@misc{YasenchukGuntherMarchenkoetal., author = {Yasenchuk, Yuri and Gunther, Victor and Marchenko, Ekaterina and Chekalkin, Timofey and Baigonakova, Gulsharat and Hodorenko, Valentina and Gunther, Sergey and Kang, Ji-hoon and Weiß, Sabine and Obrosov, Aleksei}, title = {Formation of mineral phases in self-propagating high-temperature synthesis (SHS) of porous TiNi alloy}, series = {Materials Research Express}, volume = {6}, journal = {Materials Research Express}, number = {5}, issn = {2053-1591}, doi = {10.1088/2053-1591/ab01a1}, pages = {13}, abstract = {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.}, language = {en} } @misc{ShtinNovikovChekalkinetal., author = {Shtin, Valentin and Novikov, Valeriy and Chekalkin, Timofey and Gunther, Victor and Marchenko, Ekaterina and Choynzonov, Evgeniy and Baik Kang, Seung and Jong Chang, Moon and Hoon Kang, Ji and Obrosov, Aleksei}, title = {Repair of Orbital Post-Traumatic Wall Defects by Custom-Made TiNi Mesh Endografts}, series = {Journal of Functional Biomaterials}, volume = {10}, journal = {Journal of Functional Biomaterials}, number = {3}, issn = {2079-4983}, doi = {10.3390/jfb10030027}, pages = {9}, abstract = {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.}, language = {en} } @misc{ObrosovYasenchukMarchenkoetal., author = {Obrosov, Aleksei and Yasenchuk, Yuri and Marchenko, Ekaterina and Gunther, Victor and Radkevich, Andrey and Kokorev, Oleg and Gunther, Sergey and Baigonakova, Gulsharat and Hodorenko, Valentina and Chekalkin, Timofey and Kang, Ji-hoon and Weiß, Sabine}, title = {Biocompatibility and Clinical Application of Porous TiNi Alloys Made by Self-Propagating High-Temperature Synthesis (SHS)}, series = {Materials}, volume = {12}, journal = {Materials}, number = {15}, issn = {1996-1944}, doi = {10.3390/ma12152405}, pages = {25}, abstract = {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.}, language = {en} } @misc{MarchenkoYasenchukGuntheretal., author = {Marchenko, Ekaterina and Yasenchuk, Yuri and Gunther, Sergey and Baigonakova, Gulsharat and Gunther, Victor and Chekalkin, Timofey and Weiß, Sabine and Obrosov, Aleksei and Dubovikov, Kirill}, title = {Structural-phase surface composition of porous TiNi produced by SHS}, series = {Materials Research Express}, volume = {6}, journal = {Materials Research Express}, number = {11}, issn = {2053-1591}, doi = {10.1088/2053-1591/ab4e32}, pages = {12}, abstract = {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.}, language = {en} } @misc{FellahHezilTouhamietal., author = {Fellah, Mamoun and Hezil, Naouel and Touhami, Mohamed Zine and Samad, Mohammed Abdul and Obrosov, Aleksei and Bokov, Dmitry O. and Marchenko, Ekaterina and Montagne, Alex and Iost, Alain and Alhussein, Akram}, title = {Structural, tribological and antibacterial properties of (α + β) based ti-alloys for biomedical applications}, series = {Journal of Materials Research and Technology}, volume = {9}, journal = {Journal of Materials Research and Technology}, number = {6}, issn = {2238-7854}, doi = {10.1016/j.jmrt.2020.09.118}, pages = {14061 -- 14074}, abstract = {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.}, language = {en} } @misc{BaigonakovaMarchenkoChekalkinetal., author = {Baigonakova, Gulsharat and Marchenko, Ekaterina and Chekalkin, Timofey and Kang, Ji-hoon and Weiß, Sabine and Obrosov, Aleksei}, title = {Influence of Silver Addition on Structure, Martensite Transformations and Mechanical Properties of TiNi-Ag Alloy Wires for Biomedical Application}, series = {Materials}, volume = {13}, journal = {Materials}, number = {21}, issn = {1996-1944}, doi = {10.3390/ma13214721}, pages = {11}, abstract = {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.