The Influence of Precipitation of Alpha2 on Properties and Microstructure in TIMETAL 6-4

Samples of Hot Isostatically Pressed (HIPped) powder of TIMETAL 6-4 (Ti-6Al-4V, compositions in wt pct unless indicated), which was HIPped at 1203 K (930 °C), and of forged bar stock, which was slowly cooled from above the beta transus, were both subsequently held at 773 K (500 °C) for times up to 5 weeks and analyzed using scanning and transmission electron microscopy and atom probe analysis. It has been shown that in the samples aged for 5 weeks at 773 K (500 °C), there is a high density of alpha2 (α₂, an ordered phase based on the composition Ti₃Al) precipitates, which are typically 5 nm in size, and a significantly smaller density was present in the slowly cooled samples. The fatigue and tensile properties of samples aged for 5 weeks at 773 K (500 °C) have been compared with those of the HIPped powder and of the forged samples which were slowly cooled from just above the transus, and although no significant difference was found between the fatigue properties, the tensile strength of the aged samples was 5 pct higher than that of the as-HIPped and slowly cooled forged samples. The ductility of the forged samples did not decrease after aging at 773 K (500 °C) despite the strength increase. Transmission electron microscopy has been used to assess the nature of dislocations generated during tensile and fatigue deformation and it has been found that not just is planar slip observed, but dislocation pairs are not uncommon in samples aged at 773 K (500 °C) and some are seen in slowly cooled Ti6Al4V.     

Tempering of Low-Temperature Bainite

Electron microscopy, X-ray diffraction, and atom probe tomography have been used to identify the changes which occur during the tempering of a carbide-free bainitic steel transformed at 473 K (200 °C). Partitioning of solute between ferrite and thin-films of retained austenite was observed on tempering at 673 K (400 °C) for 30 minutes. After tempering at 673 K (400 °C) and 773 K (500 °C) for 30 minutes, cementite was observed in the form of nanometre scale precipitates. Proximity histograms showed that the partitioning of solutes other than silicon from the cementite was slight at 673 K (400 °C) and more obvious at 773 K (500 °C). In both cases, the nanometre scale carbides are greatly depleted in silicon.

     

Nano-scale Mechanical Properties and Microstructure of Irradiated X-750 Ni-Based Superalloy

This study investigates the effect of irradiation on the mechanical properties of a Ni-based superalloy, X-750. 40 MeV Ni⁺ ions were used to irradiate the X-750 up to 1 dpa with and without 5000 appm helium pre-implantation at room temperature and 400 °C. Nano-indentation hardness tests were carried out at room temperature in the depth range of 200 to 1400 nm before and after irradiation. Cross-sectional TEM observations were performed on the irradiated materials to correlate the mechanical results with the microstructural evolution. The results show that helium pre-implantation enhances the irradiation-induced hardening due to generating a high density of small cavities and promoting the formation of larger Frank loops. In addition, nano-scale mechanical tests reveal that changing the subsequent Ni ion irradiation temperature from room temperature to 400 °C, leads to changing of the mechanical response from a softening behavior to an irradiation-induced hardening. The γ′ precipitates became disordered after irradiation at room temperature, whereas the γ′-phase remained ordered during irradiation at 400 °C. The softening effect of the γ′ instability outweighed the hardening impact of irradiation-induced defects such as cavities and Frank loops, leading to a hardness reduction for the room-temperature-irradiated material. Three different obstacle-hardening models were employed to assess the individual impact of each type of defect on the material’s overall strength enhancement. Furthermore, the superposition principle was used for each model to estimate the overall irradiation-induced strengthening, which is compared to the results from the nano-hardness measurements.     

