Properties of Coatings Based on Calcium Phosphate and Their Effect on Cytocompatibility and Bioactivity of Titanium Nickelide.

Coatings based on calcium phosphate with thicknesses of 0.5 and 2 µm were obtained by high-frequency magnetron sputtering on NiTi substrates in an argon atmosphere. The coating was characterized using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and in vitro cytocompatibility and bioactivity studies. A biphasic coating of tricalcium phosphate (Ca3(PO4)2) and hydroxyapatite (Ca10(PO4)6(OH)2) with a 100% degree of crystallinity was formed on the surface. The layer enriched in calcium, phosphorus, and oxygen was observed using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Scanning electron microscopy showed that the surface structure is homogeneous without visible defects. The 2 µm thick coating obtained by sputtering with a deposition time of 4 h and a deposition rate of 0.43 µm/h is uniform, contains the highest amount of the calcium phosphate phase, and is most suitable for the faster growth of cells and accelerated formation of apatite layers. Samples with calcium phosphate coatings do not cause hemolysis and have a low cytotoxicity index. The results of immersion in a solution simulating body fluid show that NiTi with the biphasic coating promotes apatite growth, which is beneficial for biological activity.

Regularities in the Evolution of Thermoelastic Martensitic Transformations during Cooling/Heating in the Free State and under Load of Titanium Nickelide Alloyed with Niobium.

This article presents the results of studies of the features of the development of thermoelastic martensitic transformations during cooling/heating in the free state and under load of Ti50Ni49.7-XNbXMo0.3 alloys (X = 0.5, 1.0 and 1.5 at% Nb) with shape memory effects. Using X-ray diffraction analysis, it was found that all the alloys studied at room temperature contained a multiphase mixture consisting of intermetallic compounds with the TiNi (B2, B19'), Ni56Ti29Nb15, and Ti2Ni compositions. Scanning electron microscopy was used to study the microstructure of TiNi (Nb,Mo) alloys and it was found that the distribution of fine Ni56Ti29Nb15 particles in the matrix depends significantly on the concentration of the alloying element. A correlation was established between changes in the structural-phase state in TiNi (Nb,Mo) alloys and the occurrence of the B2↔B19' martensitic transition in the free state and under load. Based on physical and mechanical studies, the temperature ranges of the martensitic transformations (MT) in the free state and under load were established. Based on the thermodynamic description of the MT and the analysis of the characteristic temperatures of the MT, it was found that the MT mechanism is strongly dependent on the concentration of the alloying element.

Phase Composition, Microstructure, Multiple Shape Memory Effect of TiNi50-xVx (x = 1; 2; 4 at.%) System Alloys.

The phase composition, microstructure, and multiple shape memory effect of TiNi50-xVx alloys were studied in this work. The phase composition of the TiNi50-xVx system is the TiNi matrix, spherical particles of TiNiV, the secondary phase Ti2Ni(V). Doping of TiNi alloys with vanadium atoms leads to an increase in the stability of high-temperature B2 and rhombohedral R-phases. An increase in the atomic volume with an increase in the concentration of the alloying element V from 1 to 4 at.% was established. Vanadium doping of the Ti-Ni-V system alloys leads to an increase in the temperature interval for the manifestation of the multiple shape memory effect. It has been established that the value of the reversible deformation of the multiple shape memory effect both during heating and during cooling increases linearly from 2 to 4% with an increase in the vanadium concentration.

Compression Relaxation of Multi-Structure Polymer Composites in Penetrating Liquid Medium.

