43 at. pct V. The platinum terminal solid solution forms a congruent melting maximum at about 1805°C. A eutectic reaction occurs at 1720° ± 10°C and a peritectic reaction is indicated at 1800° ± 10°C. Vanadium is soluble in the fcc platinum terminal solid solution up to about 57 at. pct at 1720°C. Platinum dissolves only to the extent of about 12 at. pct at 1800°C in bcc α-V.     

Effect of Mn on the Microstructure and Magnetic Properties in Cu-Fe-Co Alloys

An attempt was made to study the effect of Mn addition on the formation of supersaturated solid solution of Co and Fe in Cu during ball milling and precipitation of the solute-rich phases during subsequent annealing of the ball-milled product. It is demonstrated that the addition of Mn in the ternary CuFeCo powder blend enhances the metastable solubility of Fe and Co in Cu and facilitates the formation of the nanocrystalline supersaturated single-phase solid solution. Field emission–scanning electron microscopy (FE-SEM) also revealed notable influence of Mn on the morphological evolution of the ball-milled and annealed alloy powders. X-ray diffraction (XRD) analysis revealed that the FeCo phase having the bcc Bravais lattice forms after annealing at and above 620 K (350 °C) in both alloys. Estimation of magnetic properties showed that Mn addition in the CuFeCo alloy improved the coercivity, remanence, and magnetic saturation.     

An AEM investigation of the formation of precipitate-free zones in an AI-16 Wt Pct Ag alloy: Determination of equilibrium and metastable solvus lines

Precipitation of the equilibrium y-phase at grain boundaries in an aged Al-16 wt pct (～4.5 at. pct) Ag alloy is responsible for the formation of a solute depleted region, free of metastable Guinier-Preston (GP) zones, in the immediate vicinity of the grain boundary. Solute concentration profiles have been obtained across these grain boundary regions using Analytical Electron Microscopy (AEM) in thin foils of the alloy aged at low temperatures. The Ag concentrations at the grain boundary (between γ precipitates) and at the edge of the precipitate-free zone have been used to determine the solid solubility of Ag in Al (the α/(α + γ) solvus) and the metastable GP zone solvus line, respectively.     

Effect of the primary phase on grain coarsening in undercooled Fe-Co alloys

Fe-Co alloy melts with Co contents of 10, 30, and 60 at. pct were undercooled to investigate the dependence of the primary phase on grain coarsening. A pronounced characteristic is that the metastable fcc phase in the Fe-10 at. pct Co alloy and the metastable bcc phase in the Fe-30 at. pct Co alloy will primarily nucleate when undercoolings of the melts are larger than the critical undercoolings for the formation of metastable phases in both alloys. No metastable bcc phase can be observed in the Fe-60 at. pct Co alloy, even when solidified at the maximum undercooling of ΔT = 312 K. Microstructural investigation shows that the grain size in Fe-10 and Fe-30 at. pct Co alloys increases with undercoolings when the undercoolings of the melts exceed the critical undercoolings. The grain size of the Fe-60 at. pct Co alloy solidified in the undercooling range of 30 to 312 K, in which no metastable phase can be produced, is much finer than those of the Fe-10 and Fe-30 at. pct Co alloys after the formation of metastable phases. The model for breakage of the primary metastable dendrite at the solid-liquid interface during recalescence and remelting of dendrite cores is suggested on the basis of microstructures observed in the Fe-10 and Fe-30 at. pct Co alloys. The grain coarsening after the formation of metastable phases is analyzed, indicating that the different crystal structures present after the crystallization of the primary phase may play a significant role in determining the final grain size in the undercooled Fe-Co melts.     

A metallographic study of porosity and fracture behavior in relation to the tensile properties in 319.2 end chill castings

A metallographic study of the porosity and fracture behavior in unidirectionally solidified end chill castings of 319.2 aluminum alloy (Al-6.2 pct Si-3.8 pct Cu-0.5 pct Fe-0.14 pct Mn-0.06 pct Mg-0.073 pct Ti) was carried out using optical microscopy and scanning electron microscopy (SEM) to determine their relationship with the tensile properties. The parameters varied in the production of these castings were the hydrogen (∼0.1 and ∼0.37 mL/100 g Al), modifier (0 and 300 ppm Sr), and grain refiner (0 and 0.02 wt pct Ti) concentrations, as well as the solidification time, which increased with increasing distance from the end chill bottom of the casting, giving dendrite arm spacings (DASs) ranging from ∼15 to ∼95 /im. Image analysis and energy dispersive X-ray (EDX) analysis were employed for quantification of porosity/microstructural constituents and fracture surface analysis (phase identification), respectively. The results showed that the local solidification time(viz. DAS) significantly influences the ductility at low hydrogen levels; at higher levels, however, hydro-gen has a more pronounced effect (porosity related) on the drop in ductility. Porosity is mainly observed in the form of elongated pores along the grain boundaries, with Sr increasing the porosity volume percent and grain refining increasing the probability for pore branching. The beneficial effect of Sr modification, however, improves the alloy ductility. Fracture of the Si, β-Al₅FeSi, α- Al₁₅(Fe,Mn)₃Si₂, and Al₂Cu phases takes place within the phase particles rather than at the particle/Al matrix interface. Sensitivity of tensile properties to DAS allows for the use of the latter as an indicator of the expected properties of the alloy.     