Effects of Aging Temperature on Electrical Conductivity and Hardness of Cu-3 at. pct Ti Alloy Aged in a Hydrogen Atmosphere

To improve the balance of the electrical conductivity and mechanical strength for dilute Cu-Ti alloys by aging in a hydrogen atmosphere, the influence of aging temperature ranging from 673 K to 773 K (400 °C to 500 °C) on the properties of Cu-3 at. pct Ti alloy was studied. The Vickers hardness increases steadily with aging time and starts to fall at 3 hours at 773 K (500 °C), 10 hours at 723 K (450 °C), or over 620 hours at 673 K (400 °C), which is the same as the case of conventional aging in vacuum. The maximum hardness increases from 220 to 236 with the decrease of aging temperature, which is slightly lower than aging at the same temperature in vacuum. The electrical conductivity at the maximum hardness also increases from 18 to 32 pct of pure copper with the decrease of the temperature, which is enhanced by a factor of 1.3 to 1.5 in comparison to aging in vacuum. Thus, aging at 673 K (400 °C) in a hydrogen atmosphere renders fairly good balance of strength and conductivity, although it takes nearly a month to achieve. The microstructural changes during aging were examined by transmission electron microscopy (TEM) and atom-probe tomography (APT), and it was confirmed that precipitation of the Cu₄Ti phase occurs first and then particles of TiH₂ form as the third phase, thereby efficiently removing the Ti solutes in the matrix.     

Acceleration or Suppression of α-Phase Precipitation Using Isothermal ω Phase in Ti-20 at.pct Nb Alloy

Homogeneous precipitation of a fine α phase in the β matrix of Ti alloys is a promising method for obtaining a highly strengthened Ti-based alloy. Isothermal ω particles are known to be the nucleation sites for fine α-phase precipitation, but an understanding of the kinetics of α-phase formation on isothermal ω particles is still lacking. This study aimed to reveal the effect of isothermal ω particles on α-phase precipitation onset time. Two-step isothermal aging of a Ti-20 at.pct Nb alloy after solid solution treatment at 1273 K (1000 °C) was carried out. The first step of the aging at 633 K (360 °C) involved the formation of isothermal ω particles in the β matrix. This was followed by a second aging step at 673 K, 723 K, and 773 K (400 °C, 450 °C, and 500 °C) for α-phase precipitation. Suppression of α-phase nucleation on the isothermal ω particles occurred at 673 K (400 °C), whereas acceleration of α-phase nucleation on the isothermal ω particles was observed at 723 K and 773 K (450 °C and 500 °C). Thermodynamic stability of the isothermal ω particles and solute partitioning were controlling factors for the α-phase precipitation kinetics.     

Mechanical Performance of Ferritic Martensitic Steels for High Dose Applications in Advanced Nuclear Reactors

Ferritic/martensitic (F/M) steels are considered for core applications and pressure vessels in Generation IV reactors as well as first walls and blankets for fusion reactors. There are significant scientific data on testing and industrial experience in making this class of alloys worldwide. This experience makes F/M steels an attractive candidate. In this article, tensile behavior, fracture toughness and impact property, and creep behavior of the F/M steels under neutron irradiations to high doses with a focus on high Cr content (8 to 12) are reviewed. Tensile properties are very sensitive to irradiation temperature. Increase in yield and tensile strength (hardening) is accompanied with a loss of ductility and starts at very low doses under irradiation. The degradation of mechanical properties is most pronounced at <0.3T _M (T _M is melting temperature) and up to 10 dpa (displacement per atom). Ferritic/martensitic steels exhibit a high fracture toughness after irradiation at all temperatures even below 673 K (400 °C), except when tested at room temperature after irradiations below 673 K (400 °C), which shows a significant reduction in fracture toughness. Creep studies showed that for the range of expected stresses in a reactor environment, the stress exponent is expected to be approximately one and the steady state creep rate in the absence of swelling is usually better than austenitic stainless steels both in terms of the creep rate and the temperature sensitivity of creep. In short, F/M steels show excellent promise for high dose applications in nuclear reactors.     

