Zinc Alloy Research Articles

Study on the Enhanced Degradable Rate of the Zn-0.4Li Alloys as Biodegradable Implants by Anodization.

Biodegradable Zn-0.4Li alloys have been considered as medical implants due to their excellent mechanical properties and desirable biocompatibility. In this work, anodization was applied to modified corrosion resistance of the Zn-0.4Li alloy by forming a uniform and neat flower-like nanowire coating on the surface. After anodization for 7 min, the anodized Zn-0.4Li alloy had a yield strength of 253.6 MPa, ultimate tensile strength of 389.5 MPa, and elongation at a break of 66.0%. The corrosion rate of the Zn-0.4Li-7 min sample reached 0.5741 mm/y in the SBF, which was almost 18 times higher than that of the Zn-0.4Li alloy. The anodized Zn-0.4Li alloy exhibited higher antibacterial properties than that of the Zn-0.4Li alloy against Escherichia coli and Staphylococcus aureus. These results suggested that anodization may be an effective method to modulate the corrosion behavior of zinc alloys, which can be applied in the surface modification of biodegradable implants.

Developing high elongation of Ca-containing Zn alloys with superior osteogenic and antibacterial properties

The development of high-strength zinc (Zn) alloys significantly contributes to the field of orthopedics by enhancing their osteogenic properties. Calcium (Ca) is pivotal for bone composition; however, its incorporation into the Zn matrix often hampers elongation due to the formation of large-sized CaZn13 phases. In this study, two Zn alloys with different Ca contents were prepared, and their microstructures, mechanical properties, corrosion behavior and biocompatibility were investigated. Results indicate that the Zn alloy with high Ca content exhibits large-sized and high-volume-fraction CaZn13 phases, which do not significantly change during equal channel angular pressing (ECAP). The grain sizes of ECAPed Zn alloys decreased from 36.75 μm and 35.81 μm of as-cast state to 4.32 μm and 1.71 μm, respectively. Refined microstructures contributed to the improvement of mechanical properties of Zn alloys, which have elongation over 15 % higher than that of all Zn-Mg-Ca alloys reported so far. The high elongation of Zn alloys originates from the inhibition of the propagation of microcracks which generated from the Zn/CaZn13 interphase. Moreover, the formation of large-sized CaZn13 phases leads to the severe local corrosion through enhancing galvanic effect, finally increasing corrosion rate. During degradation, the release of metallic ions, such as Zn2+, Mg2+, and Ca2+, are beneficial to the cell viability and osteogenic properties. And the accelerated release of Zn2+ plays a role in antibacterial performance. These results are very helpful for promoting the application of biodegradable Zn alloys in the field of orthopedics.

Mechanical Properties, Microstructure, Degradation Behavior, and Biocompatibility of Zn-0.5Ti-0.5Fe and Zn-0.5Ti-0.5Mg Guided Bone Regeneration Barrier Membranes Prepared Using a Powder Metallurgy Method.

Pure zinc exhibits low mechanical properties, making it unsuitable for use in guided bone regeneration (GBR) membranes. The present study focused on the preparation of Zn alloy GBR films using powder metallurgy, resulting in Zn-0.5Ti-0.5Fe and Zn-0.5Ti-0.5Mg alloy GBR films. The tensile strength of the pure Zn GBR film measured 85.9 MPa, while an elongation at break was 13.5%. In contrast, Zn-0.5Ti-0.5Fe and Zn-0.5Ti-0.5Mg alloy GBR films demonstrated significantly higher tensile strengths of 145.3 and 164.4 MPa, respectively, whereas elongations at break were 30.2% and 19.3%. The addition of Ti, Fe, and Mg substantially enhanced the mechanical properties of the zinc alloys. Corrosion analysis revealed that Zn-0.5Ti-0.5Fe and Zn-0.5Ti-0.5Mg alloy GBR membranes exhibited corrosion potentials of -1.298 and -1.316 V, respectively, with corresponding corrosion current densities of 12.11 and 13.32 μA/cm2. These values were translated to corrosion rates of 0.181 and 0.199 mm/year, indicating faster corrosion rates compared to pure Zn GBR membranes, which displayed a corrosion rate of 0.108 mm/year. Notably, both Zn-based alloy GBR membranes demonstrated excellent cytocompatibility, with a cytotoxicity rating of 0-1 in 25% leachate. Additionally, these membranes exhibited favorable osteogenic ability, as evidenced by the quantitative bone volume/tissue volume ratios (BV/TV) of new bone formation, which reached 30.3 ± 1.4% and 65.5 ± 1.8% for the Zn-0.5Ti-0.5Fe and Zn-0.5Ti-0.5Mg alloy GBR membranes, respectively, after 12 weeks of implantation. These results highlighted the significant potential for facilitating new bone growth. The proposed Zn-0.5Ti-0.5Fe and Zn-0.5Ti-0.5Mg alloy GBR membranes showed promise as viable biodegradable materials for future clinical studies.

