Ordering transformation and spinodal decomposition in Au−Ni alloys

A transmission electron microscope (TEM) was employed to study the ordering and phase separation processes in Au-40 at. pct Ni and Au-50 at. pct Ni alloys in order to test for the possible existence of a transient long-range-order (LRO) phenomenon within a disordered miscibility gap. An L1₀ LRO phase was found in the Au-50 at. pct Ni alloy when spinodally decomposed specimens were reannealed at ∼490°C on a TEM hot stage. This observation, together with the literature results, indicates that a transient LRO did exist in the Au−Ni system, although it appeared during a reversion process. Attempts to find the L1₀ and L1₂ LRO phases during decomposition processes of a single-phase homogeneous solid solution were unsuccessful, except in very thin sections of the TEM foils. Elastic strain energy relaxation was employed to explain the experimental observations. Time-temperature—transformation (TTT) diagrams for the two Au−Ni alloys were constructed based on the TEM characterization. In bulk-annealed samples, only spinodal decomposition and discontinuous precipitation structures were observed. JI-CHENG ZHAO, formerly Graduate Student, Department of Materials Science and Engineering, Lehigh University     

Mechanical properties of Ir-Nb alloys containing Ni and Al

Two alloys made by adding 5 or 10 at. pct, respectively, of Ni-18.9 at. pct Al to an Ir-15 at. pct Nb alloy were investigated. The microstructure and compressive strength at temperatures between room temperature and 1800 °C were investigated to evaluate the potential of these alloys for ultra-high-temperature use. Their microstructural evolution indicated that the two alloys formed fcc and L1₂-Ir₃Nb two-phase structures. The fcc and L1₂ two-phase structures were examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The 0.2 pct flow stresses were above 1000 MPa at temperatures up to 1200 °C, about 150 MPa at 1500 °C, and over 100 MPa at 1800 °C. The strength of the quaternary Ir-base alloys at 1200 °C was even higher than that of Ir-base binary and ternary alloys. And the strength of quaternary Ir-Nb-Ni-Al was equivalent to that of the Ir-15 at. pct Nb binary alloy at 1800 °C. The compressive ductility of quaternary (around 20 pct) was improved drastically compared with that of the Ir-base binary alloy (lower than 10 pct) and the ternary Ir-base alloys (about 11 pct). An excellent balance of high-temperature strength and ductility was obtained in the alloy with 10 at. pct Ni-18.9 at. pct Al. The effect of Ni and Al on the strength of the Ir-Nb binary alloy is discussed.     

Optimization of composition and heat treatment of age-hardened Pt−Al−Cr−Ni alloys

The objective of this work was to produce an alloy showing a microstructure similar to Ni-base superalloys, but with Pt as base metal. The Pt-base alloys with various contents of Al, Cr, and Ni were are melted. Solution heat treatments at 1450 °C followed by water quenching lead to single-phase alloys. Ageing at 1000 °C resulted in the precipitation of L1₂ ordered particles. An alloy with 11 at. pct Al, 3 at. pct Cr, 6 at. pct Ni, and Pt balance shows cuboidal precipitates with edge lengths of 200 to 500 nm along with a volume fraction of 23 pct and a lattice misfit of −0.1 pct. Aging at 1100 °C leads to coarsening of precipitates. Volume fraction and morphology of the precipitates were investigated by scanning electron microscopy and optical microscopy. X-ray diffraction as well as transmission electron microscopy (TEM) were applied to verity the crystal structure. M. Huller, formerly with Metallic Materials, University Bayreuth, D-95440 Bayreuth, Germany     

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.     

Decomposition characteristics of Al-Mn-Zr alloys rapidly-quenched from the melt

The rapidly-quenched structures of liquid Al-Mn-Zr ternary alloys and Al-Mn binary alloys and their decomposition behaviors were investigated by hardness tests, X-ray diffraction analyses, and TEM observations. The solid solubility of Mn can be extended to about 10 wt pct irrespective of whether the alloys contain 1 wt pct Zr or not. The solidification structures are composed of fine dendritic cells and with increasing Mn content, interdendritic precipitates gather volume and branch out into the cell grains. The decomposition of rapidly-quenched alloys takes place during aging for 1 hour at temperatures of 300 to 350 °C, and the dependence of the decomposition temperatures on the Mn content varies in this range. Precipitation hardening of the ternary alloys is intensified by the addition of Mn up to about 7 wt pct and proceeds in a two-step manner during aging in the temperature range examined (350 to 450 °C). It is suggested that the precipitates contributing to the maximum hardening are pseudomorphous to the Al₆Mn equilibrium phase.     

