Effects of Process Parameters upon the Shape Memory and Pseudo-Elastic Behaviors of Laser-Welded NiTi Thin Foil

This article discusses the effects of laser welding parameters such as power, welding speed, and focus position on the weld bead profile, microstructure, pseudo-elasticity (PE), and shape memory effect (SME) of NiTi foil with thickness of 250 μm using 100W CW fiber laser. The parameter settings to produce the NiTi welds for analysis in this article were chosen from a fractional factorial design to ensure the welds produced were free of any apparent defect. The welds obtained were mainly of cellular dendrites with grain sizes ranging from 2.5 to 4.8 μm at the weld centerline. A small amount of Ni₃Ti was found in the welds. The onset of transformation temperatures (A _s and M _s ) of the NiTi welds shifted to the negative side as compared to the as-received NiTi alloy. Ultimate tensile stress of the NiTi welds was comparable to the as-received NiTi alloy, but a little reduction in the pseudo-elastic property was noted. Full penetration welds with desirable weld bead profiles and mechanical properties were successfully obtained in this study.     

Production of Ni3Ti-TiC x intermetallic-ceramic composites employing combustion synthesis reactions

Combustion synthesis (CS) of nickel, titanium, and carbon (graphite) reactant particles can result in NiTi-TiC (stoichiometric) or Ni₃Ti-TiC _x (nonstoichiometric) composites. Since NiTi exhibits both superelasticity and shape memory properties while Ni₃Ti does not, it is important to understand the SHS reaction conditions under which each of these composite systems may be synthesized. The stoichiometry of TiC _x , for which 0.3 ≤ x ≤ 0.5, has an important controlling effect on the formation of either Ni₃Ti or NiTi; i.e., formation of TiC_0.7 results in a depletion of titanium and formation of Ni₃Ti. This deficiency should be considered when developing the SHS reaction. This article examines the SHS conditions under which Ni₃Ti-TiC _x composites are produced. Ignition, combustion, and microstructure characteristics of nickel, titanium, and carbon (graphite) particles were investigated as a function of initial relative density and thermophysical properties of the reactant mixture. Combination of the thermophysical properties and burning velocities controlled TiC _x particle size, yielding a dependence of particle size on cooling rate. Theoretical calculations were performed and are in good agreement with the experimental data presented.     

Production of Ni3Ti?TiC x intermetallic-ceramic composites employing combustion synthesis reactions

Combustion synthesis (CS) of nickel, titanium, and carbon (graphite) reactant particles can result in NiTi−TiC (stoichiometric) or Ni₃Ti−TiC _x (nonstoichiometric) composites. Since NiTi exhibits both superelasticity and shape memory properties while Ni₃Ti does not, it is important to understand the SHS reaction conditions under which each of these composite systems may be synthesized. The stoichiometry of TiC _x , for which 0.3≤x≤0.5, has an important controlling effect on the formation of either Ni₃Ti or NiTi; i.e., formation of TiC_0.7 results in a depletion of titanium and formation of Ni₃Ti. This deficiency should be considered when developing the SHS reaction. This article examines the SHS conditions under which Ni₃Ti−TiC _x composites are produced. Ignition, combustion and microstructure characteristics of nickel, titanium, and carbon (graphite) particles were investigated as a function of initial relative density and thermophysical properties of the reactant mixture. Combination of the thermophysical properties and burning velocities controlled TiC _x particle size, yielding a dependence of particle size on cooling rate. Theoretical calculations were performed and are in good agreement with the experimental data presented. Guglielmo Gottoli, formerly Graduate Research Assistant, Metallurgical and Materials Engineering Department, Institute for Space Resources, Colorado School of Mines     

Production of Ni3Ti?TiC x intermetallic-ceramic composites employing combustion synthesis reactions