Microstructure, crystallographic texture and mechanical properties of the Zn–1%Mg–1%Fe alloy subjected to severe plastic deformation

The paper covers the production, analysis of the microstructure, crystallographic texture and deformation mechanisms of the ultrafine-grained (UFG) Zn–1%Mg–1%Fe zinc alloy demonstrating unique physical and mechanical properties compared to its coarse-crystalline analogs. The zinc alloy with improved mechanical properties was developed in two stages. At the first stage, based on the analysis of literature data, an alloy with the following chemical composition was cast: Zn–1%Mg–1%Fe. Then, the alloy was subjected to high-pressure torsion (HPT) to improve mechanical properties due to grain structure refinement and implementation of dynamic strain aging. The conducted mechanical tensile tests of the samples and assessment of the alloy hardness showed that HPT treatment leads to an increase in its tensile strength to 415MPa, an increase in hardness to 144HV, and an increase in ductility to 82%. The obtained mechanical characteristics demonstrate the suitability of using the developed alloy in medicine as some implants (stents) requiring high applied loads. To explain the reasons for the improvement of the mechanical properties of this alloy, the authors carried out comprehensive tests using microscopy and X-ray diffraction analysis. The microstructure analysis showed that during the formation of the ultrafine-grained structure, a phase transition is implemented according to the following scheme: Zneutectic + Mg2Zn11eutectic + FeZn13 → Znphase + Mg2Zn11phase + MgZn2particles + Znparticles. It was found that as a result of high pressure torsion in the main phases (Zn, Mg2Zn11), the grain structure is refined, the density of introduced defects increases, and a developed crystallographic texture consisting of basic, pyramidal, prismatic, and twin texture components is formed. The study showed that the resistance of pyramidal, prismatic and twin texture components at the initial stages of high-pressure torsion determines the level and anisotropy of the strength properties of this alloy. The relationship between the discovered structural features of the produced alloy and its unique mechanical properties is discussed.

Preparation, Mechanical Properties, and Degradation Behavior of Zn-1Fe-xSr Alloys for Biomedical Applications.

As biodegradable materials, zinc (Zn) and zinc-based alloys have attracted wide attention owing to their great potential in biomedical applications. However, the poor strength of pure Zn and binary Zn alloys limits their wide application. In this work, a stir casting method was used to prepare the Zn-1Fe-xSr (x = 0.5, 1, 1.5, 2 wt.%) ternary alloys, and the phase composition, microstructure, tensile properties, hardness, and degradation behavior were studied. The results indicated that the SrZn13 phase was generated in the Zn matrix when the Sr element was added, and the grain size of Zn-1Fe-xSr alloy decreased with the increase in Sr content. The ultimate tensile strength (UTS) and Brinell hardness increased with the increase in Sr content. The UTS and hardness of Zn-1Fe-2Sr alloy were 141.65 MPa and 87.69 HBW, which were 55.7% and 58.4% higher than those of Zn-1Fe alloy, respectively. As the Sr content increased, the corrosion current density of Zn-1Fe-xSr alloy increased, and the charge transfer resistance decreased significantly. Zn-1Fe-2Sr alloy had a degradation rate of 0.157 mg·cm-2·d-1, which was 118.1% higher than the degradation rate of Zn-1Fe alloy. Moreover, the degradation rate of Zn-1Fe-xSr alloy decreased significantly with the increase in immersion time.