Metastable phases produced by laser melt quenching

A Nd: glass laser has been used to produce and retain metastable phases which are similar to phases obtained by rapid quenching (“splat cooling”) techniques. A single laser pulse of 10 msec duration was focused onto the surface of an alloy specimen to provide a beam intensity of approximately 3.7 × 10⁵ watts per sq cm. A small volume of metal in the relatively large specimen immediately underwent melting. Upon cessation of the laser pulse, the molten metal solidified very quickly. Extremely rapid cooling was achieved due to the presence of nearly ideal conditions for conduction cooling. Laser melting of various alloys of the eutectic Ag-Cu system resulted in a complete series of solid solutions, as verified by X-ray analysis. In addition, the laser melt quenching technique provided a threefold increase in microhardness of the resolidified metal. Formerly Western Electric Engineering Research Center, Princeton, N. J. 08540     

Microstructure and properties of a Cu-Ni-Cr spinodal alloy

A commercial Cu-28 pct Ni-2.8 pct Cr alloy has been heat treated to produce spinodal structures. Conventional transmission electron microscopy (TEM) and diffraction have been used to study the spinodally decomposed product and to measure the wavelengths in the specimens. It is found that the coarsening of coherent particles obeys the relation λαt ^1/3 at 700δC and λ αt ^1/4 at 600°C. Loss of coherency is observed only when aging at 700°C and λ ~ 1000?, when interfacial dislocations with b = a/2 (110) are created after which the coarsening rate is accelerated. Tensile tests were performed to measure mechanical properties of the aged samples, and the fracture surfaces were examined by scanning electron microscopy. The correlations of microstructural changes and mechanical properties are discussed.     

Stress-assisted transformation in Ti-60 wt pct Ta alloys

An investigation of the influence of processing variables on mechanical properties and phase development for a Ti-60 wt pct Ta (Ti-28.5 at. pct Ta) alloy was conducted. The alloy was hot-rolled, subjected to heat-treatment temperatures above the β (bcc) transus (1 hour at 700 °C, 800 °C, or 900 °C), and water quenched. All heat treatment produced a combination of metastable β (bcc) and metastable α″ (orthorhombic martensite), with the amount of retained β essentially independent of heat treatment, ranging from 20 to 33 vol pct. Deformation of as-rolled and heat-treated tension specimens showed an anomalous leveling of the stress-strain curve in the stress-strain curves at low strains. X-ray diffraction (both simple 2ϑ diffractometry and texture analysis) on both deformed and undeformed material determined that the leveling of the stress-strain curve was a result of the β→α″ martensitic transformation. The stress required to initiate the transformation increased with prequench temperature. This was determined to be due to the presence of athermal ω. Grain growth kinetics have been determined in the course of this work.     

The compctition between martensite and omega in quenched Ti-Nb alloys

A careful experimental study of the phase transformations which occur in annealed β phase Ti-Nb alloys during quenching has been completed. The compctition of the α″ and ω phases to form in alloys of 20 to 70 at. pct Nb was investigated as a function of quench rate and alloy composition. Particular attention was paid to the interstitial content and chemical homogeneity of the alloys. The martensitic α″ phase was found only in 20 and 25 at. pct Nb alloys, and then only using fast water quenches of ~300 °C/sec. Under slower quench conditions,e.g., ~0.3 to 3 °C/sec, ω phase precipitates were found in these alloys and in 30 and 35 at. pct Nb alloys. Evidence of “diffuse” ω phase precipitation was observed in alloys up to 50 at. pct Nb. Only alloys of 60 and 70 at. pct Nb were found to retain the single phaseβ structure upon quenching. These results constitute the first part of a study of the stable and metastable equilibria of the Ti-Nb alloy system. Formerly a Graduate Student in the Materials Science Program at the University of Wisconsin-Madison.