Combustion synthesis (CS) of nickel, titanium, and carbon (graphite) reactant particles can result in NiTi−TiC (stoichiometric) or Ni₃Ti−TiC _x (nonstoichiometric) composites. Since NiTi exhibits both superelasticity and shape memory properties while Ni₃Ti does not, it is important to understand the SHS reaction conditions under which each of these composite systems may be synthesized. The stoichiometry of TiC _x , for which 0.3≤x≤0.5, has an important controlling effect on the formation of either Ni₃Ti or NiTi;i.e., formation of TiC_0.7 results in a depletion of titanium and formation of Ni₃Ti. This deficiency should be considered when developing the SHS reaction. This article examines the SHS conditions under which Ni₃Ti−TiC _x composites are produced. Ignition, combustion and microstructure characteristics of nickel, titanium, and carbon (graphite) particles were investigated as a function of initial relative density and thermophysical properties of the reactant mixture. Combination of the thermophysical properties and burning velocities controlled TiC _x particle size, yielding a dependence of particle size on cooling rate. Theoretical calculations were performed and are in good agreement with the experimental data presented. Guglielmo Gottoli, formerly Graduate Research Assistant, Metallurgical and Materials Engineering Department, Institute for Space Resources, Colorado School of Mines     

Effects of ternary additions on the thermoelastic martensitic transformation of NiAl

Nickel-rich β-NiAl alloys, which are potential materials for high-temperature shape-memory alloys, show a thermoelastic martensitic transformation, which produces their shape memory effect. However, the transformation to Ni₅Al₃ phase during heating of NiAl martensite can interrupt the reversible martensitic transformation; consequently, the shape memory effect in NiAl martensite might not appear after heating. The phase transformation process in binary Ni-(34 to 37)Al martensite was investigated by differential thermal analysis (DTA) method, and we found that the condition of reversible martensitic transformation was not the β → Ni₅Al₃ transformation, but rather the M → Ni₅Al₃ transformation occurring at 250 °C to 300 °C. Therefore, the transformation temperature of M → Ni₅Al₃ determined the highest operating temperature for the shape memory effect. For verifying the critical temperature, the phase transformation process was investigated for eight ternary Ni-33Al-X alloys (X=Cu, Co, Fe, Mn, Cr, Ti, Si, and Nb). Only Ti, Si, and Nb additions were found to be effective in dropping the M _s temperature, and they facilitated the shape memory effect in Ni-33Al-X alloys. In particular, the addition of Si and Nb raised the transformation temperature of M → Ni₅Al₃, a potentially beneficial effect for shape memory at higher temperatures. This article is based on a presentation made in the symposium entitled “Fundamentals of Structural Intermetallics,” presented at the 2002 TMS Annual Meeting, February 21–27, 2002, in Seattle, Washington, under the auspices of the ASM and TMS Joint Committee on Mechanical Behavior of Materials.     

Combustion characteristics of the Ni3Ti-TiB2 intermetallic matrix composites

Combustion synthesis (SHS) of Ni₃Ti-TiB₂ metal matrix composites (MMCs) was selected to investigate the effect of gravity in a reaction system that produced a light, solid ceramic particle (TiB₂) synthesized in situ in a large volume (>50 pct) of the liquid metallic matrix (Ni₃Ti). The effects of composition, green density of pellets, and nickel particle size on the combustion characteristics are presented. Combustion reaction temperature, wave velocity, and combustion behavior changed drastically with change in reaction parameters. Two types of density effects were observed when different nickel particle sizes were used. The structures of the combustion zones were characterized using temperature profile analysis. The combustion zone can be divided into preflame, reaction, and after-burning zones. The combustion mechanism was studied by quenching the combustion front. It was found that the combustion reactions proceeded in the following sequence: formation of liquid Ni-Ti eutectic at 940 °C → Ni₃Ti+NiTi phases → reduction of NiTi with B→TiB₂+Ni₃Ti.     

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.     

Phase equilibria in the Ni-Al-Ti system at 1173 k

The phase equilibria at 1173 K have been determined in the Ni-AI-Ti system for Al contents less than 50 at. pct. The extent of theH (Ni₂AlTi) phase field has been established as well as the extent of solubility in the binary compounds γ (Ni₃Al), ν(Ni₃Ti), β₂(NiTi), NiTi₂, and ζ(AlTi₃). Substantial differences were found between the phase equilibria determined in this study and previous studies, in part due to the large solubility of Al in NiTi₂.     

