Porous NiTi Alloy Research Articles

Pore Control in Porous NiTi Alloy Produced by Combustion Synthesis Method with the Utilization of Space Holders

Pore Control in Porous NiTi Alloy Produced by Combustion Synthesis Method with the Utilization of Space Holders

Exploring the Potential of MIM-Manufactured Porous NiTi as a Vascular Drug Delivery Material.

Porous nickel-titanium (NiTi) manufactured using metal injection molding (MIM) has emerged as an innovative generation of drug-loaded stent materials. However, an increase in NiTi porosity may compromise its mechanical properties and cytocompatibility. This study aims to explore the potential of porous NiTi as a vascular drug delivery material and evaluate the impact of porosity on its drug loading and release, mechanical properties, and cytocompatibility. MIM, combined with the powder space-holder method, was used to fabricate porous NiTi alloys with three porosity levels. The mechanical properties of porous NiTi were assessed, as well as the surface cell growth capability. Furthermore, by loading rapamycin nanoparticles onto the surface and within the pores of porous NiTi, we evaluated the in vitro drug release behavior, inhibitory effect on cell proliferation, and inhibition of neointimal hyperplasia in vivo. The results demonstrated that an increase in porosity led to a decrease in the mechanical properties of porous NiTi, including hardness, tensile strength, and elastic modulus, and a decrease in the surface cell growth capability, affecting both cell proliferation and morphology. Concurrently, the loading capacity and release duration of rapamycin were extended with increasing porosity, resulting in enhanced inhibitory effects on cell proliferation in vitro and inhibition of neointimal hyperplasia in vivo. In conclusion, porous NiTi holds promise as a desirable vascular drug delivery material, but a balanced consideration of the influence of porosity on both mechanical properties and cytocompatibility is necessary to achieve an optimal balance among drug-loading and release performance, mechanical properties, and cytocompatibility.

Biocompatibility and Antibacterial Properties of NiTiAg Porous Alloys for Bone Implants.

In order to reduce infections, porous NiTi alloys with 62% porosity were obtained by self-propagating high-temperature synthesis with the addition of 0.2 and 0.5 at. % silver nanoparticles. Silver significantly improved the alloys' antibacterial activity without compromising cytocompatibility. An alloy with 0.5 at. % Ag showed the best antibacterial ability against Staphylococcus epidermidis. All alloys exhibited good biocompatibility with no cellular toxicity against embryonic fibroblast 3T3 cells. Clinical evaluation of the results after implantation showed a complete absence of purulent-inflammatory complications in all animals. Even distribution of silver nanoparticles in the surface layer of the porous NiTi alloy provides a uniform antibacterial effect.

Microstructure-dependent deformation mechanisms and fracture modes of gradient porous NiTi alloys

Gradient porous structures based on triply periodic minimal surfaces offer exceptional specific strength and multi-functionality. However, strain heterogeneity complicates their deformation mechanisms and fracture modes. In this study, we fabricated a series of gradient porous NiTi alloys based on gyroid (G), diamond (D), and I-WP (I) unit cells, with porosities ranging from 50% to 70%. Surprisingly, the I structure exhibited an abnormally high compressive strength of nearly 600 MPa at around 50% porosity, more than twice that of the G and D structures. This performance gap was attributed to the activation of mixed deformation mechanisms and distinct fracture modes. While the G structure showed a uniform radial strain distribution, the D and I structures displayed pronounced radial strain gradients with concentrated central strains. The D structure deformed through relative sliding of oblique struts, while the I structure maintained macrostructural stability, with thick edge struts providing continuous strain hardening until monolithic fracture. This unique deformation behavior results from the synergistic effects of its intrinsic macrostructural stability, significant radial strain gradients, and sufficiently thicker edge struts. The integration of metallurgical and architectural design principles represents a novel approach to tailoring the mechanical properties of gradient porous metals for advanced applications.

