TY - GEN A1 - Yasenchuk, Yuri A1 - Gunther, Victor A1 - Marchenko, Ekaterina A1 - Chekalkin, Timofey A1 - Baigonakova, Gulsharat A1 - Hodorenko, Valentina A1 - Gunther, Sergey A1 - Kang, Ji-hoon A1 - Weiß, Sabine A1 - Obrosov, Aleksei T1 - Formation of mineral phases in self-propagating high-temperature synthesis (SHS) of porous TiNi alloy T2 - Materials Research Express N2 - The complex structural-phase composition, morphology and elemental composition of surface and nonmetallics in porous TiNi compounds produced by self-propagating high-temperature synthesis (SHS) in a flow reactor in the layer-by-layer combustion mode were analyzed. The samples were investigated using light microscopy (LM), X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and energy dispersive X-ray spectroscopy (EDS). The findings indicate that in addition to the TiNi and Ti2Ni intermetallic constituents, the pore's surface contains numerous Ti4Ni2(O,N,C) nanocrystalline oxycarbonitrides, spinels, polysilicates, and residual amorphous phases. The elemental composition of the surface and crystalline inclusions is investigated by the EDS method. LM, SEM, TEM, and EDS instrumental examination revealed the entire surface comprising a continuous shell of intermetallic superficial bulb-shaped structures, as well as crystalline inclusions of polysilicates and spinels in the intergranular peritectic phase. Prominent morphology was confirmed to appear throughout the pore's surface owing to the interaction of the peritectic liquid (PL) with reaction gases. The epitaxial, nanocrystalline strata of intermetallic oxycarbonitrides were shown to have the intricate nature. Reaction gases chemisorbed by the PL are responsible for the continuous and dense substrate, which ultrafine structure modulates a high corrosion resistance. On the contrary, the sparse and foamy overlay resulted from a convective transfer of the PL by reaction gases facilitates in vivo bio-integration of the alloy. Overall, this sheds light on and may be more indicative of the complex role of superficial strata and nonmetallic crystals in enhanced biocompatibility of the unwrought porous TiNi alloy. KW - Porous TiNi alloys KW - SHS KW - Pore formation KW - Surface structures KW - Reaction gases KW - Amorphous layer Y1 - 2019 UR - https://iopscience.iop.org/article/10.1088/2053-1591/ab01a1 U6 - https://doi.org/10.1088/2053-1591/ab01a1 SN - 2053-1591 VL - 6 IS - 5 ER - TY - GEN A1 - Shtin, Valentin A1 - Novikov, Valeriy A1 - Chekalkin, Timofey A1 - Gunther, Victor A1 - Marchenko, Ekaterina A1 - Choynzonov, Evgeniy A1 - Baik Kang, Seung A1 - Jong Chang, Moon A1 - Hoon Kang, Ji A1 - Obrosov, Aleksei T1 - Repair of Orbital Post-Traumatic Wall Defects by Custom-Made TiNi Mesh Endografts T2 - Journal of Functional Biomaterials N2 - Repairs of orbital post-traumatic and extensive malignant defects remain a major surgical challenge, in view of follow-up outcomes. Incorrect surgical management of injured facial structures results in cosmetic, ophthalmic, and social aftereffects. A custom-made knitted TiNi-based mesh (KTNM) endograft was employed to overcome post-surgical complications and post-resected lesions of the orbital area. Preoperative high-resolution computed tomography (CT) imaging and CAD modelling were used to design the customized KTNM in each case. Twenty-five patients underwent surgery utilizing the suggested technique, from 2014 to 2019. In all documented cases, resolution of the ophthalmic malfunction was noted in the early period. Follow-up observation evidenced no relapsed enophthalmos, hypoglobus, or diplopia as late complications. The findings emanating from our clinical observations allow us to claim that the KTNM indicated a high level of biocompatibility. It is simply modified intraoperatively to attach any desired shape/size for implantation and can also be screw-fixed, providing a good supporting ability. The KTNM precisely renders orbitozygomatic outlines and orbital floor, thus recovering the anatomical structure, and is