Reverse Shape Memory Effect Related to α → γ Transformation in a Fe-Mn-Al-Ni Shape Memory Alloy

In this study, we investigated the shape memory behavior and phase transformations of solution-treated Fe_43.61Mn_34.74Al_13.38Ni_8.27 alloy between room temperature and 1173 K (900 °C). This alloy exhibits the reverse shape memory effect resulting from the phase transformation of α (bcc) → γ (fcc) between 673 K and 1073 K (400 °C and 800 °C) in addition to the shape memory effect resulting from the martensitic reverse transformation of γ′ (fcc) → α (bcc) below 673 K (400 °C). There is a high density of hairpin-shaped dislocations in the α phase undergoing the martensitic reverse transformation of γ′ → α. The lath γ phase, which preferentially nucleates and grows in the reversed α phase, has the same crystal orientation with the reverse-transformed γ′ martensite. However, the vermiculate γ phase, which is precipitated in the α phase between lath γ phase, has different crystal orientations. The lath γ phase is beneficial to attaining better reverse shape memory effect than the vermiculate γ phase.     

Effect of Aging on Microstructure and Shape Memory Properties of a Ni-48Ti-25Pd (At. Pct) Alloy

The microstructure and properties of a precipitation-hardenable Ni-48Ti-25Pd (at. pct) shape memory alloy have been investigated as a function of various aging conditions. Both the hardness and martensitic transformation temperatures increased with increasing aging time up to 100 hours at 673 K (400 °C), while no discernable differences were observed after heat treatment at 823 K (550 °C), except for a slight decrease in hardness. For aging at 673 K (400 °C), these effects were attributed to the formation of nano-scale precipitates, while precipitation was absent in the 823 K (550 °C) heat-treated specimens. The precipitation-strengthened alloy exhibited stable pseudoelastic behavior and load-biased-shape memory response with little or no residual strains. The precipitates had a monoclinic base-centered structure, which is the same structure as the P-phase recently reported in Ni(Pt)-rich NiTiPt alloys. 3D atom probe analysis revealed that the precipitates were slightly enriched in Ni and deficient in Pd and Ti as compared with the bulk alloy. The increase in martensitic transformation temperatures and the superior dimensional stability during shape memory and pseudoelastic testing are attributed to the fine precipitate phase and its effect on matrix chemistry, local stress state because of the coherent interface, and the ability to effectively strengthen the alloy against slip.     

Effect of heat-treatment conditions on the structure and physicomechanical and chemical properties of a Ni-Cr-Cu-Ti maraging steel

The effects of quenching (from 950°C or from 950 and 850°C) and the aging conditions on the structure, properties, and delayed fracture (DF) of 03Kh11N10M2DT maraging steel has been studied by dilatometry, X-ray diffraction, and fracture tests. The DF-crack growth rate is maximal after aging at 400°C irrespective of the quenching conditions, and the corrosion rate is maximal after aging at 350–400°C in the case of single quenching and at 350°C after double quenching. The kinetics and mechanism of the early stages of the decomposition of a supersaturated α solid solution are investigated by electrical-resistance measurements and transmission electron microscopy. In the state after single quenching, aging occurs in two stages at all isothermal heat treatments; in the state after double quenching, aging occurs in one stage at a time exponent n = 0.2 in the Johnson-Mehl equation. Upon aging at 400°C, the intermediate ordered Fe₃(Ni,Ti) phase with a complex cubic lattice precipitates, and the intermetallic compound Ni₃Ti precipitates upon subsequent aging. Moreover, copper-rich ε-phase precipitates form only in the case of single quenching. The substantial increase in the crack growth rate during DF with n < 0.2 is likely to be caused by the formation of Guinier-Preston zones enriched in nickel and titanium.     