Boosting Suzuki coupling reaction via pore expanding and palladium–zinc alloying

A palladium–zinc alloy nanoparticles decorated nitrogen-doped porous carbon catalyst (PdZn30–NC) was synthesized and utilized for Suzuki coupling reaction. The alloying palladium (Pd) with zinc (Zn) and pore expanding are realized simultaneously. Density functional theory (DFT) calculations and experimental studies reveal that the alloying Pd with Zn can lower the energy barrier in Suzuki coupling reaction. Nitrogen adsorption–desorption measurements uncover that pore expansion caused by the zinc nitrate hexahydrate assisted calcination gives rise to the multiplication of mesopore with a pore diameter of 6 nm, which facilitates mass transfer during the reaction. As a result, the alloying Pd with Zn and pore expanding together endow PdZn30–NC with excellent catalytic activity. PdZn30–NC demonstrates exceptional catalytic activity and stability in Suzuki coupling reaction. A high biphenyl yield of 97.7 % within 40 min and stable reusability of 93.3 % yield after five reuse cycles can be achieved. This work not only offers a viable method for Suzuki coupling reaction, but also provides insights for designing new catalysts toward Suzuki coupling reaction.

Effect of Surface Morphologies on the In Vitro and In Vivo Properties of Biomedical Metallic Materials.

Metallic biomaterials, including traditional bioinert materials (such as stainless steel, cobalt-chromium alloys, pure titanium, and titanium alloys), novel biodegradable metals (such as pure magnesium and magnesium alloys, pure zinc and zinc alloys, and pure iron and iron alloys), and biomedical metallic glasses, have been widely used and studied as various biomedical implants and devices. Many scientists and researchers have investigated their superior biomechanical properties, corrosion behavior, and biocompatibility. However, their surface characteristics are of extreme importance due to continuing interactions between the surface/interface of an implanted metallic biomaterial and the surrounding physiological environment. Surface morphologies on these metallic biomaterials can modulate their in vitro and in vivo biological responses. In this review, we have summarized and investigated the effect of various surface morphologies on the corrosion behavior, cellular response, antibacterial activity, and osteogenesis of biomedical metallic materials. In addition, future research directions and challenges of surface morphologies on biomedical metallic materials have been elaborated. This review can lay a theoretical and practical foundation for further research and development on biomedical metallic materials.

Synergistic release of copper and lithium components in biodegradable zinc alloy for osteoimmunomodulation

Synergistic release of copper and lithium components in biodegradable zinc alloy for osteoimmunomodulation

Uniformly dispersed zinc-tin alloy as high-performance anode for aqueous zinc ion batteries

Uncontrolled dendrite and side reactions of aqueous zinc ion batteries (AZIBs) hinder their commercial application. To overcome these obstacles, a novel zinc alloy anode for multifunctional AZIBs was designed by incorporating metal elements into the zinc anode. The metal elements are intended to improve the overall electrochemical performance of the battery by solving the zinc anode problem in an “incorporation” manner. In this study, the effect of Sn-induced surface structure reconstruction on the diffusion and deposition behavior of Zn2+ was investigated using binary zinc alloy (Zn@Sn) as a zinc anode. The zinc anode with Zn (002) crystal plane as the preferred crystal plane was able to inhibit the disordered growth of zinc dendrites, and the introduction of Sn elements enhanced the anti-hydrogen evolution reaction ability of the zinc anode. At a current density of 1.2 mA cm–2, the Zn@Sn symmetric cell was able to maintain stable operation for 1000 h, demonstrating a more prominent deposition/stripping stability. This work provides a promising strategy and new insights into the design of electrolyte-anode interfacial protection.

Research Progress on Laser Powder Bed Fusion Additive Manufacturing of Zinc Alloys.