regarded as an attractive alternative to Ti-based meshes and plates. Additionally, we report one of the studied cases, where good functional and cosmetic outcomes have been achieved. KW - diplopia KW - enophthalmos KW - orbital defect repair KW - TiNi mesh Y1 - 2019 UR - https://www.mdpi.com/2079-4983/10/3/27 U6 - https://doi.org/10.3390/jfb10030027 SN - 2079-4983 VL - 10 IS - 3 ER - TY - GEN A1 - Obrosov, Aleksei A1 - Yasenchuk, Yuri A1 - Marchenko, Ekaterina A1 - Gunther, Victor A1 - Radkevich, Andrey A1 - Kokorev, Oleg A1 - Gunther, Sergey A1 - Baigonakova, Gulsharat A1 - Hodorenko, Valentina A1 - Chekalkin, Timofey A1 - Kang, Ji-hoon A1 - Weiß, Sabine T1 - Biocompatibility and Clinical Application of Porous TiNi Alloys Made by Self-Propagating High-Temperature Synthesis (SHS) T2 - Materials N2 - 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. KW - porous SHS TiNi KW - biocompatibility KW - rheological similarity KW - corrosion resistance KW - bone substitution Y1 - 2019 UR - https://www.mdpi.com/1996-1944/12/15/2405/htm#B2-materials-12-02405 U6 - https://doi.org/10.3390/ma12152405 SN - 1996-1944 VL - 12 IS - 15 ER - TY - GEN A1 - Marchenko, Ekaterina A1 - Yasenchuk, Yuri A1 - Gunther, Sergey A1 - Baigonakova, Gulsharat A1 - Gunther, Victor A1 - Chekalkin, Timofey A1 - Weiß, Sabine A1 - Obrosov, Aleksei A1 - Dubovikov, Kirill T1 - Structural-phase surface composition of porous TiNi produced by SHS T2 - Materials Research Express N2 - The study aimed to characterize the structural-phase composition of the porous SHS TiNi surface explored by the GIXRD method. The surface layers at a depth of up to 100 nm mainly consist of amorphous nanocrystalline intermetallic oxycarbonitrides Ti₄Ni₂(O,N,C) with nonmetallic inclusions of different structural variants and routes of origin. Fine-porous alloys were synthesized at ignition temperatures of 450-480 °C. A distinct feature of the surface of crystalline phases therein was shown to be a low degree of crystallinity (up to 40%) and presence of multifarious glass and cermet phases evident as NiSi₂, NaAlSiO (SO₄), SiO₂, MgSi₂, and CaCO₃. Conversely, large-pore alloys ignited at temperatures of 280-330 °C have a higher degree of crystallinity (up to 70%). An individually selected GIXRD technique and precision structural phase analysis are capable to determine a set of other superficial nonmetallic and cermet phases reported as CaTiO₃, Si (P2O₇), CaSiO₃, MgAl₂O₄, TiNiAl, as well as the Ti₃SiC₂MAX phase. Y1 - 2019 UR - https://iopscience.iop.org/article/10.1088/2053-1591/ab4e32/pdf U6 - https://doi.org/10.1088/2053-1591/ab4e32 SN - 2053-1591 VL - 6 IS - 11 ER - TY - GEN A1 - Fellah, Mamoun A1 - Hezil, Naouel A1 - Touhami, Mohamed Zine A1 - Samad, Mohammed Abdul A1 - Obrosov, Aleksei A1 - Bokov, Dmitry O. A1 - Marchenko, Ekaterina A1 - Montagne, Alex A1 - Iost, Alain A1 - Alhussein, Akram T1 - Structural, tribological and antibacterial properties of (α + β) based ti-alloys for biomedical applications T2 - Journal of Materials Research and Technology N2 - Implant-related follow up complications resulting from poor implant integration, delamination, chipping, mechanical instability, inflammation or graft-vs-host reaction may lead to low patient tolerance, prolonged care and sometimes leading to a second surgery. Hence, there is an urgent need for developing biomaterials which will help to overcome the above compatibility problems. Ti based alloys have been widely used for biomedical applications, due to their excellent properties, such as low modulus, high biocompatibility and high corrosion resistance. In order to further improve the physical, mechanical and tribological properties of these alloys, microstructural modification is often required. Hence, this study aims to develop and evaluate the structural and tribological behavior of Hot Isostatic Pressed (HIPed) and sintered Ti-6Al-7Nb samples containing niobium, which is less toxic and less expensive as compared to the usual alloying element, vanadium (Ti-6Al-4 V). The Ti-6Al-7Nb