Structure and initial precipitation in a rapidly solidified nickel superalloy

A nickel base superalloy (Nimonic 80A) has been rapidly solidified at cooling rates of between 10⁵ to 10⁶ K.S^-1 by pendant drop melt extraction and by chill block melt spinning in an evacuated chamber backfilled with helium or argon. The internal structure is described in terms of process variables pertaining to rotating chill block quenching techniques. Both transmission electron microscopy and atom-probe field-ion microscopy have been employed to give structural and constitutional data on quenched and aged specimens. The as-quenched structure is homogeneous apart from fluctuations in titanium concentration which upon aging undergoes a spinodal phase decomposition to form disordered Ni₃(Ti,Al,Cr) precipitates in the matrix, which after prolonged aging produces ordered γ (Ni₃(Ti,Al)). inin6 particles form readily on grain boundaries and also appear in conjunction with ordered γ, via a discontinuous reaction, after short aging times.     

High-Temperature Mechanical Behavior of Extruded Mg-Y-Zn Alloy Containing LPSO Phases

The high-temperature mechanical behavior of extruded Mg_97?3x Y_2x Zn _x (at. pct) alloys is evaluated from 473 K to 673 K (200 °C to 400 °C). The microstructure of the extruded alloys is characterized by Long Period Stacking Ordered structure (LPSO) elongated particles within the magnesium matrix. At low temperature and high strain rates, their creep behavior shows a high stress exponent (n = 11) and high activation energy. Alloys behave as a metal matrix composite where the magnesium matrix transfers part of its load to the LPSO phase. At high-temperature and/or low stresses, creep is controlled by nonbasal dislocation slip. At intermediate and high strain rates at 673 K (400 °C) and at intermediate strain rates between 623 K and 673 K (350 °C and 400 °C), the extruded alloys show superplastic deformation with elongations to failure higher than 200 pct. Cracking of coarse LPSO second-phase particles and their subsequent distribution in the magnesium matrix take place during superplastic deformation, preventing magnesium grain growth.     

Phase Equilibria of the Cu-Ti-Er System at 773?K (500?°C) and Stability of the CuTi3 Phase

The phase relationships of the Cu-Ti-Er ternary phase diagram at 773?K (500?°C) were investigated mainly by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), and differential thermal analysis (DTA). It is confirmed in this work that the binary compounds Cu₉Er₂ and Cu₇Er₂ exist in the Cu-Er binary system at 773?K (500?°C). The stability of the CuTi₃ phase is confirmed in the Cu-Ti system. After heat treatment at 1023?K (750?°C) for 90 hours, the phase CuTi₃ is observed in the microstructure of the alloy 25Cu75Ti. The temperature of the eutectoid transformation, namely, ??-Ti ? ??-Ti?+?CuTi₃, is determined to be 1078?K (805?°C) in this work. The 773?K (500?°C) isothermal section consists of 14 single-phase regions, 25 two-phase regions, and 12 three-phase regions. None of the phases in this system reveals a remarkable homogeneity range at 773?K (500?°C).     

Dry Sliding Wear Behavior of Ti-6.5Al-3.5Mo-1.5Zr-0.3Si Alloy

Dry sliding wear tests were performed for Ti-6.5Al-3.5Mo-1.5Zr-0.3Si alloy against AISI 52100 steel under the loads of 50 to 250 N at 298 K to 873 K (25 °C to 600 °C). The wear behavior of the alloy varied with the change of test conditions. More or less tribo-oxides TiO₂ and Fe₂O₃ formed on worn surfaces under various conditions. At lower temperature [298 K to 473 K (25 °C to 200 °C)], less and scattered tribo-oxide layers did not show wear-reduced effect. As more number of and continuous tribo-oxide layers appeared at higher temperatures [773 K to 873 K (500 °C to 600 °C)], the wear rate would be substantially reduced. It can be suggested that Ti-6.5Al-3.5Mo-1.5Zr-0.3Si alloy possessed excellent wear resistance at 773 K to 873 K (500 °C to 600 °C). The wear-reduced effect of tribo-oxides seemed to depend on the appearance of Fe₂O₃ and the amount of tribo-oxides.     