Multi-structural polymer composites are widely used in the mechanical engineering, automotive, aviation and oil refining industries, as well as in the printing industry as a shock-absorbing deckle on the offset cylinders of printing machines. During offset printing, composites come into contact with inks and washing solutions, the components of which penetrate the material and cause the polymers to swell. This process degrades the print quality, and for this reason the study of its features is relevant. The prerequisites for this work are the study of the fundamental laws of diffusion and sorption of liquids by polymers with different micro- and macro-structures in different physical states and in different forms (e.g., films, sheets, fibers and fabrics). The combination of polymer materials in the composition of multi-structural fabric blankets makes it possible to obtain materials with unique mechanical properties and high resistance to liquid penetrating media and to use them in high-tech processes of multi-color printing with high resolution and color rendering. This article reports for the first time the kinetics and thermodynamics results obtained from the swelling of multi-structural polymeric blankets in solvents used in printing, and the effect of sorption of different polar liquids on the viscoelastic strain under compression during the operation of the damping systems of printing machines. Using mathematical models of activated liquid diffusion in polymers and deformation of a viscoelastic body, the swelling rate constants, solvent diffusion coefficients (the kinetic characteristics of the swelling process) and Flory−Huggins parameters (the thermodynamic characteristics of the interaction of the solvent with the composite) for composite−solvent systems with several chemical composition variants were determined. The elastic modulus and the viscosity coefficient of the composite under liquid saturation were calculated based on the experimental cyclic compression data. The range of change in the compression and restoration times of the polymeric blankets (0.09 s ÷ 0.78 s) was determined. It was shown that the composite swelled to a limited extent in all the studied liquids. All solvents used were thermodynamically poor (χ > 0.5). It has been established that rubber−fabric blankets coated with nitrile rubber are the least resistant to the action of dichloroethane, and that blankets with layers of polyolefins are not resistant to ethyl acetate. Water significantly affects the physicochemical properties of rubber−fabric blankets with a large proportion of cotton fabric layers. The data obtained can serve as a basis for optimizing the compositions of inks and cleaning solutions, as well as a theoretical basis for the thermodynamics of composite−solvent systems.

Thickness Effects on the Martensite Transformations and Mechanical Properties of Nanocrystalline NiTi Wires.

This paper studied the features of the martensitic transformations and mechanical properties of 40, 60, and 90 µm thick NiTi wires with nanocrystalline B2 structures. It was established that the wires were composites and consisted of a TiNi matrix and a TiO2 + TiNi3 surface layer. Structural methods showed that the wire matrix was formed by grains of up to 20 nm in size. The method of measuring the electrical resistivity during cooling and heating revealed a two-stage nature of the martensitic transformation. Cyclic loading-unloading demonstrated that all the samples exhibited superelasticity effects and completely restored their shape when unloaded from a 4-8% relative strain at room temperature. An increase in mechanical characteristics with respect to the wire thickness was experimentally established. This was due to the change in the composition of the TiNi matrix during drawing.

Functionalization of the Surface of Porous Nickel-Titanium Alloy with Macrocyclic Compounds.

For the first time, we performed functionalization of the surface of porous titanium nickelide alloys with bambusuril[6]-based macrocyclic compounds by different methods in order to provide the basis for saturation with therapeutic agents to impart antibacterial activity and accelerate its osteogenesis. It has been shown for the first time that the vacuum modification method is preferable for bambusuril deposition, since it provides a uniform deposition of organic matter on both the outer and inner surfaces of the pores. The effect of bambusuril deposition methods on the continuity, structure, and cytocompatibility of the porous titanium nickelide surface was evaluated. In vitro tests proved high biocompatibility and low toxicity of porous TiNi treated with BU[6] under vacuum. The SEM study of the structure of the surface layer of TiNi modified with BU[6] under the vacuum method showed that BU[6] agglomerates are uniformly deposited on the inner and outer surfaces of TiNi pores, which will provide an even saturation of BU[6] cavities with various pharmaceuticals, including antibiotics and inhibitors.

Softening Effects in Biological Tissues and NiTi Knitwear during Cyclic Loading.

Samples of skin, tendons, muscles, and knitwear composed of NiTi wire are studied by uniaxial cyclic tension and stretching to rupture. The metal knitted mesh behaves similar to a superelastic material when stretched, similar to soft biological tissues. The superelasticity effect was found in NiTi wire, but not in the mesh composed of it. A softening effect similar to biological tissues is observed during the cyclic stretching of the mesh. The mechanical behavior of the NiTi mesh is similar to the biomechanical behavior of biological tissues. The discovered superelastic effects allow developing criteria for the selection and evaluation of mesh materials composed of titanium nickelide for soft tissue reconstructive surgery.

Fertility-Sparing Surgery Using Knitted TiNi Mesh Implants and Sentinel Lymph Nodes: A 10-Year Experience.