alloys were fabricated by using nanoparticle powders milled for different durations (2, 6, 12 and 18 h) to evaluate the effect of milling time on the morphological and structural properties. Friction and wear tests were carried out on the (HIPed) and finally sintered Ti-6Al-7Nb alloy samples, to evaluate their tribological properties under different applied loads (2, 8 and 16 N), with an alumina α-Al2O3 ball as a counter face using an oscillating tribometer. The physical characterization of the nanopowders formed using different milling times indicated that the particle and crystallite size continually decreased with increasing milling time, while the microstrain increased. It is observed that the friction coefficient and wear rate for the samples prepared by powders milled for 18 h and tested under 2 N were lowest with values of 0.25 and 1.51 × 10−2 μm3∙N-1 μm-1, respectively compared to other milled samples. This improvement in tribological properties is attributed to the grain refinement at high milling times. The antibacterial evaluation of the fabricated alloys showed an improvement in antibacterial performance of the samples milled at 18 h compared to the other milling times. KW - Mechanical properties KW - Hot Isostatic Pressure KW - Ti-6Al-7Nb KW - Powder metallurgy KW - Milling time KW - Physical characterization KW - biomaterials KW - microstructure Y1 - 2020 UR - https://www.sciencedirect.com/science/article/pii/S2238785420318421 U6 - https://doi.org/10.1016/j.jmrt.2020.09.118 SN - 2238-7854 VL - 9 IS - 6 SP - 14061 EP - 14074 ER - TY - GEN A1 - Baigonakova, Gulsharat A1 - Marchenko, Ekaterina A1 - Chekalkin, Timofey A1 - Kang, Ji-hoon A1 - Weiß, Sabine A1 - Obrosov, Aleksei T1 - Influence of Silver Addition on Structure, Martensite Transformations and Mechanical Properties of TiNi–Ag Alloy Wires for Biomedical Application T2 - Materials N2 - 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. KW - shape memory alloy KW - silver KW - doping KW - mechanical properties KW - nanostructured material KW - wire Y1 - 2020 UR - https://www.mdpi.com/1996-1944/13/21/4721 U6 - https://doi.org/10.3390/ma13214721 SN - 1996-1944 VL - 13 IS - 21 ER - TY - GEN A1 - Kokorev, Oleg A1 - Chekalkin, Timofey A1 - Marchenko, Ekaterina A1 - Yasenchuk, Yuri A1 - Gunther, Sergey A1 - Serebrov, Vladimir A1 - Chernyshova, Alena A1 - Obrosov, Aleksei A1 - Kang, Ji-hoon T1 - Exploring the role of surface modifications of TiNi-based alloys in evaluating in vitro cytocompatibility: a comparative study T2 - Surface Topography: Metrology and Properties N2 - The aim of this study was the comparative analysis of in vitro bio-testing of solid and porous TiNi samples with modified surfaces (intact, oxidated, and etched). Tests for cytocompatibility, hemolysis, and cytotoxicity (MTT) as well as visualization by confocal and scanning electron microscopy have shown that the chemically modified samples are the most cytocompatible. The intact and etched samples did not induce hemolysis greater than 2%, and thus they comply with the ISO 10993-4:2018 standard for hemolysis by blood-contacting biomaterials. Direct culture of etched samples with MCF-7 cells and human leukocytes showed low cytotoxicity. At the same time, the cytotoxicity of samples oxidated at 500 °C was significantly greater than that of the etched samples. Confocal and electron microscopy also confirmed the abovementioned quantitative data. The cells attached to the etched surface in numbers sufficient for them to be able to grow and proliferate on this substrate in vitro. These findings indicate that solid and porous TiNi alloy with surface modifications achieved by a cost-effective method is biotolerable and promising for clinical use and for tissue engineering. KW - biocompatibility KW - cytocompatibility KW - TiNi alloys KW - tissue engineering KW - surface modification Y1 - 2020 UR - https://iopscience.iop.org/article/10.1088/2051-672X/abc0f9/meta U6 - https://doi.org/10.1088/2051-672X/abc0f9 SN - 2051-672X VL - 8 IS - 4 ER - TY - GEN A1 - Yasenchuk, Yuri A1 - Marchenko, Ekaterina A1 - Baigonakova, Gulsharat A1 - Gunther, Sergey A1 - Kokorev, Oleg A1 - Gunther, Victor A1 - Chekalkin, Timofey A1 - Topolnitskiy, Evgeniy A1 - Obrosov, Aleksei A1 - Kang, Ji-hoon T1 - Study on tensile, bending, fatigue, and in-vivo behavior of porous SHS-TiNi alloy used as a bone substitute T2 - Biomedical Materials N2 - Intermetallic porous SHS–TiNi alloys exhibit tangled and specific stress-strain characteristics. The article aims to evaluate the findings emanated from experiments using standard and proprietary instruments. Fatigue testing under repeated complex loading was used to measure the total number of load cycles to failure of SHS-TiNi samples. 70% of the tested samples, 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 SEM and confocal laser scanning instruments. Microscopic studies showed that the entire surface of the sample is concealed with the miscellaneous strata resulted from the SHS process, which 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 and degradation, having a long operational life, often greater than 17 million cycles. It acknowledges the potential benefits of SHS–TiNi as a superior osteoplastic material and its high resistance to corrosion fatigue. KW - porous TiNi KW - self-propagating high-temperature synthesis KW - fatigue strength KW - corrosion fatigue KW - biocompatibility Y1 - 2021 UR - https://iopscience.iop.org/article/10.1088/1748-605X/aba327/meta U6 - https://doi.org/10.1088/1748-605X/aba327 SN - 1748-605X VL - 16 IS - 2 ER - TY - GEN A1 - Marchenko, Ekaterina A1 - Baigonakova, Gulsharat A1 - Dubovikov, Kirill A1 - Yasenchuk, Yuri A1 - Chekalkin, Timofey A1 - Obrosov, Aleksei T1 - Comparative study on the high-temperature oxidation resistance of porous and solid TiNi-based alloys T2 - Surface Topography: Metrology and Properties N2 - The present work aims to characterize the surface features of solid and porous (sintered and SHS) TiNi-based alloys subjected to oxidation at 1000 °C in static air in the context of their resistance to high-temperature atmospheric attack. Clear differences between the intact and oxidated surfaces indicate the complexity of a chemicothermal diffusion process evolving therein. Microscopic and XRD studies showed that the dominant superficial constituent in all oxidated samples is titanium dioxide in the rutile modification. The phase and structural properties of the surface layers suggest that porous sintered and solid alloys are most susceptible to high-temperature corrosion due to bare reactive surfaces, which negatively affects their overall biocompatibility. Surface morphology analysis revealed microporous and loose superficial layers having a thickness of 8–10 and 50–60 μm, respectively in the solid and sintered alloy. Also, these alloys showed a high content of leaching NiO and free Ni within the surface layer. Conversely, a thin (0.5–0.6 μm), dense, and multifarious layer of oxycarbonitrides Ti4Ni2(O,N,C) concealing the porous SHS-TiNi matrix inhibits the negative effect of high-temperature oxidation. KW - high-temperature oxidation KW - TiNi alloys KW - rutile KW - oxycarbonitrides KW - diffusion Y1 - 2021 UR - https://iopscience.iop.org/article/10.1088/2051-672X/abf324/meta U6 - https://doi.org/https://doi.org/10.1088/2051-672X/abf324 SN - 2051-672X VL - 9 IS - 2 ER - TY - GEN A1 - Topolnitskiy, Evgeniy A1 - Chekalkin, Timofey A1 - Marchenko, Ekaterina A1 - Yasenchuk, Yuri A1 - Kang, Seung-Baik A1 - Kang, Ji-Hoon A1 - Obrosov, Aleksei T1 - Evaluation of Clinical Performance of TiNi-Based Implants Used in Chest Wall Repair after Resection for Malignant Tumors T2 - Journal of Functional Biomaterials N2 - In this study, we assessed the outcomes after surgical treatment of thoracic post-excision defects in 15 patients, using TiNi knitted surgical meshes and customized artificial TiNi-based ribs. Methods: Eight patients were diagnosed with advanced non-small cell lung cancer (NSCLC) invading the chest wall, of which five patients