Precipitation processes in near-equiatomic TiNi shape memory alloys

Metallographic studies have been made of precipitation processes in Ti-50 pct Ni and Ti-52 pct Ni (at. pct) shape memory alloys. The eutectoid and peritectoid reactions previously reported for near-equiatomic and Ni-rich TiNi alloys were not observed for either composition. In the Ti-52Ni alloy, diffusional transformations take place, similar to those in supersaturated alloys. The precipitation sequence can be written asβ ₀ → Ti₁₁Ni₁₄ → Ti₂Ni₃ → TiNi₃. The solidus line of the TiNi phase in the Ti-52Ni alloy lies at 812 ± 22 °C. Morphological characteristics of the various precipitate phases are described in detail. M. NISHIDA, formerly with the University of Illinois     

High Cycle Fatigue of (Fe,Ni, Co)3V type alloys

High cycle fatigue tests in vacuum have been performed on ordered (Fe, Co, Ni)₃V alloys between 25 °C and 850 °C. Heat-to-heat variations in fatigue properties of a Co-16.5 wtpct Fe-25 pct alloy, LRO-1, appeared to be due to differing quantities of grain boundary precipitates. Modification of this alloy with 0.4 pct Ti, to produce an alloy designated LRO-23, reduced the density of grain boundary precipitates and increased ductility, resulting in superior fatigue strength at high temperatures. The fatigue lives of LRO-1 and LRO-23 decreased rapidly above 650 °C, and increased intergranular failure was noted. The fatigue resistance of a cobalt-free alloy, Fe-29 pct Ni-22 pct V-0.4 pct Ti (LRO-37), was examined at 25 °C, 400 °C, and 600 °C; there was little evidence for intergranular fracture at any of these temperatures. Fatigue behavior of the LRO alloys is compared to that of conventional high temperature alloys.     

Microstructure of Cu-Co alloys solidified at various supercoolings

The effects of supercooling on the microstructure of Cu-Co alloys containing 10 to 65 wt pct Co were investigated. Supercooling of the alloys below a characteristic temperature,t _SEP, resulted in a metastable phase separation into two liquids: one Co rich (L1) and the other Cu rich (L2). The microstructure of the phase-separated alloys consisted of spherulites of one phase embedded in a matrix of the other. The spherulites in alloys containing less than 40 wt pct Co were solidified from the L1 melt and from L2 in alloys containing more than 55 wt pct Co. Supercooling of copper alloys containing around 50 wt pct Co resulted in a duplex structure of fine and coarse dendrites. Microstructural evidence was presented for the formation of aε-Cu metastable phase in alloys containing less than 30 wt pct Co.     

Microstructural development in NiAl/Ni-Si-B/Ni transient liquid phase bonds

A transmission electron microscopy (TEM) based investigation of microstructural development during transient liquid phase bonding of near-stoichiometric NiAl to commercial purity nickel is presented in this article. The work described employed Ni-4.5 wt pct Si-3.2 wt pct B (BNi-3) melt-spun interlayers. The precipitation of both Ni-Al based phases and borides within the joint and adjacent substrate regions is discussed. The article considers martensite formation (within the NiAl substrate) and the precipitation of Ll₂ type phases (both within the joint and at the interface with the NiAl substrate). The relative roles of the two substrate materials (NiAl and Ni) in the isothermal resolidification process are identified. The preferential formation of Ni₃B boride phases in the Ni substrate near the original location of the Ni substrate-joint interface is discussed and contrasted with the absence of similar events in the NiAl substrate.     

Design of quaternary Ir-Nb-Ni-Al refractory superalloys

We propose a method for developing new quaternary Ir-Nb-Ni-Al refractory superalloys for ultra-high-temperature uses, by mixing two types of binary alloys, Ir-20 at. pct Nb and Ni-16.8 at. pct Al, which contain fcc/L1₂ two-phase coherent structures. For alloys of various Ir-Nb/Ni-Al compositions, we analyzed the microstructure and measured the compressive strengths. Phase analysis indicated that three-phase equilibria—fcc, Ir₃Nb-L1₂, and Ni₃Al-L1₂—existed in Ir-5Nb-62.4Ni-12.6Al (at. pct) (alloy A), Ir-10Nb-41.6Ni-8.4Al (at. pct) (alloy B), and Ir-15Nb-20.8Ni-4.2Al (at. pct) (alloy C) at 1400 °C; at 1300 °C, three phase equilibria—fcc, Ir₃Nb, and Ni₃Al—existed in alloys A and C and four-phase equilibria—fcc, Ir₃Nb, Ni₃Al, and IrAl-B2—existed in alloy B. The fcc/L1₂ coherent structure was examined by using transmission electron microscopy (TEM). At a temperature of 1200 °C, the compressive strength of these quaternary alloys was between 130 and 350 MPa, which was higher than that of commercial Ni-based superalloys, such as MarM247 (50 MPa), and lower than that of Ir-based binary alloys (500 MPa). Compared to Ir-based alloys, the compressive strain of these quaternary alloys was greatly improved. The potential of the quaternary alloys for ultra-high-temperature use is also discussed.     