}, language = {en} } @misc{KokorevChekalkinMarchenkoetal., author = {Kokorev, Oleg and Chekalkin, Timofey and Marchenko, Ekaterina and Yasenchuk, Yuri and Gunther, Sergey and Serebrov, Vladimir and Chernyshova, Alena and Obrosov, Aleksei and Kang, Ji-hoon}, title = {Exploring the role of surface modifications of TiNi-based alloys in evaluating in vitro cytocompatibility: a comparative study}, series = {Surface Topography: Metrology and Properties}, volume = {8}, journal = {Surface Topography: Metrology and Properties}, number = {4}, issn = {2051-672X}, doi = {10.1088/2051-672X/abc0f9}, pages = {14}, abstract = {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.}, language = {en} } @misc{YasenchukMarchenkoBaigonakovaetal., author = {Yasenchuk, Yuri and Marchenko, Ekaterina and Baigonakova, Gulsharat and Gunther, Sergey and Kokorev, Oleg and Gunther, Victor and Chekalkin, Timofey and Topolnitskiy, Evgeniy and Obrosov, Aleksei and Kang, Ji-hoon}, title = {Study on tensile, bending, fatigue, and in-vivo behavior of porous SHS-TiNi alloy used as a bone substitute}, series = {Biomedical Materials}, volume = {16}, journal = {Biomedical Materials}, number = {2}, issn = {1748-605X}, doi = {10.1088/1748-605X/aba327}, pages = {14}, abstract = {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.}, language = {en} } @misc{MarchenkoBaigonakovaDubovikovetal., author = {Marchenko, Ekaterina and Baigonakova, Gulsharat and Dubovikov, Kirill and Yasenchuk, Yuri and Chekalkin, Timofey and Obrosov, Aleksei}, title = {Comparative study on the high-temperature oxidation resistance of porous and solid TiNi-based alloys}, series = {Surface Topography: Metrology and Properties}, volume = {9}, journal = {Surface Topography: Metrology and Properties}, number = {2}, issn = {2051-672X}, doi = {https://doi.org/10.1088/2051-672X/abf324}, abstract = {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.}, language = {en} } @misc{TopolnitskiyChekalkinMarchenkoetal., author = {Topolnitskiy, Evgeniy and Chekalkin, Timofey and Marchenko, Ekaterina and Yasenchuk, Yuri and Kang, Seung-Baik and Kang, Ji-Hoon and Obrosov, Aleksei}, title = {Evaluation of Clinical Performance of TiNi-Based Implants Used in Chest Wall Repair after Resection for Malignant Tumors}, series = {Journal of Functional Biomaterials}, volume = {12}, journal = {Journal of Functional Biomaterials}, number = {4}, issn = {2079-4983}, doi = {10.3390/jfb12040060}, pages = {11}, abstract = {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.}, language = {en} } @misc{HezilAissaniFellahetal., author = {Hezil, Naouel and Aissani, Linda and Fellah, Mamoun and Samad, Mohammed Abdul and Obrosov, Aleksei and Chekalkin, Timofey and Marchenko, Ekaterina}, title = {Structural, and tribological properties of nanostructured α + β type titanium alloys for total hip}, series = {Journal of Materials Research and Technology}, journal = {Journal of Materials Research and Technology}, number = {19}, issn = {2238-7854}, doi = {10.1016/j.jmrt.2022.06.042}, pages = {3568 -- 3578}, abstract = {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.}, language = {en} } @misc{MarchenkoYasenchukKlopotovetal., author = {Marchenko, Ekaterina and Yasenchuk, Yuri and Klopotov, Anatoliy and Ustinov, Artem and Abzaev, Yuri and Vetrova, Anna and Chekalkin, Timofey and Obrosov, Aleksei}, title = {Study of macroplastic flow in surface layers of porous SHS-TiNi by digital image correlation}, series = {ISSS Journal of Micro and Smart Systems}, volume = {11}, journal = {ISSS Journal of Micro and Smart Systems}, number = {2}, issn = {2509-7997}, doi = {10.1007/s41683-022-00104-w}, pages = {343 -- 347}, abstract = {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.}, language = {en} }