Effect of solution treatment under load on microstructure and fabrication of porous NiTi shape memory alloy by self-propagating high temperature synthesis

Abstract

Porous NiTi shape memory alloy was fabricated by self-propagating high temperature synthesis. Effects of solution treatment under load applied on the microstructure were investigated. The densities of the phases changed insignificantly with solution treatment but the intermetallic phases such as Ti₂Ni, Ni₄Ti₃ and Ni₃Ti₂ disappeared and the density of B2(NiTi) phase increased with the load applied during solution treatment. Consequently, porous NiTi SMA with ideal pore characteristics, high chemical homogeneity and high strength for hard tissue implants was obtained.     

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.     

Microstructure and Shape Memory Characteristics of Powder-Metallurgical-Processed Ti-Ni-Cu Alloys

Even though Ti-Ni-Cu alloys have attracted a lot of attention because of their high performance in shape memory effect and decrease in thermal and stress hysteresis compared with Ti-Ni binary alloys, their poor workability restrains the practical applications of Ti-Ni-Cu shape memory alloys. Consolidation of Ti-Ni-Cu alloy powders is useful for the fabrication of bulk near-net-shape shape memory alloy. Ti₅₀Ni₃₀Cu₂₀ shape memory alloy powders were prepared by gas atomization, and the sieved powders with the specific size range of 25 to 150???m were chosen for this study. The evaluation of powder microstructures was based on a scanning electron microscope (SEM) examination of the surface and the polished and etched powder cross sections. The typical images showed cellular/dendrite morphology and high population of small shrinkage cavities at intercellular regions. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis showed that a B2-B19 one-step martensitic transformation occurred in the as-atomized powders. The martensitic transformation start temperature (M_s) of powders ranging between 25 and 50???m was 304.5?K (31.5?°C). The M_s increased with increasing powder size. However, the difference of M_s in the as-atomized powders ranging between 25 and 150???m was only 274?K (1?°C). A dense cylindrical specimen of 10?mm diameter and 15?mm length were fabricated by spark plasma sintering (SPS) at 1073?K (800?°C) and 10?MPa for 20?minutes. Then, this bulk specimen was heat treated for 60?minutes at 1123?K (850?°C) and quenched in ice water. The M_s of the SPS specimen was 310.5?K (37.5?°C) whereas the M_s of conventionally cast ingot is found to be as high as 352.7?K (79.7?°C). It is considered that the depression of the M_s in rapidly solidified powders is ascribed to the density of dislocations and the stored energy produced by rapid solidification.     

Two-way shape memory effect of TiNi alloys induced by hydrogenation

An investigation on the two-way shape memory effect (TWSME) induced by an electrochemical hydrogenation has been conducted on two TiNi shape memory alloys (SMAs) (Ti_49.2Ni_50.8 and Ti_51.1Ni_48.9 denoted as materials A and B, respectively). While a bending constraint has been applied during hydrogenation, the effects of current density, solution temperature, and charging period are studied. A two-way shape memory behavior was observed on the bent, hydrogenated specimens. The measured ratio of TWSME of specimen A is greater than that of specimen B. The variation of the TWSME of the specimens is relatively small during the first 50 thermal cycles. The TWSME increases first and then decreases with increasing either current density or charging period of the electrochemical hydrogenation. The X-ray diffraction peak corresponding to hydrides in the hydrogenated specimen still exists but becomes weaker after three months of “resting,” and the TWSME obviously decreases with decreasing amount of hydrides.     

