Diffusion in the titanium-nickel system: I. occurrence and growth of the various intermetallic compounds

Various types of diffusion couples have been prepared and the growth of the layers, formed in these couples, has been studied in the temperature range between 550 and 940°C. All phases which, on the basis of the equilibrium diagram, could be expected under the circumstances, were found in the diffusion zone. The layer growth of β-Ti(Ni), Ti₂Ni and TiNi in all types of couples obeyed the parabolic law; the TiNi layer was the only exception. It is supposed that in this case grain boundary diffusion is responsible for the observed abnormal growth. The shape of the β-Ti/β-Ti + Ti₂Ni boundary in the equilibrium diagram was constructed using data, both from recorded penetration curves and from equilibrated two-phase alloys. Excellent agreement between the results of these two methods was obtained. The eutectoid composition at 77Q°C has been placed at about 7 at. pct Ni, in contrast with earlier results. Furthermore, the composition range of TiNi has been determined from penetration curves. This paper is based on a Thesis submitted by G. F. BASTIN in fulfillment or requirements for the degree of Doctor in Technological Sciences.     

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     

TiNi Shape Memory Alloys with High Sintered Densities and Well-Defined Martensitic Transformation Behavior

This study demonstrates that a high density and a high transformation heat can be attained for PM TiNi. With the use of fine elemental powders, a composition of Ti₅₁Ni₄₉, two-step heating, and persistent liquid-phase sintering at 1553 K (1280 °C), a 95.3 pct sintered density was attained for compacts with a green density of 66 pct. A transformation heat, ΔH, of 31.9 J/g was also achieved, which is much higher than reported previously for sintered TiNi and is approaching the highest ΔH reported to date, 35 J/g, for wrought TiNi with low C, O, and N contents. The main reason for having these properties in powder metal TiNi with higher amounts of C, O, and N is that the extra Ti, that over the equiatomic portion in the Ti-rich Ti₅₁Ni₄₉, forms Ti₂Ni compound, which traps most of the C, O, and N. This results in low interstitial contents and a high Ti/Ni ratio of 50.5/49.5 in the TiNi matrix. The tensile strength, elongation, and shape recovery rate after five training cycles were 638 MPa, 14.6, and 99.1 pct, respectively, despite the presence of Ti₂Ni compounds at grain boundaries.     

Diffusion of Au in the Intermetallic Compound Ti<Subscript>3</Subscript>Al

The Au diffusion in the Ti₃Al compound was investigated at six compositions from 25 to 35 at. pct Al by using the diffusion couples (Ti-X at. pct Al/Ti-X at. pct Al-2 at. pct Au; X = 25, 27, 29, 31, 32, and 35) at 1273 to 1423 K. The diffusion coefficients of Au in Ti₃Al ( D_\textAu^{\textTi₃ \textAl} ) \left( {D_{\text{Au}}^{{{\text{Ti}}_{3} {\text{Al}}}} } \right) are relatively close to those of Ti. The D_\textAu^{\textTi₃ \textAl} \texts {D}_{\text{Au}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}} slightly increase with Al concentration within the same order of magnitude. The activation energies of Au diffusion, Q_\textAu^{\textTi₃ \textAl} \texts, Q_{\text{Au}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}}, evaluated from the Arrhenius plots were relatively close to those of Ti diffusion, Q_\textTi^{\textTi₃ \textAl} \texts, Q_{\text{Ti}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}}, rather than those of Al diffusion, Q_\textAl^{\textTi₃ \textAl} \texts; {Q}_{\text{Al}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}}; therefore, it was suggested that Au atoms diffuse by the sublattice diffusion mechanism in which Au atoms substitute for Ti sites preferentially in Ti₃Al and diffuse by vacancy mechanism on Ti sublattice. The influence of the D0₁₉ ordered structure (hcp base) of Ti₃Al on diffusion of Au and other elements is discussed by comparing the diffusivities in Ti₃Al and α-Ti.     

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.     

Synthesis of nanodispersed phases during rapid solidification and crystallization of glasses in Ti75Ni25 alloys

The formation of the metallic glass and crystalline phases and related microstructures and the decomposition behavior of rapidly solidified Ti₇₅Ni₂₅ alloys obtained under different processing conditions have been investigated in detail. The competition between glass transition and nucleation of β-Ti during rapid solidification leads to the possibility of synthesizing the nanocomposites of β-Ti and glass. Additionally, it is shown that the presence of a small amount of Si also promotes simultaneous nucleation of fine Ti₂Ni intermetallic compound. Thermodynamic calculation of the metastable phase diagram indicates the presence of a metastable eutectic reaction between α-Ti and Ti₂Ni. Evidence of this reaction at lower cooling rates has been presented. On heating, the glass decomposes through this reaction. Finally, on the basis of understanding of the microstructural evolution during decomposition, a new approach has been adopted to synthesize a nanodispersed composite of α-Ti in the crystalline Ti₂Ni matrix with a narrow size distribution by controlling the devitrification heat treatment of the metallic glass.     