Zinc, along with magnesium and iron, is considered one of the most promising biodegradable metals. Compared with magnesium and iron, pure Zn exhibits poor mechanical properties, despite its mild biological corrosion behavior and beneficial biocompatibility. Laser powder bed fusion (LPBF), unlike traditional manufacturing techniques, has the capability to rapidly manufacture near-net-shape components. At present, although the combination of LPBF and Zn has made great progress, it is still in its infancy. Element loss and porosity are common processing problems for LPBF Zn, mainly due to evaporation during melting under a high-energy beam. The formation quality and properties of the final material are closely related to the alloy composition, design and processing. This work reviews the state of research and future perspective on LPBF zinc from comprehensive assessments such as powder characteristics, alloy composition, processing, formation quality, microstructure, and properties. The effects of powder characteristics, process parameters and evaporation on formation quality are introduced. The mechanical, corrosion, and biocompatibility properties of LPBF Zn and their test methodologies are introduced. The effects of microstructure on mechanical properties and corrosion properties are analyzed in detail. The practical medical application of Zn is introduced. Finally, current research status is summarized together with suggested directions for advancing knowledge about LPBF Zn.

Corrosion behavior, antibacterial properties and in vitro and in vivo biocompatibility of biodegradable Zn-5Cu-xMg alloy for bone-implant applications

Reasonable optimization of degradation rate, antibacterial performance and biocompatibility is crucial for the development of biodegradable zinc alloy medical implant devices with antibacterial properties. In this study, various amounts of Mg elements were incorporated into Zn5Cu alloy to modulate the degradation rate, antibacterial properties and biocompatibility. The effects of Mg contents on the microstructure, corrosion behavior, antibacterial properties and biocompatibility of Zn-5Cu-xMg alloy were extensively investigated. The results revealed that with an increase of Mg content, the amount of Mg2Zn11 phase increased and its galvanic effect with the Zn matrix was enhanced, which accelerated the corrosion process and led to higher corrosion rate and high degradation rate of the alloy. Additionally, there was an increased release of Mg2+ and Zn2+ ions from the alloy which imparted excellent resistance against Escherichia coli and Staphylococcus aureus bacteria and improved biocompatibility, subcutaneous antibacterial and immune microenvironment regulation properties. Zn-5Cu-2 Mg exhibited superior antibacterial ability, cell compatibility, proliferation effect, subcutaneous antibacterial and immune microenvironment regulation performances, which can work as a promising candidate of biodegradable antibacterial medical implants.

Optimization of mechanical, corrosion properties and cytotoxicity of biodegradable Zn-Mn alloys by synergy of high-pressure solidification and cold rolling process

Zinc (Zn) and Zn-based alloys are biodegradable materials, that have recently gained significant research attention due to their moderate degradation rate and good biocompatibility. However, their clinical applications are limited by their inferior mechanical properties. In this study, Zn-0.5Mn, Zn-1.0Mn, and Zn-1.5Mn (wt%) alloys were prepared via high-pressure solidification (HPS) and cold rolling (CR) procedures. Further, the microstructure, mechanical properties, corrosion behavior, and in-vitro cytotoxicity of these Zn-Mn alloys were systematically investigated. The results revealed that their yield strength (σys) and ultimate tensile strength (σUTS) enhanced significantly after synergy of HPS-CR treatment compared to CR alone. Notably, among these alloys, the Zn-1.5Mn alloy exhibited the highest σys and σUTS after HPS-CR, at 296.4±5.4 MPa and 322.6±3.5 MPa, respectively. The primary reason for this phenomenon is attributed to the combination of grain refinement and solid solution strengthening performance. Furthermore, these newly designed biodegradable Zn-Mn alloys exhibited appropriate in-vitro degradation rates and acceptable in vitro cytocompatibility when tested in Hanks' solution.

(Invited) Development of Mildly Acidic Aqueous Zinc Batteries: Anode, Cathode, and Electrolyte

Aqueous zinc batteries use earth abundant materials and has stable supply chains, making them one of the promising battery technologies for grid-scale energy storage applications. However, the limited cycle life because of the dendrite formation of zinc anodes, poor reversibility of cathodes, and consumption of electrolyte has greatly hampered its practical application. Recently, extensive research effort has been made on the development of rechargeable alkaline batteries and mildly acidic zinc ion batteries. Novel structured zinc anodes, intercalation cathode materials and new electrolytes have been developed to improve the performance. Here, we would like to present our effort towards aqueous zinc batteries under practical conditions. Zinc alloy anodes, organic cathode materials, and the use of new binders and electrolyte additives will be discussed.