Study of the biocompatibility of porous 3D-TiNi implants in vivo

Introduction. Porous TiNi alloys are widely used in medicine as osteoreplacement implants due to their unique properties of superelasticity and biocompatibility, but their clinical use is severely limited by time-consuming manual fabrication and the inability to create precise geometries. Reconstructive surgery for the replacement of bone defects requires biocompatible endoprostheses of individual shape and complex geometry. The use of porous 3D-TiNi implants can be a solution to many problems in traumatology and bone oncology.Aim: To evaluate the possibility of using porous 3D-TiNi implants in osteoplastic surgery based on a study of the structure and biocompatibility of the material under in vivo conditions.Material and Methods. Porous samples in the form of cones and a single implant for maxillofacial surgery were prepared from TiNi powder by selective laser melting. To print an individual implant for maxillofacial surgery, the personal data of the patient at the Oncology Research Institute were used. The macrostructure, elemental and phase composition of porous titanium nickelide samples were investigated using scanning microscopy and X-ray diffraction analysis. The biocompatibility of porous cone-shaped samples was evaluated in vivo using guinea pigs whose condition was analysed by CT scanning.Results. Structural studies of porous titanium nickelide samples showed that selective laser melting can be used to obtain a continuous porous structure with strong contact bridges between particles of a three-phase powder. In vivo testing of the cone-shaped implants showed no local inflammatory changes, rejection or deformation of the hind limb axes of the experimental animals. The basic feasibility of fabricating a custom implant of complex geometry from TiNi powder using selective laser melting according to a patient’s MSCT data was demonstrated.Conclusions. Porous 3D-TiNi implants obtained by selective laser melting showed high biocompatibility under in vivo conditions. An experimental study confirmed the efficacy and ease of use of 3D TiNi implants, their excellent self-fixation in bone tissue, and bone tissue augmentation at the interface with the implant. The macrostructure, chemical and phase composition of the implant material was found to be close to traditional porous TiNi alloys. It was shown that the method of selective laser melting makes it possible to create complex geometric defects in bone tissue from TiNi.

Effect of Sintering Temperature on Microstructure Characteristics of Porous NiTi Alloy Fabricated via Elemental Powder Sintering.

To investigate the effect of the sintering temperature on the microstructure characteristics of porous NiTi alloys, two types of porous NiTi alloys with equal atomic ratios were fabricated via elemental powder sintering at 950 °C and 1000 °C. Afterwards, optical microscopy (OM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were collectively applied to investigate the pore characteristics and microstructure of the fabricated porous NiTi alloy. The results show that when the sintering temperature increases from 950 °C to 1000 °C, the average pore size increases from 36.00 μm to 181.65 μm, owing to the integration of these newly formed small pores into these pre-existing large-sized pores. The measured density increases from 2.556 g/cm3 to 3.030 g/cm3, while the porosity decreases from 60.4% to 51.8%. This is due to the occurrence of shrinkage after the sufficient diffusion of atoms. Furthermore, the characterization results confirm that a change in the sintering temperature would not change the phase types within a porous NiTi alloy; namely, the matrix consists primarily of B2 NiTi, with a significant amount of Ni4Ti3 precipitates and a small amount of Ni3Ti precipitates and Ti2Ni precipitates. However, as the sintering temperature increases, the number of Ni4Ti3 precipitates decreases significantly. The formation of a Ni4Ti3 phase in the present study is closely related to the enrichment of Ni content in the matrix owing to the diffusion rate difference between Ni atoms and Ti atoms and the absence of a transient liquid phase (TLP) during the sintering process owing to the relatively low sintering temperature (lower than the eutectic temperature). Moreover, the increasing sintering temperature speeds up the atom diffusion, which contributes to a reduction in the enrichment of Ni as well as the number of formed Ni4Ti3 precipitates.