OBJECTIVES: The aim of this cohort study is to improve the procedure of fertility-sparing surgery and to assess oncological and reproductive follow-up outcomes after radical trachelectomy (RT) for cervical cancer (T1a2-1bNxM0). METHODS: We have suggested the method combining sentinel lymph nodes (SLNs) and cervicoisthmic cerclage using a superelastic knitted TiNi mesh (KTNM) implant to facilitate the primary biomechanical/retention function of the uterus. Sixty-eight consented patients, who underwent fertility-sparing surgery using both transabdominal and laparoscopic route from 2009 through 2019, were recruited in the study and prospectively followed for a mean of 69 months. RESULTS: There were no intraoperative or postoperative complications. No cervical stenoses or mesh failures were noted in all cases. The 5-year overall and recurrence-free survival rates were 100% and 97%, respectively. Two patients indicated recurrence, it occurred in 3 and 36 months. There were 19 (28%) spontaneous pregnancies, 6 resulted in full-term delivery, whereas 2 and 11 ended in miscarriage and early abortion, respectively. CONCLUSIONS: This sparing-surgery technique is turned out to be feasible and efficient as allows to achieve well oncologic and fertility outcomes, mimicking the effect of the cervix. It complements existing surgical approaches and may provide further insight into how to overcome challenges even in aggravated cases or previously failed procedures.

Study on tensile, bending, fatigue, and in vivo behavior of porous SHS-TiNi alloy used as a bone substitute.

Intermetallic porous SHS-TiNi alloys exhibit tangled and specific stress-strain characteristics. This article aims to evaluate the findings emanating from experiments using standard and proprietary instruments. Fatigue testing under repeated complex loading was used to measure the total number of load cycles before failure of the SHS-TiNi samples occurred. Of the tested samples, seventy percent passed through 106 cycles without failure due to the reversible martensite transformation in the TiNi phase, one of the prevailing constituents of a multiphase matrix. The fractured surfaces were analyzed using scanning electron microscopy and confocal laser scanning instruments. Microscopy studies showed that the entire surface of the sample is concealed by miscellaneous strata that result from the SHS processand effectively protect the porous alloy in a corrosive environment. Numerous non-metallic inclusions, which are also attributed to the SHS reaction, do not have a significant impact on the deformation behavior and fatigue performance. In this context, the successful in vivo functioning of porous grafts assessed in a canine rib-plasty model allows the bone substitute to be congruentially deformed in the body without rejection or degradation; it thus has a long operational life, often greater than 17 ×106 (22 × 60 × 24 × 540) cycles. It acknowledges the potential benefits of SHS-TiNi as a superior osteoplastic material and its high resistance to corrosion fatigue.

Influence of Silver Addition on Structure, Martensite Transformations and Mechanical Properties of TiNi-Ag Alloy Wires for Biomedical Application.

The microstructural and functional behavior of TiNi-based wires with a silver content of 0-1.5 at.% was evaluated. The concentration range for Ag doping determined for the TiNi wires with potential for the medical industry was 0-0.2 at.%. Microstructure analysis of TiNi wires with different silver contents at room temperature indicated a multiphase structural state. Various internal structures with tangled grain boundaries were formed by intense plastic deformation. The nanocrystalline structure and phase state of wire with the minimum silver content (0.1 at.% Ag) provide full shape recovery, the greatest reversible strain, and optimal strength and ductility. TiNi ingots with a high Ag content (0.5-1.5 at.%) cracked under minimum load due to excess silver that crystallized along the grain boundaries and broke cohesion bonds between the TiNi grains.

Biocompatibility and Clinical Application of Porous TiNi Alloys Made by Self-Propagating High-Temperature Synthesis (SHS).

Porous TiNi alloys fabricated by self-propagating high-temperature synthesis (SHS) are biomaterials designed for medical application in substituting tissue lesions and they were clinically deployed more than 30 years ago. The SHS process, as a very fast and economically justified route of powder metallurgy, has distinctive features which impart special attributes to the resultant implant, facilitating its integration in terms of bio-mechanical/chemical compatibility. On the phenomenological level, the fact of high biocompatibility of porous SHS TiNi (PTN) material in vivo has been recognized and is not in dispute presently, but the rationale is somewhat disputable. The features of the SHS TiNi process led to a multifarious intermetallic Ti4Ni2(O,N,C)-based constituents in the amorphous-nanocrystalline superficial layer which entirely conceals the matrix and enhances the corrosion resistance of the unwrought alloy. In the current article, we briefly explore issues of the high biocompatibility level on which additional studies could be carried out, as well as recent progress and key fields of clinical application, yet allowing innovative solutions.