Microstructure and phase identification in type 304 stainless steel-zirconium alloys

Stainless steel-zirconium alloys have been developed at Argonne National Laboratory to contain radioactive metal isotopes isolated from spent nuclear fuel. This article discusses the various phases that are formed in as-cast alloys of type 304 stainless steel and zirconium that contain up to 92 wt pct Zr. Microstructural characterization was performed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), and crystal structure information was obtained by X-ray diffraction. Type 304SS-Zr alloys with 5 and 10 wt pct Zr have a three-phase microstructure—austenite, ferrite, and the Laves intermetallic, Zr(Fe,Cr,Ni)_2+x. whereas alloys with 15, 20, and 30 wt pct Zr contain only two phases—ferrite and Zr(Fe,Cr,Ni)_2+x. Alloys with 45 to 67 wt pct Zr contain a mixture of Zr(Fe,Cr,Ni)_2+x and Zr₂(Ni,Fe), whereas alloys with 83 and 92 wt pct Zr contain three phases—α-Zr, Zr₂(Ni,Fe), and Zr(Fe,Cr,Ni)_2+x. Fe₃Zr-type and Zr₃Fe-type phases were not observed in the type 304SS-Zr alloys. The changes in alloy microstructure with zirconium content have been correlated to the Fe-Zr binary phase diagram.     

Control of ordered structure and ductility of (Fe,Co, Ni)3V alloys

This study is directed toward improvement of the ductility of long-range ordered alloys through control of their ordered crystal structure. A series of ordered alloys was prepared with a base composition of Co₃V, where Co was partially replaced with Fe and Ni. The stability and structure of the ordered phases in these (Fe,Co,Ni)₃V alloys were characterized by various metallurgical methods. The results indicate that the ordered structure in this alloy system can be controlled by adjusting the electron density, and that the L1₂ type cubic ordered structure (α′) is stable in the alloys with electron density less than 7.888. The phase relation in the cubic ordered alloys depends on the Fe concentration. For the alloys containing <20 pct Fe, the disordered α solid solution transforms to the cubic α′ ordered on the fcc lattice at temperatures below 1000°C. For the alloys containing >20 pct Fe, the α′ is formed through a peritectoid reaction, namely, α+σ→α′. Tensile tests indicate that the alloys with multilayered hexagonal ordered structure are very brittle, while the alloys with the cubic ordered structure are ductile at room temperature. The ductility of the cubic ordered alloys increases with decreasing Co content. The alloys with <55 pct Co showed dimple type ductile rupture with elongation over 40 pct at room temperature. The correlation of ductility with ordered structure is discussed.     

Decomposition of Fe-Ni martensite: Implications for the low-temperature (≤500 °C) Fe-Ni phase diagram

The low-temperature (<500 °C) decomposition of Fe-Ni martensite was studied by aging martensitic Fe-Ni alloys at temperatures between 300 °C and 450 °C and by measuring the composition of the matrix and precipitate phases using the analytical electron microscope (AEM). For aging treatments between 300 °C and 450 °C, lath martensite in 15 and 25 wt pct Ni alloys decomposed with γ [face-centered cubic (fcc)] precipitates forming intergranularly, and plate martensite in 30 wt pct Ni alloys decomposed with γ (fcc) precipitates forming intragranularly. The habit plane for the intragranular precipitates is {111}_fcc parallel to one of the {110}_bcc planes in the martensite. The compositions of the γ intergranular and intragranular precipitates lie between 48 and 58 wt pct Ni and generally increase in Ni content with decreasing aging temperature. Diffusion gradients are observed in the matrix α [body-centered cubic (bcc)] with decreasing Ni contents close to the martensite grain boundaries and matrix/precipitate boundaries. The Ni composition of the matrix α phase in decomposed martensite is significantly higher than the equilibrium value of 4 to 5 wt pct Ni, suggesting that precipitate growth in Fe-Ni martensite is partially interface reaction controlled at low temperatures (<500 °C). The results of the experimental studies modify the γ/α + γ phase boundary in the present low-temperature Fe-Ni phase diagram and establish the eutectoid reaction in the temperature range between 400 °C and 450 °C. Formerly Research Assistant, Department of Materials Science and Engineering, Lehigh University     