Electrochemical Codeposition and Heat Treatment of Nickel-Titanium Alloy Layers

The fabrication of nickel-titanium (Ni-Ti) alloy layers via the electrochemical codeposition and heat treatment is proposed and investigated herein. The codeposition of a Ti-dispersed Ni-matrix layer on an indium tin oxide-coated glass substrate was systematically conducted over varied current densities, Ti-particle loadings in an electrolyte and Ti particle sizes to investigate their effects on the Ti content and morphology of the layers. A moderate particle loading of approximately 2 to 6 g/dm³ led to relatively high Ti contents, whereas a decrease of particle size gave a dense and uniform layer with relatively low Ti contents. Following heat treatment, the Ni-Ti composite layers completely transformed into the Ni-Ti alloys with varying dominant phases of NiTi, Ni₃Ti, and Ni solid solution depending on the alloy compositions. The assessment of the Ni-Ti phase diagram and the Ni-Ti interdiffusivity are discussed to verify the resultant phases present in the post-annealed layers. The results and analyses from this work entail the construction of the codeposition’s mechanistic views and the interaction of the hydrodynamic, gravitational, and electrophoretic forces on particles suspended in an electrolyte, which are critical to the development of the Ni-Ti component fabrication via the combined codeposition-heat treatment route.     

An Investigation on Phase Formations and Microstructures of Ni-rich Ni-Ti Shape Memory Alloy Thin Films

Ni-rich Ni-Ti alloy thin films were fabricated by radio frequency (RF)-direct-current (DC) magnetron sputtering using elemental Ni and Ti as sputter targets. Si (100) was chosen as a substrate that was either held at room temperature or at 573 K (300 °C) during the depositions. The 380-nm-thick films were characterized by field emission scanning electron microscopy, energy dispersive spectroscopy, grazing incidence X-ray diffraction, atomic force microscopy, high-resolution transmission electron microscopy, and Vickers microhardness tester. The results suggests that because of the lack of surface mobility of the adatoms at the room temperature, the deposited films were smooth and amorphous, with a crystallite size of 15 nm accompanied with a porous morphology. At higher substrate temperatures, an increase in the surface diffusion leads to the formation of partially crystalline, rougher films with a denser, compact, fibrous grain microstructure. The formation of Ni-rich precipitates such as Ni₄Ti₃, Ni₂Ti, and Ni₃Ti along with small amount of the NiTi phase were attributed to the localized heating and cooling within the grains. Few grains exhibited band structures that are believed to be a result of <110> type II twins.     

Effect of Bonding Time on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

In the current study, solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200-μm thickness as an intermediate material was carried out in vacuum. Uniaxial compressive pressure and temperature were kept at 4 MPa and 1023 K (750 °C), respectively, and the bonding time was varied from 30 to 120 minutes in steps of 15 minutes. Scanning electron microscopy images, in backscattered electron mode, revealed the layerwise Ti-Ni-based intermetallics like either Ni₃Ti or both Ni₃Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) interface was free from intermetallic phases for all the joints. Chemical composition of the reaction layers was determined by energy dispersive spectroscopy (SEM–EDS) and confirmed by X-ray diffraction study. Maximum tensile strength of ~382 MPa along with ~3.7 pct ductility was observed for the joints processed for 60 minutes. It was found that the extent of diffusion zone at Ni/SS interface was greater than that of TiA/Ni interface. From the microhardness profile, fractured surfaces, and fracture path, it was demonstrated that the failure of the joints was initiated and propagated apparently at TiA/Ni interface near Ni₃Ti intermetallic for bonding time less than 90 minutes, and through Ni for bonding time 90 minutes and greater.     

Grain-size effect on shape-memory behavior of Ti35.0Ni49.7Zr15.4 thin films

The grain-size effect on shape-memory behavior of fine-grained Ti_35.0Ni_49.7Zr_15.4 thin films was investigated by transmission electron microscopy. The films, with various grain sizes ranging from about 150 to about 400 nm, were prepared by heat treatment of amorphous films at the three different annealing temperatures of 773, 873, and 973 K, for three different annealing times of 5 minutes, 1 hour, and 10 hours. The film annealed at 773 K for 5 minutes showed a nearly single phase of (Ti,Zr)Ni, while the films annealed at high annealing temperatures and/or long annealing times showed λ ₁ precipitates. For a high annealing temperature of 973 K, the critical yield stress (σ _c) was dominantly dependent on the grain size of the matrix, obeying the Hall-Petch equation. On the other hand, for a low annealing temperature of 773 K, σ _c was dominantly dependent on the amount of λ ₁ precipitates. The M _S temperature decreases almost linearly with increasing σ _c. The films showed sufficient fracture toughness, probably due to the nanometer scale of the grain size and the agglomerated shape of λ ₁ particles.     