Nickel and nitrogen ion irradiation induced void swelling and defect microstructures in Ni-Al,Ni-Cr and Ni-Ti solid solutions

The effects of solute content, temperature, and irradiation dose on the void swelling characteristics of pure nickel and several nickel base solid solutions (Ni-Al and Ni-Ti containing up to 8 at. pct solute and Ni-Cr containing up to 16 pct Cr) have been iN_vesti-gated. Samples were irradiated in the temperature range 400 to 650°C to a maximum dose of 70 dpa using 3.5 MeV⁵⁸Ni⁺, 400 keV¹⁴N⁺ and 400 keV¹⁴N⁺ ₂ ions. The irradiation in-duced microstructures were studied using transmission electron microscopy. In general, the addition of Al, Cr or Ti to Ni is found to decrease the void swelling and mean void diameter and to increase the dislocation density. The behavior of the void number den-sity, N_v, as a function of solute content is found to be dependent upon the irradiation con-ditions as well as the particular solute addition. N_v passes through a maximum at approxi-mately 2 pct solute content for Ni-AI and Ni-Cr alloys irradiated at 550°C, but through a minimum at 4 pct for Ni-Ti alloys irradiated at 550 and 600°C. N_v decreases monotoni-cally as a function of Al content at 600 and 650°C. The results are discussed in terms of recent theories of void swelling suppression due to impurity or solute additions and in light of several correlations between void swelling and material parameters. The be-havior of N_v is found to be best described by the actions of two compcting processes. The first enhances void nucleation, is not strongly temperature dependent and is dominant at low solute contents. The second suppresses void swelling, is probably diffusion con-trolled and dominates in the more concentrated alloys. R.F.PINIZZOTTO, JR., formerly Graduate student, UCLA, This paper is based on a presentation made at a symposium on “Radiation Induced Atomic Rearrangements in Ordering and Clustering Alloys” held at the annual meeting of the AIME, Atlanta, Georgia, March 7 to 8, 1977, under the sponsorship of the Physical Metallurgy and Nuclear Metallurgy Committees of     

Irradiation-Induced Mo2C Precipitation in Ni-Mo

Precipitates observed in Ni₄Mo after nickel ion irradiation between 773 and 948 K were examined by analytical electron microscopy and found to be hexagonal Mo₂C. The precipitate particle size increases with irradiation time; diffraction effects from the precipitate are complex when the particles are small, but distinctly different from those due to either short- or long-range order known to occur in Ni₄Mo. Formation of the precipitates in the pure binary alloy is attributed to carbon contamination during the irradiation experiment. The degree of carbon contamination was dose dependent. formerly with Oak Ridge National Laboratory, Oak Ridge, TN     

High resolution electron microscopic studies of Ni-9.3 and 14.7 at.%Ti alloys

The early stages of decomposition in Ni-9.3 and 14.7 at.% Ti alloys are studied by means of high resolution electron microscopy. The microstructure of the as-quenched Ni-9.3 at.% Ti alloy shows contrast of broad circular regions, and local lattice images show some difference in lattice spacing suggesting compositional modulations. Electron and optical diffraction patterns indicate faintly ordered regions. After ageing for 15 min at 570°C, the ordered regions, approx. 50 Å in diameter, appear as clear lattice images surrounded by dark areas of the f.c.c. γ-solid solution. The Ni-14.7at.% Ti alloy aged for 15 min at 570°C shows ordered lattice images in wide areas of the matrix, apart from some large needle-like precipitates of the equilibrium η-phase formed during the homogenization at 1200°C. As the atomic arrangement in the ordered regions corresponds to the (110) projection of the L1₂ structure, the image is interpreted as the structure image of ordered L1₂, Ni₃(Ti_xNi_1−x). The lattice spacings locally change in the ordered regions, suggesting some modulation in composition and degree of order.     