Oxygen diffusion in alpha and beta titanium in the temperature range of 932° to 1142°C

An attempt is made to determine the diffusion coefficient of oxygen in α-Ti from oxidation studies of oxygen-unsaturated and oxygen-saturated β-Ti. Knowledge about the rates of movements of the α/β interface permits evaluation of oxygen diffusivity in α-Ti. The results conform to the relationship:D _α=0.778 exp (?48,600/RT), sq cm per sec, for the temperature range of 932° to 1142°C. From microhardness measurements, the diffusion coefficient of oxygen in β-Ti can be expressed as:D _β=3.30×10² exp (?58,800/RT), sq cm per soc, for the same temperature range.     

Interface microstructures in the diffusion bonding of a titanium alloy Ti 6242 to an INCONEL 625

A Ti6242 alloy has been diffusion bonded to a superalloy INCONEL 625. The microstructures of the as-processed products have been analyzed using optical metallography, scanning electron microscope (SEM), and scanning transmission electron microscope (STEM) techniques. The interdiffusion of the different elements through the interface has been determined using energy-dispersive spectroscopy (EDS) microanalysis in both a SEM and a STEM. Several regions around the original interface have been observed. Starting from the superalloy INCONEL 625, first a sigma phase (Cr₄Ni₃Mo₂), followed by several phases like NbNi₃, Ŋ/Ni₃Ti, Cr(20 pct Mo), β Cr₂Ti, NiTi, TiO, TiNi, and Ti₂Ni intermetallics, just before the Ti6242 have been identified. Because the diffusion of Ni in Ti is faster than the diffusion of Ti in the superalloy, a Kirkendall effect was produced. The sequence of formation of the different phases were in agreement with the ternary Ti-Cr-Ni diagram.     

The nitridation of chromium and Cr-Ti alloys

Reaction zones and growth kinetics were studied after exposing high-purity chromium and alloys containing 0.5, 3.0, and 5.0 wt pct Ti to 1 atm of nitrogen between 1000° and 1400°C. Outer layers of Cr₂N and regions of internal nitridation, containing dispersed TiN particles, grew in a parabolic manner. An exact solution of Maak’s simplified analysis for internal oxidation provided calculations of nitrogen diffusion in the internal-nitride zone of each alloy. Extrapolation gave the relationshipD = 9.6 × 10^-3 exp (-28,500/RT) cm² sec^-1 for nitrogen diffusion in high-purity chromium. Increasing titanium to 5.0 wt. pct gaveD = 2.5 × 10^-3 exp (-24,000/RT) cm² sec^-1.     

Microstructure of Ti-48.2 at. Pct Ni shape memory thin films

Amorphous thin films of Ti-48.2 at. pct Ni formed by sputtering were annealed at 773 K for 5 minutes, 1 hour, and 10 hours. It was found by transmission electron microscopy (TEM) that the microstructure changes in the sequence of (1) Guinier-Preston (GP) zones for 5 minutes, (2) GP zones and Ti₂Ni precipitates for 1 hour, and (3) Ti₂Ni precipitates for 10 hours. A high-resolution electron microscope (HREM) revealed that Ti₂Ni precipitates have partial coherency with the TiNi matrix.     

Diffusion of cobalt,chromium, and titanium in Ni3Al

Diffusion studies of cobalt, chromium, and titanium in Ni₃Al (γ′) at temperatures between 1298 and 1573 K have been performed using diffusion couples of (Ni-24.2 at. pct Al/Ni-24.4 at. pct Al-2.91 at. pct Co), (Ni-24.2 at. pct Al/Ni-23.1 at. pct Al-2.84 at. pct Cr), and (Ni-24.2 at. pct Al/Ni-20.9 at. pct Al-3.17 at. pct Ti). The diffusion profiles were measured by an electron probe microanalyzer, and the diffusion coefficients of cobalt, chromium, and tita-nium in γ′ containing 24.2 at. pct Al were determined from those diffusion profiles by Hall’s method. The temperature dependencies of their diffusion coefficients (m[su2]/s) are as follows: ~D_(Co) = (4.2 ± 1.2) × 1O^-3exp {-325 ± 4 (kJ/mol)/RT} ~D_(Cr) = (1.1 ± 0.3) × 10^-1 exp {-366 ± 3 (kJ/mol)/RT} and D_(Ti) = (5.6 ± 3.1) × 10¹ exp {-468 ± 6 (kJ/mol)/RT} The values of activation energy increase in this order: cobalt, chromium, and titanium. These activation energies are closely related to the substitution behavior of cobalt, chromium, and titanium atoms in the Ll₂ lattice sites of γ′; the cobalt atoms occupying the face-centered sites in the Ll₂ structure diffuse with the normal activation energy, whereas the titanium atoms oc-cupying the cubic corner sites diffuse with a larger activation energy that includes the energy due to local disordering caused by the atomic jumps. The chromium atoms which can occupy both sites diffuse with an activation energy similar to that of cobalt atoms.     