Optimization of composition and heat treatment of age-hardened Pt-Al-Cr-Ni alloys

The objective of this work was to produce an alloy showing a microstructure similar to Ni-base superalloys, but with Pt as base metal. The Pt-base alloys with various contents of Al, Cr, and Ni were arc melted. Solution heat treatments at 1450 °C followed by water quenching lead to single-phase alloys. Ageing at 1000 °C resulted in the precipitation of Ll₂ ordered particles. An alloy with 11 at. pct Al, 3 at. pct Cr, 6 at. pct Ni, and Pt balance shows cuboidal precipitates with edge lengths of 200 to 500 nm along with a volume fraction of 23 pct and a lattice misfit of −0.1 pct. Aging at 1100 °C leads to coarsening of precipitates. Volume fraction and morphology of the precipitates were investigated by scanning electron microscopy and optical microscopy. X-ray diffraction as well as transmission electron microscopy (TEM) were applied to verify the crystal structure.     

Isothermal section of the ternary Sn-Cu-Ni system and interfacial reactions in the Sn-Cu/Ni couples at 800 °C

The isothermal section of the Sn-Cu-Ni system at 800 °C has been experimentally determined. There is no ternary compound. A solid solution with a very wide compositional range, the γ phase is formed between the Ni₃Sn(H) phase and Cu₄Sn(H) phase; however, both of these two binary phases are not stable at 800 °C. The binary Ni₃Sn₂ phase also has extensive ternary solubility. The homogeneity ranges of both the γ and Ni₃Sn₂ phases are very large in parallel to the Cu-Ni side, but relatively narrow along the Sn direction. This phenomenon indicates that Cu and Ni are exchangeable in both phases. Three kinds of reaction couples, Sn-55 at. pct Cu/Ni, Sn-65 at. pct Cu/Ni, and Sn-75 at. pct Cu/Ni, were prepared and reacted at 800 °C for 5 to 20 minutes. The reaction paths are liquid/Ni₃Sn₂/γ/Ni₃Sn(L)/Ni for the Sn-55 at. pct Cu/Ni and Sn-65 at. pct Cu/Ni couples, and the reaction path is liquid/γ/Ni₃Sn(L)/Ni for the Sn-75 at. pct Ni couples.     

Investigation of the Effects of Ni, Fe, and Mn on the Formation of Complex Intermetallic Compounds in Al-Si-Cu-Mg-Ni Alloys

The aim of this work is to partially substitute Fe and Mn for Ni in the 3HA piston alloy and to study the consequences through microstructural evaluation and the thermal analysis technique. Three types of near-eutectic alloys containing (2.6 wt pct Ni-0.2 wt pct Fe-0.1 wt pct Mn), (1.8 wt pct Ni-0.75 wt pct Fe-0.3 wt pct Mn), and (1 wt pct Ni-1.15 wt pct Fe-0.6 wt pct Mn) were produced, and their solidification was studied at the cooling rate of 0.9 K/s (°C/s) using the computer-aided thermal analysis technique. Optical microscopy and scanning electron microscopy were used to study the microstructure of the samples, and energy dispersive X-ray (EDX) analysis was used to identify the composition of the phases. Also, the quantity of the phases was measured using the image analysis technique. The results show that Ni mainly participates as Al₃Ni, Al₉FeNi, and Al₃CuNi phases in the high Ni-containing alloy (2.6 wt pct Ni). In addition, substitution of Ni by Fe and Mn makes Al₉FeNi the only Ni-rich phase, and Al₁₂(Fe,Mn)₃Si₂ appears as an important Fe-rich intermetallic compound in the alloys with the higher Fe and Mn contents.     

