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The increasing incidence of trauma in medicine brings with it new demands on the materials used for the surgical treatment of bone fractures. Titanium, its alloys, and steel are used worldwide in the treatment of skeletal injuries. These metallic materials, although inert, are often removed after the injured bone has healed. The second-stage procedure-the removal of the plates and screws-can overwhelm patients and overload healthcare systems. The development of suitable absorbable metallic materials would help us to overcome these issues. In this experimental study, we analyzed an extruded Zn-0.8Mg-0.2Sr (wt.%) alloy on a rabbit model. From this alloy we developed screws which were implanted into the rabbit tibia. After 120, 240, and 360 days, we tested the toxicity at the site of implantation and also within the vital organs: the liver, kidneys, and brain. The results were compared with a control group, implanted with a Ti-based screw and sacrificed after 360 days. The samples were analyzed using X-ray, micro-CT, and a scanning electron microscope. Chemical analysis revealed only small concentrations of zinc, strontium, and magnesium in the liver, kidneys, and brain. Histologically, the alloy was verified to possess very good biocompatibility after 360 days, without any signs of toxicity at the site of implantation. We did not observe raised levels of Sr, Zn, or Mg in any of the vital organs when compared with the Ti group at 360 days. The material was found to slowly degrade in vivo, forming solid corrosion products on its surface.
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Implantes Absorvíveis , Ligas , Teste de Materiais , Tíbia/metabolismo , Fraturas da Tíbia , Ligas/química , Ligas/farmacocinética , Ligas/farmacologia , Animais , Humanos , Magnésio/química , Magnésio/farmacocinética , Magnésio/farmacologia , Coelhos , Estrôncio/química , Estrôncio/farmacocinética , Estrôncio/farmacologia , Tíbia/patologia , Fraturas da Tíbia/metabolismo , Fraturas da Tíbia/cirurgia , Zinco/química , Zinco/farmacocinética , Zinco/farmacologiaRESUMO
Bone fractures and critical-size bone defects are significant public health issues, and clinical treatment outcomes are closely related to the intrinsic properties of the utilized implant materials. Zinc (Zn)-based biodegradable metals (BMs) have emerged as promising bioactive materials because of their exceptional biocompatibility, appropriate mechanical properties, and controllable biodegradation. This review summarizes the state of the art in terms of Zn-based metals for bone repair and regeneration, focusing on bridging the gap between biological mechanism and required bioactivity. The molecular mechanism underlying the release of Zn ions from Zn-based BMs in the improvement of bone repair and regeneration is elucidated. By integrating clinical considerations and the specific bioactivity required for implant materials, this review summarizes the current research status of Zn-based internal fixation materials for promoting fracture healing, Zn-based scaffolds for regenerating critical-size bone defects, and Zn-based barrier membranes for reconstituting alveolar bone defects. Considering the significant progress made in the research on Zn-based BMs for potential clinical applications, the challenges and promising research directions are proposed and discussed.
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In this study, advanced techniques such as atom probe tomography, atomic force microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy were used to determine the corrosion mechanism of the as-ECAPed Zn-0.8Mg-0.2Sr alloy. The influence of microstructural and surface features on the corrosion mechanism was investigated. Despite its significance, the surface composition before exposure is often neglected by the scientific community. The analyses revealed the formation of thin ZnO, MgO, and MgCO3 layers on the surface of the material before exposure. These layers participated in the formation of corrosion products, leading to the predominant occurrence of hydrozincite. In addition, the layers possessed different resistance to the environment, resulting in localized corrosion attacks. The segregation of Mg on the Zn grain boundaries with lower potential compared with the Zn-matrix was revealed by atom probe tomography and atomic force microscopy. The degradation process was initiated by the activity of micro-galvanic cells, specifically Zn - Mg2Zn11/SrZn13. This process led to the activity of the crevice corrosion mechanism and subsequent attack to a depth of 250 µm. The corrosion rate of the alloy determined by the weight loss method was 0.36 mm·a-1. Based on this detailed study, the degradation mechanism of the Zn-0.8Mg-0.2Sr alloy is proposed.
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In this study, the Zn-0.8Mg-0.28CaO wt.% composite was successfully prepared using different conditions of ball milling (rotations and time) followed by a direct extrusion process. These materials were characterized from the point of view of microstructure and compressive properties, and the correlation between those characteristics was found. Microstructures of individual materials possessed differences in grain size, where the grain size decreased with the intensified conditions (milling speed and time). However, the mutual relation between grain size and compressive strength was not linear. This was caused by the effect of other factors, such as texture, intermetallic phases, and pores. Material texture affects the mechanical properties by a different activity ratio between basal and pyramidal
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Zinc (Zn) alloys seem to be promising candidates for application in orthopaedic or cardiovascular medical implants. In this area, high standards are required regarding the biocompatibility as well as excellent mechanical and tailored degradation properties. In the presented study, a novel Zn-0.8Mg-0.2Sr (wt%) alloy has been fabricated by the combination of casting, homogenization annealing and extrusion at 200 °C. As a consequence of its fine-grained homogenous microstructure, the prepared material is characterized by an excellent combination of tensile yield strength, ultimate tensile strength and elongation corresponding to 244 MPa, 324 MPa and 20% respectively. The in vitro corrosion rates of the Zn-0.8Mg-0.2Sr alloy in the physiological solution and the simulated body fluid were 244 µm/a and 69.8 µm/a, respectively. Furthermore, an extract test revealed that Zn-0.8Mg-0.2Sr extracts diluted to 25% had no adverse effects towards L929 fibroblasts, TAg periosteal cells and Saos-2 osteoblasts. Moreover, the Zn-0.8Mg-0.2Sr surface showed effective inhibition of initial Streptococcus gordonii adhesion and biofilm formation. These results indicated the Zn-0.8Mg-0.2Sr alloy, which has superior mechanical properties, might be a promising candidate for materials used for load-bearing applications.