Near-spherical micron-porous NiTi alloys with high performances fabricated via metal injection molding

In this study, NiTi alloys with different porosity were prepared using metal injection molding combined with the powder space-holder method (MIM-PSH). The microstructures, transformation temperatures, compression and its recovery properties were investigated. The porous structure consisted of near-spherical pores (40.8 and 44.9 μm). The pore size was tied to the size of space-holder but not porosity, which was beneficial to controllability of pore diameter. The matrix was dominated by B2 austenite, with small amounts of B19′ martensite and Ti2Ni inclusions. Ni4Ti3 precipitates were also observed, not only in micrometer scale, but also as nanodomains. Highly broadened R peaks were observed in the differential scanning calorimetry thermograms, which were attributed to extensive, non-uniform, multi-scale precipitation. Overall, pores at this scale shown no influence on the transformation behaviors. Due to the low final oxygen content (0.19 % and 0.23 %) and homogeneous near-spherical pores, high compressive properties had been exhibited. The compressive recovery was almost complete at 3 %, 6 % and 8 % pre-strains. Irreversible strain increased with increasing pre-strain. The average volume variation of the pores under different deformations was analyzed in detail. In the future, MIM-PSH should be used to further enhance the customized fabrication of porous NiTi alloys.

Lightweight and Highly Porous Ni-Ti Alloy Foams Synthesized by Powder Metallurgy using NaCl as Space Holder

Lightweight and Highly Porous Ni-Ti Alloy Foams Synthesized by Powder Metallurgy using NaCl as Space Holder

A Unified Empirical Equation for Determining the Mechanical Properties of Porous NiTi Alloy: From Nanoporosity to Microporosity

The mechanical characteristics of a monolithic (non-porous) crystalline or amorphous material are described by a well-defined set of quantities. It is possible to change the mechanical properties by introducing porosity into this material; as a rule, the strength values decrease with the introduction of porosity. Thus, porosity can be considered an additional degree of freedom that can be used to influence the hardness, strength and plasticity of the material. In the present work, using porous crystalline NiTi as an example, it is shown that the mechanical characteristics such as the Young’s modulus, the yield strength, the ultimate tensile strength, etc., demonstrate a pronounced dependence on the average linear size l¯ of the pores. For the first time, an empirical equation is proposed that correctly reproduces the dependence of the mechanical characteristics on the porosity ϕ and on the average linear size l¯ of the pores in a wide range of sizes: from nano-sized pores to pores of a few hundred microns in size. This equation correctly takes into account the limit case corresponding to the monolithic material. The obtained results can be used directly to solve applied problems associated with the design of materials with the necessary combination of physical and mechanical characteristics, in particular, porous metallic biomaterials.

High-strength porous NiTi shape memory alloys with stable cyclic recovery properties fabricated using elemental powders

Based on previous research regarding the high-vacuum sintering of elemental powder (EP) NiTi alloys, this study investigates the preparation of high-strength, highly cyclically stable porous NiTi shape memory alloys. The microstructures, martensitic transformation behaviors, compressive and compressive recovery properties, and cyclic stabilities of the sintered and aged porous NiTi alloys were compared and analyzed. The porosity and average pore size increased with the addition of NaCl, with the oxygen content increasing slightly. The sintered alloy displayed an inhomogeneous distribution of the Ni4Ti3 precipitate, which exhibited a dispersed and homogeneous distribution after aging. The sintered porous NiTi alloy exhibited a multistage phase transformation. The martensitic transformation was suppressed after aging owing to changes in the size and distribution of the precipitates, and only R-phase transformation was observed. Porosity and aging precipitation influenced the dual yield points and recovery properties of porous NiTi. The pinning effect of aging precipitation increased the yield point and reduced the residual strain in the recovery. However, at a high porosity, the volume fraction of NiTi matrix decreased, resulting in a small strengthening contribution of precipitation. The disruption of porous structure was the dominant causes of irreversible strain. As the porosity increased, the porous structure became increasingly susceptible to damage during cyclic loading. Overall, the EP porous NiTi alloy exhibited a higher compressive strength, enhanced compression recovery properties and cyclic stability compared to those reported in previous studies. This is because of the optimization of high-temperature homogenization via sintering at 1250 °C and enhancement effects of aging precipitation. This study provides a novel approach for developing porous EP NiTi alloys.