The interdiffusivity matrix of Fe2O3-CaO-SiO2 melt at 1693 to 1773 K

The diffusion couple method was used at 1693 to 1773 °K on liquid slags with their average compositon of 20 wt pct Fe₂O −₃−35 wt pct CaO-45 wt pet SiO₂. After diffusion runs for 40 min, the samples have been quenched to glassy state. The samples were sectioned, polished, and analyzed by a X-ray micro analyzer. The diffusivities matrix obtained from the penetration curves can be expressed by the following equations,D ³⁰ ₁₀₋₁₀ = 3.27 exp (−50000―RT)(cm²/s)D ³⁰ ₁₀₋₂₀ = -11.1 exp (−50000―RT)(cm²/s)D ³⁰ ₂₀₋₁₀ = 8.30 exp (−56300―RT)(cm²/s)D ³⁰ ₂₀₋₂₀ = 11.5 exp (−56200―RT)(cm²/s) where 10, 20, and 30 mean Fe₂O₃, CaO and SiO₃, respectively and the activation energies are in Cal per mol. The elements obtained satisfy the restriction derived from the second law of thermodynamics. The diffusion-composition paths obtained are consistent with the Cooper's parallelogram.     

Diffusion of titanium in copper

Interdiffusion coefficients in copper-titanium alloys have been determined by Matano's method in the temperature range between 973 and 1283 K on (pure Cu)-(Cu-1.98 at. pct Ti alloy) and (pure Cu)-(Cu-2.91 at. pct Ti alloy) couples. Temperature dependence of the impurity diffusion coefficient of titanium in copper, determined by extrapolation of the concentration dependence of the interdiffusion coefficient to zero mole fraction of titanium, is expressed by the following Arrhenius equation along with the probable errors:D _Ti/Cu=(0.693 _−0.135 ^+0.169 )×10⁻⁴exp[−(196±2)kJ mol⁻¹/RT] m²/s. The difference in the activation energies for the impurity diffusion of the 3d-transition metals and self-diffusion in copper has been calculated by applying LeClaire's model with the oscillating potential of the impurity atom in copper. The calculated values agree well with the experimental values including the present one. Kazutomo Hoshino, formerly Graduate Student, Tohoku University     

The diffusion of hydrogen in liquid iron alloys

Rates of absorption of hydrogen in stagnant liquid iron and ten (Fe-X) binary iron alloy systems were studied by an unsteady-state gas-liquid metal diffusion cell technique. These rates were found to be controlled by diffusion of hydrogen in the liquid phase. Chemical diffusion coefficients (D _h) were measured in pure iron and Fe-X alloys in the following (at. pct) composition ranges: Mn (0 to 5), Cr (0 to 25), V (0 to 25), Nb (0 to 10), Mo (0 to 25), W (0 to 5), Ni (0 to 75), Co (0 to 75), Sn (0 to 10), and Cu (0 to 25). All measuredD _H values at 1600°C lie between 7 × 10^-4 and 16 × 10^-4 sq cm per sec. The diffusion coefficients found for pure iron can be represented by D_H ^Fe = 4.37 × 10⁻³ exp (−4134 ± 1012)/RT cm²/sec where the uncertainty in the activation energy, Q, in cal per mole, corresponds to the 90 pct confidence level. A linear relationship was found between the logarithm of the hydrogen diffusion coefficient D_H ^Fe-X and the interaction parameter ε_H ^X for low and medium concentrations of alloying elementX, when applied to a fixed concentration ofX(5 or 25 at. pct) and to individual periods in the periodic table. A useful linear correlation also appears to exist between logD_H ^Fe-X and hydrogen solubility for fixed concentration ofX and with respect to the period in whichX is found. Formerly Research Assistant, Department of Mineral Engineering, Stanford University, Stanford, Calif. This paper is based upon a thesis submitted by P. J. DEPUYDT in partial fulfillment of the requirements of the degree of Doctor of Philosophy at Stanford University and part of a presentation made at the 1970 Annual AIME Meeting.     