A Critical Review of Biodegradable Zinc Alloys toward Clinical Applications.

Biodegradable zinc (Zn) alloys stand out as promising contenders for biomedical applications due to their favorable mechanical properties and appropriate degradation rates, offering the potential to mitigate the risks and expenses associated with secondary surgeries. While current research predominantly centers on the in vitro examination of Zn alloys, notable disparities often emerge between in vivo and in vitro findings. Consequently, conducting in vivo investigations on Zn alloys holds paramount significance in advancing their clinical application. Different element compositions and processing methods decide the mechanical properties and biological performance of Zn alloys, thus affecting their suitability for specific medical applications. This paper presents a comprehensive overview of recent strides in the development of biodegradable Zn alloys, with a focus on key aspects such as mechanical properties, toxicity, animal experiments, biological properties, and molecular mechanisms. By summarizing these advancements, the paper aims to broaden the scope of research directions and enhance the understanding of the clinical applications of biodegradable Zn alloys.

The effect of Silver addition and deformation parameters on mechanostructure, biodegradation, antimicrobial and mechanical properties of Zn-based biodegradable alloys.

Although low mechanical properties, Zinc (Zn) alloy systems with Copper (Cu) and Silver (Ag) as alloying elements have strong biocompatibility and biodegradability characteristics. This study examined the effects of rolling parameters and Ag alloying on the mechanical, biodegradable, and final structure of an alloy based on Zn. Comparing treated and untreated specimens, the addition of Ag led to a considerable improvement in both hardness and compressive strength. The produced alloys with varying amounts of Ag (between 1 and 4wt%) were cold rolled at 400-800r/min and friction coefficients between 0.3 and 0.5. The alloys' ultimate strength rose with an increase in rolling speed for Zn1Cu4Ag, and hardness and compressive strengths rose to 80HV and 470MPa, respectively. It was demonstrated that rolling force rose somewhat with Ag concentration but significantly increased with rolling speed and friction. E. Coli and S. aureus were used to assess the biodegradable alloys' antibacterial properties. For the Zn-1Cu-2Ag alloy, the inclusion of Ag resulted in a considerable (50%) rise in antibacterial activity that exceeded the effects seen in other alloy systems.

Influence of heat treatment on the microstructure evolution and corrosion performance of biodegradable Zn-Mg alloys

Zinc and zinc-based alloys have garnered increasing attention as biodegradable materials due to their excellent mechanical properties, lower degradation rates compared to magnesium, and favorable biocompatibility. This study investigates the impact of homogenization treatment on the microstructure and corrosion behavior of Zn-Mg alloys using scanning electron microscopy, X-ray diffraction, hardness testing, and accelerated corrosion immersion tests. The results reveal that homogenization treatment induces the fusion of eutectic cells within the alloys, causing significant morphological alternations in the eutectic structure and varying proportions of the Mg2Zn11 phase, These changes notably affect material properties. The raised content of Mg2Zn11 phase in the eutectic structure correlates with higher hardness but reduced corrosion resistance, whereas the reduced Mg2Zn11 phase content leads to enhanced corrosion resistance. Furthermore, in-situ corrosion observations demonstrate that corrosion initiates at the eutectic phase, with corrosion pits forming due to the ion release as corrosion progresses, leading to gradual enlargement of the corrosion pits. In summary, this study provides comprehensive insights into the microstructural changes in Zn-Mg alloys and their impact on corrosion resistance, offering valuable references for their engineering applications.

Evaluating the Biocompatibility of Zinc Alloys for the Development of Bioresorbable Cardiovascular Stents

Evaluating the Biocompatibility of Zinc Alloys for the Development of Bioresorbable Cardiovascular Stents

Quaternary Zinc Alloys with Magnesium, Calcium and Strontium after Hydrostatic Extrusion-Microstructure and Its Impact on Mechanical and Corrosion Properties.