Shape memory properties of Ni-Ti based melt-spun ribbons

Shape-memory properties of equiatomic NiTi, Ni₄₅Ti₅₀Cu₅, and Ni₂₅Ti₅₀Cu₂₅ ribbons made by melt spinning have been studied by temperature inducing the martensitic transformation under constant tensile loads. Recoverable strains above 4 pct can be obtained under ∼100 MPa loads for the NiTi and Ni₄₅Ti₅₀Cu₅ ribbons, transforming to B19’ martensite. The B19 martensite is formed in the Ni₂₅Ti₅₀Cu₂₅ ribbon after crystallization, and according to the lowering in transformation strain as Cu content increases, the recoverable strain is close to 2.5 pct for ∼150 MPa load. The transformation temperatures exhibit a linear dependence on the applied stress, which can be quantitatively described by means of a Clausius-Clapeyron type equation. The NiTi and Ni₄₅Ti₅₀Cu₅ ribbons exhibited some degree of two-way shape-memory effect (TWSME) after thermomechanical cycling. Texture analyses performed on the different ribbons allow us to better understand the transformation strains obtained in each ribbon. The amounts of shape-memory effect (SME) and nonrecoverable strain shown by the studied ribbons are of the same order as those already observed in bulk materials, which makes melt spinning an ideal substitute to complicated manufacturing processes if really thin samples are needed. However, applicable stresses in melt-spun ribbons are limited by a relatively “premature” brittle fracture caused by irregularities in ribbon thickness.     

Effect of Postweld Heat Treatment on the Microstructure and Cyclic Deformation Behavior of Laser-Welded NiTi-Shape Memory Wires

NiTi wires of 0.5 mm diameter were laser welded using a CW 100-W fiber laser in an argon shielding environment with or without postweld heat-treatment (PWHT). The microstructure and the phases present were studied by scanning-electron microscopy (SEM), transmission-electron microscopy (TEM), and X-ray diffractometry (XRD). The phase transformation behavior and the cyclic stress–strain behavior of the NiTi weldments were studied using differential scanning calorimetry (DSC) and cyclic tensile testing. TEM and XRD analyses reveal the presence of Ni₄Ti₃ particles after PWHT at or above 623 K (350 °C). In the cyclic tensile test, PWHT at 623 K (350 °C) improves the cyclic deformation behavior of the weldment by reducing the accumulated residual strain, whereas PWHT at 723 K (450 °C) provides no benefit to the cyclic deformation behavior. Welding also reduces the tensile strength and fracture elongation of NiTi wires, but the deterioration could be alleviated by PWHT.     

Role of Si in Improving the Shape Recovery of FeMnSiCrNi Shape Memory Alloys

The effect of Si addition on the microstructure and shape recovery of FeMnSiCrNi shape memory alloys has been studied. The microstructural observations revealed that in these alloys the microstructure remains single-phase austenite (γ) up to 6 pct Si and, beyond that, becomes two-phase γ + δ ferrite. The Fe₅Ni₃Si₂ type intermetallic phase starts appearing in the microstructure after 7 pct Si and makes these alloys brittle. Silicon addition does not affect the transformation temperature and mechanical properties of the γ phase until 6 pct, though the amount of shape recovery is observed to increase monotonically. Alloys having more than 6 pct Si show poor recovery due to the formation of δ-ferrite. The shape memory effect (SME) in these alloys is essentially due to the γ to stress-induced ε martensite transformation, and the extent of recovery is proportional to the amount of stress-induced ε martensite. Alloys containing less than 4 pct and more than 6 pct Si exhibit poor recovery due to the formation of stress-induced α′ martensite through γ-ε-α′ transformation and the large volume fraction of δ-ferrite, respectively. Silicon addition decreases the stacking fault energy (SFE) and the shear modulus of these alloys and results in easy nucleation of stress-induced ε martensite; consequently, the amount of shape recovery is enhanced. The amount of athermal ε martensite formed during cooling is also observed to decrease with the increase in Si.