Tracer diffusion of63Ni in Fe-17 wt pct Cr-12 wt pct Ni

The tracer diffusion of⁶³Ni in Fe-17 Cr-12 Ni by both volume and grain boundary transport has been studied from 600° to 1250°C. The use of an RF sputtering technique for serial sectioning allowed the determination of very small volume diffusion coefficients at the lower temperatures. Volume diffusion of nickel in this alloy was observed to be much slower than in pure iron or austenitic stainless steel at comparable temperatures. The volume diffusion coefficient is described byD _v =8.8 exp (−60,000/RT) cm²/s and grain boundary diffusion is described by σD _gb =3.7×10⁻⁹ exp (−32,000/RT) cm³/s. R. A. PERKINS, formerly Presidential Intern, Metals and Ceramics Division, Oak Ridge National Laboratory, Oak, Ridge, Tenn. 37830, is     

Microstructures, Mechanical Properties, and Shape Memory Characteristics of Powder Metallurgy Ti51Ni49 Modified with Boron

Ti₅₁Ni₄₉ compacts consolidated with persistent liquid-phase sintering usually contain Ti₂Ni networks at the grain boundaries, which cause adverse effects on mechanical properties. With 0.5 and 1.0 at pct B additions, fine TiB forms during heating and sintering and acts as a nucleation site for Ti₂Ni to precipitate within the grain during cooling. The resultant uniform distribution of TiB and Ti₂Ni impedes grain growth and prevents the formation of continuous Ti₂Ni precipitates at grain boundaries. As a result, a significant increase in tensile elongation, and not a decrease, as in most as-cast titanium alloys, is obtained because of these changes. The tensile strength also increases, without deterioration of the shape memory characteristics. The tensile strength and elongation are close to those of wrought TiNi alloys.     

Growth of semicoherent TiFe nanoparticles in β-Ti matrix in the Ti73Fe27 rapidly quenched ribbon

A thin Ti₇₃Fe₂₇ ribbon was prepared by rapid quenching from the melt. The as-quenched ribbon was in a metastable condition with a small amount of nanoparticles of TiFe, of a size of 138±31 nm, embedded in the β-Ti matrix. The β-Ti matrix was supersaturated with Fe, and the fraction of the matrix was higher than that in the equilibrium state. High-resolution imaging of the interface of the TiFe/β-Ti showed that a periodic array of dislocations were present in the interface to accommodate the lattice mismatch. The spacing between the dislocations in the as-quenched specimen was 5.0±0.5 nm. When the ribbon was heated to 700 °C, growth of the TiFe nanoparticles to a size of 228±37 nm took place in the β-Ti matrix. The amount of β-Ti was reduced, as well as the Fe content in β-Ti. The interface between the TiFe and β-Ti remained semicoherent, except that the spacing between the interfacial dislocations was reduced to 3.5±0.6 nm. The persistence of the semicoherent interface was ascribed to the same crystal structure and close lattice parameters shared by TiFe and β-Ti. The growth kinetics of the TiFe nanoparticles during heating was examined based on the modified theory of isothermal heating. It can be considered to be controlled by the diffusion of Fe atoms in the β-Ti matrix to the TiFe phase. Prolonged heating of the ribbon below the eutectoid temperature led to partial transformation of β-Ti to α-Ti.     

The diffusivity and solubility of oxygen in liquid tin and solid silver and the diffusivity

The diffusivity and solubility of oxygen in liquid tin and solid silver in the temperature range of about 750° to 950°C (1023 to 1223 K) and the diffusivity of oxygen in solid nickel at 1393°C (1666 K) were determined using the electrochemical cell arrangement of cylindrical geometry: Liquid or Solid Metal + O (dissolved) | ZrO₂ + (3 to 4%)CaO | Pt, air The diffusivity and solubility of oxygen in liquid tin are given by:D _O(Sn) = 9.9 × 10⁻⁴ exp(−6300/RT) cm²/s (9.9 × 10⁻⁸ exp − 6300/RT m²/s) andN _O ^S (Sn) = 1.3 × 10⁵ exp(−30,000/RT) at. pct The diffusivity and solubility of oxygen in solid silver follow the relations:D _O(Ag) = 4.9 × 10⁻³ exp (−11,600/RT) cm²/s ( 4.9 × 10⁻⁷ exp − 11,600/RT m²/s) andN _O ^S (Ag) = 7.2 exp (−11,500/RT) at. pct The experimental value for the preexponential in the expression forD _O(Ag) is lower than the value calculated according to Zener’s theory of interstitial diffusion by a factor of 11. The diffusivity of oxygen in solid nickel at 1393°C (1666 K) was found to be 1.3 × 10⁻⁶ cm²/s (1.3 × 10⁻¹⁰ m²/s). Formerly Graduate Student, Department Formerly Graduate Student, Department Formerly Graduate Student, Department This paper is based upon a This paper is based upon a This paper is based upon a This paper is based upon a