Diffusion Bonding of 17-4 Precipitation Hardening Stainless Steel to Ti Alloy With and Without Ni Alloy Interlayer: Interface Microstructure and Mechanical Properties

In the present study, the diffusion bonding of 17-4 precipitation hardening stainless steel to Ti alloy with and without nickel alloy as intermediate material was carried out in the temperature range of 1073 K to 1223 K (800 °C to 950 °C) in steps of 298 K (25 °C) for 60 minutes in vacuum. The effects of bonding temperature on interfaces microstructures of bonded joint were analyzed by light optical and scanning electron microscopy. In the case of directly bonded stainless steel and titanium alloy, the layerwise α-Fe + χ, χ, FeTi + λ, FeTi + β-Ti phase, and phase mixture were observed at the bond interface. However, when nickel alloy was used as an interlayer, the interfaces indicate that Ni₃Ti, NiTi, and NiTi₂ are formed at the nickel alloy-titanium alloy interface and the PHSS-nickel alloy interface is free from intermetallics up to 1148 K (875 °C) and above this temperature, intermetallics were formed. The irregular-shaped particles of Fe₅Cr₃₅Ni₄₀Ti₁₅ have been observed within the Ni₃Ti intermetallic layer. The joint tensile and shear strength were measured; a maximum tensile strength of ~477 MPa and shear strength of ~356.9 MPa along with ~4.2 pct elongation were obtained for the direct bonded joint when processed at 1173 K (900 °C). However, when nickel base alloy was used as an interlayer in the same materials at the bonding temperature of 1148 K (875 °C), the bond tensile and shear strengths increase to ~523.6 and ~389.6 MPa, respectively, along with 6.2 pct elongation.     

Experimental Investigation and Thermodynamic Calculations of the Bi-Ge-Sb Phase Diagram

A phase diagram of the Bi-Ge-Sb ternary system was investigated experimentally by differential thermal analysis (DTA), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), and X-ray powder diffraction (XRD) methods and theoretically by the CALPHAD method. The liquidus projection; invariant equilibria; and three vertical sections, Sb-Bi_0.5Ge_0.5, Ge-Bi_0.5Sb_0.5, and Bi-Ge_0.5Sb_0.5, as well as isothermal sections at 773 K and 373 K (500 °C and 100 °C), were predicted using optimized thermodynamic parameters for constitutive binary systems from the literature. In addition, phase transition temperatures of the selected samples with compositions along calculated isopleths were experimentally determined using DTA. Predicted isothermal sections at 773 K and 373 K (500 °C and 100 °C) were compared with the results of the SEM-EDS and XRD analysis from this work. In both cases, good agreement between the extrapolated phase diagram and experimental results was obtained. Alloys from the three studied vertical sections were additionally analyzed using the Brinell hardness test.     

Thermal Behavior and Phase Transformation of TiO2 Nanocrystallites Prepared by a Coprecipitation Route

TiO₂ freeze-dried precursor powders were synthesized using a coprecipitation route that includes titanium tetrachloride (TiCl₄) as initial material prepared at 348 K (75 °C) and pH 7. Differential scanning calorimetry/thermogravimetry (DSC/TG), X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) and high resolution TEM were utilized to characterize the thermal behavior and phase transformation of the TiO₂ freeze-dried precursor powders after calcination. The main compound of the TiO₂ freeze-dried precursor powders was TiO₂·H₂O based on a TG analysis conducted at a heating rate of 20 K (20 °C)/min. The anatase TiO₂ (a-TiO₂) first appeared at 473 K (200 °C), then from a-TiO₂ transformed to rutile TiO₂ (r-TiO₂) at 773 K (500 °C). The activation energy of a-TiO₂ formation from TiO₂ freeze-dried precursor powders was 242.4 ± 33.9 kJ/mol, whereas, the activation energy of phase transformation from a-TiO₂ to r-TiO₂ was 267.5 ± 19.1 kJ/mol. The crystallite size of a-TiO₂ grew from 3.5 to 23.2 nm when raising the calcination temperature from 473 K to 873 K (200 °C to 600 °C). In addition, the crystallite size of r-TiO₂ increased from 17.4 to 48.1 nm when calcination temperature increased from 773 K to 1073 K (500 °C to 800 °C).