Plasticity of Porous NiTi Alloys Obtained by Self-propagating High-temperature Synthesis in Closed and Open Gas Flow Reactors

ABSTRACT Porous NiTi alloys were obtained by self-propagating high-temperature synthesis (SHS) using layer-by-layer combustion in closed and open gas flow reactors under a protective argon atmosphere. The maximum compressive strain of porous NiTi alloys synthesized in the closed reactor was 34% compared to 7% in the open gas flow reactor. X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, energy dispersive spectroscopy, and optical microscopy showed that the reaction products in the two-phase gas zone of peritectic crystallization are in the form of isolated Ti2Ni crystalline clusters in the TiNi matrix. The ductility and strength of the recrystallized Ti2Ni phase hard dendrites increase the effective stiffness of porous NiTi alloys and decrease the maximum compressive strain. A highly porous NiTi alloy with improved mechanical properties was obtained by the SHS method in a closed reactor.

Structure and Mechanical Properties of Porous TiNi Alloys with Ag Nanoparticles

The work studies the influence of the silver dopant (<0.5 at.%) on the structure and mechanical properties of porous TiNi alloys obtained by self-propagating high-temperature synthesis. These alloys are of high scientific and practical interest in medicine. The presence of silver in the TiNi alloy will ensure improved cytocompatibility and antibacterial properties. The TiNi porous alloys with 0.2 and 0.5 at.% Ag nanoparticles have multiphase composition. Quantitative X-ray diffraction analysis of the obtained alloys showed that an increase in the silver content is accompanied by a quantitative decrease in the austenite phase TiNi(B2) and an increase in the martensite phase TiNi(B19’), as well as in secondary phases Ti2Ni, Ti4Ni2O. Evenly distributed silver nanoparticles up to 10 nm were found in the surface layer by transmission electron microscopy. The results of the scanning electron microscopy showed that inclusions containing silver are located mainly in the zones of Ti2Ni peritectic crystallization. The mechanical characteristics were studied by means of compression tests and it was found that with an increase in the silver dopant, the elastic modulus and elastic limit decrease, but the maximum deformation to fracture increases significantly. It was found that with an increase in the volume fraction of silver, the plastic properties of the alloy increase. No dependency of the tensile strength on the amount of silver was found.

Anisotropy of elastic properties of SHS-synthesized porous titanium nickelide

Samples of porous NiTi were obtained by the method of self-propagating high-temperature synthesis. The mechanical characteristics of the porous ones were studied by quasi-static compression. When the samples of porous titanium nickelide were subject to quasi-static compression, the deformation was of an elastic-plastic nature. Three characteristic types of the fracture surface under quasi-static compression of the porous SHS – TiNi alloy were identified: 1) ductile fracture of the austenite phase in the form of a cup relief, 2) brittle fracture accompanied by the formation of cleavage steps, 3) large areas of plastic shear deformation, on which cups and cleavage facets were nucleated. To determine the anisotropy of the porous TiNi alloy properties, the volume of the porous sample was simulated, and estimated calculations were carried out. Based on the results of reconstructing 3D neutron high resolution tomography of the porous volume of titanium nickelide and the numerical parameters of the model porous medium, an algorithm was developed for obtaining a solid-state 3D model of the porous framework for using in finite element calculations. The studied porous titanium nickelide alloy, as well as spongy bone tissues, was shown to have orthotropic elastic properties conditioned by the geometric features of the porous framework. The effective moduli of elasticity and shear for the porous volume of the material were determined. The calculation results of the elastic moduli for the studied model of porous titanium nickelide numerically agree with the results obtained by compressing the samples of porous TiNi. The porous TiNi alloy under uniaxial compression was established to be destroyed under the action of tangential shear stresses at an angle of 45 degrees to the direction of uniaxial compression. The research was carried out with financial support of the Russian Science Foundation under the Grant No. 22-72-10037, https://rscf.ru/project/22-72-10037/.