Ir-base refractory superalloys for ultra-high temperatures

The microstructure and compression strengths of Ir-15 at. pct X (X=Ti, Ta, Nb, Hf, Zr, or V) binary alloys at temperatures between room temperature and 1800 °C were investigated to evaluate the potential of these alloys for ultra-high-temperature use. The fcc and L1₂ two-phase structures of these alloys were examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The strengths of the Ir-Ta, -Nb, -Hf, and -Zr alloys were above 800 MPa at temperatures up to 1200 °C and about 200 MPa at 1800 °C. The strengths of these alloys under 1000 °C are equivalent to or higher than those of the commercially used Ni-base superalloys, MAR-M247 and CMSX-10. The Nb concentration dependence of strength was investigated using a series of Ir-Nb alloys with Nb concentrations from 0 to 25 at. pct. It was found that the Ir-base alloys were strengthened by L1₂ precipitation hardening. The potential of the Ir-base alloys for ultra-high temperature use is discussed.     

Phase equilibria of the ternary Al-Cu-Ni system and interfacial reactions of related systems at 800 °C

A series of Al-Cu-Ni alloys of various compositions were made and annealed at 800 °C. The equilibrium phases were studied by metallography, X-ray diffraction (XRD) analysis, and electron probe microanalysis. The isothermal section of the ternary Al-Cu-Ni system at 800 °C was then determined based on these experimental results and the available phase relationship knowledge of the three constituent binary systems. No ternary compound was found. All three phases, AlNi₃, AlNi, and Al₃Ni₂, have very high ternary solubility, especially the AlNi phase, which almost reaches the binary Al-Cu side. However, no continuous solid solution was formed between the AlNi phase and any of the binary Al-Cu phases. Interfacial reactions of Al/Ni, Al/Cu, Al-Cu/Ni, and Al-Ni/Cu at 800 °C were investigated by using reaction couple techniques. The results showed that Al₃Ni and Al₃Ni₂ phases were formed in the Al/Ni couples; β-AlCu₄, γ ₁-Al₄Cu₉, and ɛ ₂-Al₂Cu₃ phases were formed in the Al/Cu couples. As for the results in the Al-2 at. pct Ni/Cu, Al-5 at. pct Ni/Cu, and Al-2 at. pct Cu/Ni, Al-4.5 at. pct Cu/Ni, and Al-6 at. pct Cu/Ni were similar to those in the binary Al/Cu and Al/Ni couples, respectively. A different reaction path was found in the Al-7.5 at. pct Cu/Ni couples, and an AlNi solid solution layer was formed instead of the Al₃Ni and Al₃Ni₂ phases.     

Determination of the Fe−Ni phase diagram below 400°C

The phase diagram for the Fe−Ni system below 400°C has been determined experimentally in the composition range from 0 to 52 wt pct Ni using analytical electron microscopy techniques. High spatial resolution X-ray microanalysis and electron diffraction were conducted on the Fe−Ni regions of meteorites. Both stable and metastable phase boundaries were defined. Our phase diagram is consistent with the available theoretical diagram in that firm experimental evidence was found for a miscibility gap and an associated, asymmetrical spinodal decomposition region. The spinodal decomposition resulted in a two-phase, isotropic microstructure, as expected. The miscibility gap is a metastable construction arising from the presence of a tricritical point due to magnetic interactions. Our experimental diagram differs from the theoretical diagram in three ways. First, observations of meteorite structures show that Fe−Ni solid solution containing 4.0 wt pct Ni is in local equilibrium with ordered FeNi containing 51.4 wt pct Ni and not Ni₃Fe as in the theoretical diagram. Second, our miscibility gap below 400°C, located between 11.7 and 51.9 wt pct Ni at 200°C, is wider than the calculated miscribility gap, especially at the high Ni end. Third, we also find evidence for an ordered structure around ∼25 wt pct Ni. This structure may be either Fe₃Ni or a two-phase structure incorporating ordered FeNi.     

Slip transfer and dislocation nucleation processes in multiphase ordered Ni-Fe-Al alloys

Directionally solidified (DS) alloys with the nominal composition Ni-30 at. pct Fe-20 at. pct Al having eutectic microstructures were used to study slip transfer across interphase boundaries and dislocation nucleation at the interfacial steps. The slip transfer from the ductile second phase, γ(fcc) containing ordered γ′(L1₂) precipitates, to the ordered β(B2) phase and the generation of dislocations at the interface steps were interpreted using the mechanisms proposed for similar processes involving grain boundaries in polycrystalline single-phase materials. The criteria for predicting the slip systems activated as a result of slip transfer across grain boundaries were found to be applicable for interphase boundaries in the multiphase ordered Ni-Fe-Al alloys. The potential of tailoring the microstructures and interfaces to promote slip transfer and thereby enhance the intrinsic ductility of dislocation-density-limited intermetallic alloys is discussed.