were T3N0M0, two were T3N1M0, and one was T3N2M0. Squamous cell carcinoma was identified in three of these patients and adenocarcinoma in five. In two cases, chest wall resection and repair were performed for metastases of kidney cancer after radical nephrectomy. Three-dimensional CT reconstruction and X-ray scans were used to plan the surgery and customize the reinforcing TiNi-based implants. All patients received TiNi-based devices and were prospectively followed for a few years. Results: So far, there have been no lethal outcomes, and all implanted devices were consistent in follow-up examinations. Immediate complications were noted in three cases (ejection of air through the pleural drains, paroxysm of atrial fibrillation, and pleuritis), which were conservatively managed. In the long term, no complications, aftereffects, or instability of the thoracic cage were observed. Conclusion: TiNi-based devices used for extensive thoracic lesion repair in this context are promising and reliable biomaterials that demonstrate good functional, clinical, and cosmetic outcomes. KW - non-small cell lung cancer (NSCLC) KW - thoracic lesion KW - chest wall reconstruction KW - TiNi artificial rib KW - TiNi mesh implant Y1 - 2021 UR - https://www.mdpi.com/2079-4983/12/4/60/htm U6 - https://doi.org/10.3390/jfb12040060 SN - 2079-4983 VL - 12 IS - 4 ER - TY - GEN A1 - Hezil, Naouel A1 - Aissani, Linda A1 - Fellah, Mamoun A1 - Samad, Mohammed Abdul A1 - Obrosov, Aleksei A1 - Chekalkin, Timofey A1 - Marchenko, Ekaterina T1 - Structural, and tribological properties of nanostructured α + β type titanium alloys for total hip T2 - Journal of Materials Research and Technology N2 - Titanium alloys are in demand for various biomedical applications and the most popular among them being, Ti–6Al–4V. Hence, in this study, Ti–6Al–7Nb are fabricated through the route of mechanical milling using different sintering temperatures. X-ray diffraction and hardness tests were conducted to characterize the developed sams to evaluate the effect of sintering temperatures on the structural and mechanical properties. It is observed that the sams sintered at a temperature of 1250 °C had the smallest crystallite and pore size, with enhanced relative density and mechanical properties. Tribological tests were conducted at varying normal loads to characterize the wear and frictional behaviour and showed that the sams sintered at 1250 °C presented the lowest friction coefficient and wear rate. KW - Ti–6Al–7Nb KW - Ti-alloys KW - Wear resistance KW - Sintering KW - Biomedical applications Y1 - 2022 UR - https://www.sciencedirect.com/science/article/pii/S2238785422009036#! U6 - https://doi.org/10.1016/j.jmrt.2022.06.042 SN - 2238-7854 IS - 19 SP - 3568 EP - 3578 ER - TY - GEN A1 - Marchenko, Ekaterina A1 - Yasenchuk, Yuri A1 - Klopotov, Anatoliy A1 - Ustinov, Artem A1 - Abzaev, Yuri A1 - Vetrova, Anna A1 - Chekalkin, Timofey A1 - Obrosov, Aleksei T1 - Study of macroplastic flow in surface layers of porous SHS-TiNi by digital image correlation T2 - ISSS Journal of Micro and Smart Systems N2 - In this work, we studied the evolution and features of localized strain fields in porous SHS-TiNi samples. Using the Vic-3D optical system and spayed speckle patterns, a localized plastic flow on the surface of porous plates of 0.85 mm and 2.7 mm thick loaded up to fracture in a quasi-static mode was traced and characterized. As seen, a 0.85 mm thick specimen indicated two strain-hardening distinctive parts in the stress-strain curve. Moreover, regions of localized strain are found that be wider than that of a 2.7 mm thick sample. It can be argued that by combining speckle patterns and quasi-static tension, one can effectively explore and predict the deformation behavior of a designing bone substitute made of porous SHS-TiNi. KW - Localized plastic flow KW - Porous SHS-TiNi KW - Digital image correlation KW - Speckle patterns Y1 - 2022 U6 - https://doi.org/10.1007/s41683-022-00104-w SN - 2509-7997 VL - 11 IS - 2 SP - 343 EP - 347 ER -