Influence of the Gas Reaction Atmosphere on the Structure, Phase Composition, Functional Properties and Cytocompatibility of Porous Titanium–Nickel Alloys

This work studies the effect that argon and nitrogen atmospheres have on the structure, phase composition, cytocompatibility, and functional properties of porous NiTi alloys obtained by self-propagating high-temperature synthesis. Porous alloys obtained in the nitrogen atmosphere (NiTi-(N)) are characterized by brittle interstitial phases Ti4Ni2O(N) and the appearance of a finely dispersed TiNi3 phase in comparison with the alloy obtained in an argon atmosphere (NiTi-(Ar)). An increase in the volume fraction of the Ti4Ni2O(N) phase as well as an increase in the content of nitrogen in the surface layer of the NiTi-(N) alloy favorably affects the surface cytocompatibility with bone marrow mesenchymal stem cells. It was found that the mechanisms of martensitic transformations in porous NiTi alloys under load and without load are different. It has been established that the mechanical characteristics of NiTi-(N) alloys are noticeably lower than those of NiTi-(Ar) alloys. Thus, according to the data obtained, porous NiTi-(N) alloys can be considered more biocompatible under low physiological load. However, it is necessary to increase their reversible deformation and tensile strength in order to use porous NiTi-(N) alloys under high physiological load.

Influence of Solid Loading on the Gel-Casting of Porous NiTi Alloys

Porous NiTi alloys are widely applied in the field of medical implant materials due to their excellent properties. In this paper, porous NiTi alloys were prepared by non-aqueous gel-casting. The influence of solid loading on the process characteristics of slurries and the microstructure and mechanical properties of sintered samples were investigated. The viscosity and the stability of slurry significantly increased with the growth of solid loading, and the slurry had better process characteristics in the solid loading range of 40-52 vol.%. Meanwhile, the porosity and average pore diameter of the sintered NiTi alloys decreased with a rise in the solid loading, while the compressive strength increased. Porous NiTi alloys with porosities of 43.3-48.6%, average pore sizes of 53-145 µm, and compressive strengths of 87-167 MPa were fabricated by gel-casting. These properties meet the requirements of cortical bone. The results suggest that the pore structure and mechanical properties of porous NiTi products produced by gel-casting can be adjusted by controlling the solid loading.

INVESTIGATION OF THE EFFECT OF SINTERING TEMPERATURES ON THE PRODUCTION OF POROUS NITI ALLOY BY LOOSEN SINTERING METHOD

This article aims to produce NiTi shape memory alloys, which show superelasticity and shape memory effect, as well as good biocompatibility and corrosion properties, in open and porous sizes ranging from 100-500 μm, which are required for use as implants. This structure of pores is necessary to allow tissue growth and fluid flow inside the implants. Many powder metallurgy methods have been used in producing porous NiTi shape memory alloys. However, the packaging pressure used in these methods has not successfully created the desired pore distribution, shape, and size. The methods by which it can be produced are costly in terms of cost. In the study, production was carried out by sintering the powder mixture poured into molds without pressure with the help of binder polymers. This sintering process was carried out in an argon atmosphere for 1 hour at temperatures 1050, 1125, and 1200 °C. The study shows that pressureless loosen sintering can produce porous NiTi alloys, which is the more straightforward method. The pore distribution and proportions were examined. Homogeneous distribution and pores in desired sizes are created. It has also been determined that the binder polymer has a space-retaining effect. It was determined at which temperature the alloy sintered at different temperatures contained the desired B2 austenite phase for superelasticity. Austenite start and finish temperatures were determined for the alloy produced at each sintering temperature. As a result of this research, it was determined which phase was denser at which temperature, and the phase transformation temperatures were found. The exact temperature measurements can be calculated by changing the sintering time parameter. In addition, the change in phase transformation temperatures can be measured by heat treatment after sintering. Porous NiTi alloys can be used as dental and medical implants thanks to their excellent biocompatibility and corrosion resistance. This method will decrease production costs, and more people will have access to this material. In general, the mechanism of sintering methods is joining the points in contact with the packaging pressure by necking. In this study, the combination of the grains with the polymer without packaging pressure with the thermal expansion mechanism reveals the originality of the study.