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Ligas , Zinco , Implantes Absorvíveis , Materiais Biocompatíveis , Corrosão , Teste de Materiais , Resistência à TraçãoRESUMO
A new severe plastic deformation technique, known as the complex shearing of extruded tube (CSET), was applied to a 3003 based model aluminium alloy. This technique, consisting of a combination of extrusion and two consecutive Equal Chanel Angular Pressing (ECAP) passes accompanied with concurrent torsional straining, is capable to produce a fine-grained tubular sample directly from a bulk metallic cylinder in one forming operation. In the present paper, the microstructural development of the alloy during partial processes of CSET was studied in detail using light microscopy, electron backscatter diffraction, and transmission electron microscopy. It was found that CSET technique refines the grain size down to 0.4 µm and, consequently, increases the microhardness from the initial value of 40 HV to the final value of 120 HV. The contributions of partial processes of CSET to the total strain were estimated.
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In this pilot study, we investigated the biocompatibility and degradation rate of an extruded Zn-0.8Mg-0.2Sr (wt.%) alloy on a rabbit model. An alloy screw was implanted into one of the tibiae of New Zealand White rabbits. After 120 days, the animals were euthanized. Evaluation included clinical assessment, microCT, histological examination of implants, analyses of the adjacent bone, and assessment of zinc, magnesium, and strontium in vital organs (liver, kidneys, brain). The bone sections with the implanted screw were examined via scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS). This method showed that the implant was covered by a thin layer of phosphate-based solid corrosion products with a thickness ranging between 4 and 5 µm. Only negligible changes of the implant volume and area were observed. The degradation was not connected with gas evolution. The screws were fibrointegrated, partially osseointegrated histologically. We observed no inflammatory reaction or bone resorption. Periosteal apposition and formation of new bone with a regular structure were frequently observed near the implant surface. The histological evaluation of the liver, kidneys, and brain showed no toxic changes. The levels of Zn, Mg, and Sr after 120 days in the liver, kidneys, and brain did not exceed the reference values for these elements. The alloy was safe, biocompatible, and well-tolerated.
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Zinc and its alloys belong to a group of biodegradable materials, which can be potentially used for the preparation of temporary orthopedic implants. The research of biodegradable zinc materials revealed a lot of limitations; however, the new processing approaches of those materials can enhance their properties, which are insufficient for now. In this study, the zinc composite with 8 wt.% of hydroxyapatite (Zn/HA8) prepared for the first time by extrusion process was characterized from the point of view of the structural, mechanical and corrosion properties. The extrusion process led to good integrity of the interfaces between the zinc and hydroxyapatite particles. Mechanical behavior confirmed the role of hydroxyapatite as a defect in the material structure, which led to a decrease of the Zn/HA8 mechanical properties by approximately 30% (compressive yield strength (CYS) = 154 MPa Zn, 113 MPa Zn/HA8). Despite that, the Zn/HA8 composite showed sufficient mechanical properties for cancellous bone replacement and reached the lower limit for cortical bone. Additionally, the presence of hydroxyapatite caused the preferential precipitation of hydroxyapatite (HA) from the solution and can lead to a significant enhancement of the tissue/implant interface interactions.
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The Zn-based alloys, alloyed with the elements of the 2nd group of the periodic table, are considered as potential biodegradable materials suitable for the fabrication of small orthopaedic implants or cardiovascular stents. Unfortunately, the as-cast Zn-based alloys do not fulfil the requirements for mechanical properties for such applications. Extrusion is a thermomechanical process which is very powerful for breaking the cast microstructure and enhancing mechanical characteristics of metallic materials. In this study, we focused on the influence of extrusion parameters, such as temperature and extrusion ratio, on microstructural and mechanical characteristics of a ZnMg0.8Ca0.2 (wt.%) alloy. The extrusion led to a significant grain refinement and the formation of a crystallographic texture. Extrusion temperature played a more significant role in the mean grain size compared to the extrusion ratio (ER). At lower extrusion temperatures, the texture was less intensive and the subsequent mechanical anisotropy was weaker. Constants for the prediction of the grain size based on the Zener-Hollomon parameter were obtained. Prediction of mechanical properties using the Hall-Petch relationship appeared to be difficult because of the dependence of the texture on the extrusion temperature. Extrusion at the temperatures of 200 °C (ER = 25:1) and 150 °C (ER = 11:1) led to mechanical performance fulfilling the requirements for implantology.
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Ligas , Materiais Biocompatíveis , Corrosão , Stents , TemperaturaRESUMO
Zinc-based alloys represent one of the most highly developed areas regarding biodegradable materials. Despite this, some general deficiencies such as cytotoxicity and poor mechanical properties (especially elongation), are not properly solved. In this work, a Zn-5Mg (5 wt.% Mg) composite material with tailored mechanical and superior corrosion properties is prepared by powder metallurgy techniques. Pure Zn and Mg are mixed and subsequently compacted by extrusion at 200 °C and an extrusion ratio of 10. The final product possesses appropriate mechanical properties (tensile yield strength = 148 MPa, ultimate tensile strength = 183 MPa, and elongation = 16%) and decreased by four times the release of Zn in the initial stage of degradation compared to pure Zn, which can highly decrease cytotoxicity effects and therefore positively affect the initial stage of the healing process.