The development of bioabsorbable implants from Zn alloys is one of the main interests in the new generation of biomaterials. The main drawbacks of Zn-based materials are their insufficient mechanical properties. In the presented studies, a quaternary alloy composed of zinc with magnesium (0.2-1 wt. %), calcium (0.1-0.5 wt. %) and strontium (0.05-0.5 wt. %) was prepared by gravity casting followed by hot extrusion and then by hydrostatic extrusion. Microstructural characterization using scanning electron microscopy (SEM) and X-ray diffraction (XRD) phase analysis was performed. The mechanical properties were examined, using static tensile tests. Corrosion properties were analyzed using immersion tests. Samples were immersed in Hanks' solution (temperature = 37 °C, pH = 7.4) for 14 days. All alloys were subjected after corrosion to SEM observations on the surface and cross-section. The corrosion rate was also calculated. The microstructure of the investigated quaternary alloy consists of the α-Zn grains and intermetallic phases Mg2Zn11, CaZn13 and SrZn13 with different grain sizes and distribution, which impacted both mechanical and corrosion properties. Thanks to the alloying by the addition of Mg, Ca, and Sr and plastic deformation using hydrostatic extrusion, outstanding mechanical properties were obtained along with improvement in uniformity of corrosion rate.

Research on the deformation behavior of pure zinc fabricated by forward extrusion and composite extrusion

Zinc and its alloys are biomedical biodegradable materials with broad application prospects. In this paper, commercially pure zinc bars were subjected to two different types of extrusion treatments, forward extrusion (FE) and composite extrusion (CE), at 120°C to study the changes in microstructure and mechanical properties. Compared to the virgin annealed state of pure zinc, the yield strength of CE decreased significantly from 73.67 MPa to 40.87 MPa, while the elongation of FE increased markedly from 9.23 % to 59 %. The anomalous phenomenon of decreasing strength and increasing ductility of extruded pure zinc is significantly different from that of extruded zinc and magnesium alloys. To investigate the reason for this anomaly, a detailed study of the microstructure evolution of pure zinc under three processing states was carried out using EBSD. Grain growth and texture weakening lead to a loss of strength, whereas the increase in ductility after extrusion is attributed to the activation of more slip systems.

Investigating the Anticancer Potential of Zinc and Magnesium Alloys: From Base Materials to Nanocoated Titanium Implants.

In this work, we show the in vitro anticancer potential of surgical wires, obtained from zinc (ZnMg0.004) or magnesium (MgCa0.7) alloys by spatial technology comprising casting, extrusion, and final drawing processes. We also present the selective anticancer effects of applied soluble multilayer nanocoatings of zinc and magnesium onto titanium surfaces using the pulse laser deposition method. In the latter, the titanium samples were produced via 3D printing using the selective laser melting method and coated with various combinations of zinc and magnesium layers. For cytotoxicity studies, human dental pulp-derived stem cells (hDPSCs) and human osteosarcoma SaOS-2 cell line were used as representatives of healthy and cancer cells. Cells were examined against the 0.3-3.0 cm2/mL material extract ratios obtained from experimental and steel surgical wires, the latter being the current clinical industry standard. The MgCa0.7 alloy wires were approx. 1.5 times more toxic to cancer cells at all examined extract ratios vs. the extracts from steel surgical wires that exhibited comparable toxicity towards healthy and cancer cells. The ZnMg0.004 alloy wires displayed increased toxicity towards cancer cells with decreasing extract ratios. This was also reflected in the increased anticancer effectiveness, calculated based on the viability ratio of healthy cells to cancer cells, from 1.1 to 4.0 times. Healthy cell viability remained at 80-100%, whereas cancer cell survival fluctuated at 20-75%, depending on the extract ratio. Furthermore, the culture of normal or cancer cells on the surface of Zn/Mg-coated titanium allowed us to select combinations of specific coating layers that yielded a comparable anticancer effectiveness to that observed with the experimental wires that ranged between 2 and 3. Overall, this work not only demonstrates the substantial anticancer properties of the studied wires but also indicates that similar anticancer effects can be replicated with appropriate nanocoatings on titanium samples. We believe that this work lays the groundwork for the future potential development of the category of new implants endowed with anticancer properties.