Electrochemical dealloying of porous NiTi alloy: Porosity evolution, corrosion resistance, and biocompatibility behavior

This study investigates the role and mechanism of electrochemical dealloying (ED) to decrease the nickel ion release and improve the biocompatibility of porous NiTi alloy. The potentiostatic dealloying was performed in an acidic solution, and the effect of ED duration on the surface morphology and composition of porous NiTi alloys was studied. The results indicated that the dealloying was initially started from the edges of primary pores by forming TiO2 clusters due to preferential Ni dissolution. Afterward, it progressively extended to the top surface and developed a fine porous structure. We proposed two atomistic and microstructural models to describe the evolution of the porous structure during ED treatment. The potentiodynamic polarization (PDP) and electrochemical impedance spectrometry (EIS) methods were employed to investigate the corrosion behavior of the treated specimens in a Ringer's solution. Atomic absorption spectroscopy (AAS) measurement revealed that 120 s ED treatment could decrease the concentration of released nickel ions during the PDP test from 4.2 ppm to <0.01 ppm. Additionally, the in-vitro cell culture and MTT assay showed that ED treatment could significantly improve the cell adhesion and proliferation on the surface of the NiTi alloy due to the formation of a superficial nickel-depleted layer with near superhydrophilic behavior.

Microstructure and Mechanical Properties of Porous NiTi Alloy Prepared by Integration of Gel-Casting and Microwave Sintering.

Porous NiTi alloys were manufactured by integration of gel-casting and microwave sintering. The effects of sintering temperature on porosity, compressive strength, pore morphology and phase composition of sintered samples were researched. The results show that the porosity and the mean pore diameter of porous NiTi alloys decrease with increasing sintering temperature, whereas the content of the NiTi phase, the elastic modulus and compressive strength of sintered samples increase. When the gel body with the solid loading of 50 vol.% is microwave sintered at 1000 °C for 30 min, porous NiTi alloys are obtained with the porosity of 38.9%, the compressive strength of 254 MPa, elastic modulus of 4 GPa, and predominant phase of NiTi. The results suggest that the method is suitable for rapid preparation of large-size and complex-shape personalized products similar to human bones at a low cost.

Investigation of the Effect of Copper Addition on Physical and Mechanical Properties of TiNi-Cu Porous Alloy

This work is devoted to the physical and mechanical properties of porous alloys based on TiNi alloyed with different amounts of Cu additive. We show that by doping a porous TiNi alloy with copper instead of nickel, it is possible to obtain characteristics acceptable for use in implantology and superior to those of known porous TiNi alloys. Cu addition in the range from 1 to 10 at.% is shown to optimize the properties of tested alloys. There is a decrease in the minimal martensitic transformation stress τMsmin from 37 to 17 MPa when compared to initial unalloyed TiNi. Alloys with 3 and 6 at.% of Cu are found to be optimal for use in medical practice. Along with a wide temperature range of reversible deformations that cover the range of operating temperatures (273–313 K), such alloys demonstrate their martensitic transformation stress values below 28 MPs. This permits to model implantable structures of complex configuration from such materials under a certain temperature regime.

The corrosion resistance of porous Ni–Ti alloys in seawater

Porous Ni–Ti alloys were fabricated by reactive synthesis of Ni and Ti elemental powders. The corrosion behavior of porous Ni–Ti alloys was explored by electrochemical methods and weight change measurements at 298 K in seawater. The polarization curves and electrochemical impedance spectroscopy data show that porous Ni–Ti (6.5:3.5) alloys provide the best corrosion resistance. The values of corrosion current density and corrosion rate are 1.6944 × 10−4 mA/cm2 and 1.9929 mm/a, respectively. The corrosion behavior and corrosion mechanism of porous Ni–Ti alloys are also discussed.