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.

Mimicking the mechanical properties of cortical bone with an additively manufactured biodegradable Zn-3Mg alloy.

Additively manufactured (AM) biodegradable zinc (Zn) alloys have recently emerged as promising porous bone-substituting materials, due to their moderate degradation rates, good biocompatibility, geometrically ordered microarchitectures, and bone-mimicking mechanical properties. While AM Zn alloy porous scaffolds mimicking the mechanical properties of trabecular bone have been previously reported, mimicking the mechanical properties of cortical bone remains a formidable challenge. To overcome this challenge, we developed the AM Zn-3Mg alloy. We used laser powder bed fusion to process Zn-3Mg and compared it with pure Zn. The AM Zn-3Mg alloy exhibited significantly refined grains and a unique microstructure with interlaced α-Zn/Mg2Zn11 phases. The compressive properties of the solid Zn-3Mg specimens greatly exceeded their tensile properties, with a compressive yield strength of up to 601 MPa and an ultimate strain of >60 %. We then designed and fabricated functionally graded porous structures with a solid core and achieved cortical bone-mimicking mechanical properties, including a compressive yield strength of >120 MPa and an elastic modulus of ≈20 GPa. The biodegradation rates of the Zn-3Mg specimens were lower than those of pure Zn and could be adjusted by tuning the AM process parameters. The Zn-3Mg specimens also exhibited improved biocompatibility as compared to pure Zn, including higher metabolic activity and enhanced osteogenic behavior of MC3T3 cells cultured with the extracts from the Zn-3Mg alloy specimens. Altogether, these results marked major progress in developing AM porous biodegradable metallic bone substitutes, which paved the way toward clinical adoption of Zn-based scaffolds for the treatment of load-bearing bony defects. STATEMENT OF SIGNIFICANCE: Our study presents a significant advancement in the realm of biodegradable metallic bone substitutes through the development of an additively manufactured Zn-3Mg alloy. This novel alloy showcases refined grains and a distinctive microstructure, enabling the fabrication of functionally graded porous structures with mechanical properties resembling cortical bone. The achieved compressive yield strength and elastic modulus signify a critical leap toward mimicking the mechanical behavior of load-bearing bone. Moreover, our findings reveal tunable biodegradation rates and enhanced biocompatibility compared to pure Zn, emphasizing the potential clinical utility of Zn-based scaffolds for treating load-bearing bony defects. This breakthrough opens doors for the wider adoption of zinc-based materials in regenerative orthopedics.

Lipid changes and molecular mechanism inducing cuproptosis in Cryptocaryon irritans after copper-zinc alloy exposure.

Cryptocaryons irritans is a ciliate parasite responsible for cryptocaryoniasis, leading to considerable economic losses in aquaculture. It is typically managed using a copper-zinc alloy (CZA), effectively diminishing C. irritans infection rates while ensuring the safety of aquatic organisms. Nevertheless, the precise mechanism underlying cuproptosis induced C. irritans mortality following exposure to CZA remains enigmatic. Therefore, this study delves into assessing the efficacy of CZA, investigate cuproptosis as a potential mechanism of CZA action against C. irritans, and determine the alterations in antioxidant enzymes, peroxidation, and lipid metabolism. The mRNA expression of dihydrolipoamide S-acetyltransferase was upregulated after 40 and 70 min, while aconitase 1 was implicated in cuproptosis following 70 min of CZA exposure. Furthermore, the relative mRNA levels of glutathione reductase experienced a significant increase after 40 and 70 min of CZA exposure. In contrast, the relative mRNA levels of glutathione S-transferase and phospholipid-hydroperoxide glutathione peroxidase were significantly decreased after 70 min, suggesting a disruption in antioxidant defense and an imbalance in copper ions. Lipidomics results also unveiled an elevation in glycerophospholipids metabolism and the involvement of the lipoic acid pathway, predominantly contributing to cuproptosis. In summary, exposure to CZA induces cuproptosis in C. irritans, impacts glutathione-related enzymes, and alters glycerophospholipids, consequently triggering lipid oxidation.

Biodegradable Zn-5Dy Alloy with Enhanced Osteo/Angio-Genic Activity and Osteointegration Effect via Regulation of SIRT4-Dependent Mitochondrial Function.

Zinc (Zn)-dysprosium (Dy) binary alloys are promising biodegradable bone fracture fixation implants owing to their attractive biodegradability and mechanical properties. However, their clinical application is a challenge for bone fracture healing, due to the lack of Zn-Dy alloys with tailored proper bio-mechanical and osteointegration properties for bone regeneration. A Zn-5Dy alloy with high strength and ductility and a degradation rate aligned with the bone remodeling cycle is developed. Here, mechanical stability is further confirmed, proving that Zn-5Dy alloy can resist aging in the degradation process, thus meeting the mechanical requirements of fracture fixation. In vitro cellular experiments reveal that the Zn-5Dy alloy enhances osteogenesis and angiogenesis by elevating SIRT4-mediated mitochondrial function. In vivo Micro-CT, SEM-EDS, and immunohistochemistry analyses further indicate good biosafety, suitable biodegradation rate, and great osteointegration of Zn-5Dy alloy during bone healing, which also depends on the upregulation of SIRT4-mediated mitochondrial events. Overall, the study is the first to report a Zn-5Dy alloy that exerts remarkable osteointegration properties and has a strong potential to promote bone healing. Furthermore, the results highlight the importance of mitochondrial modulation and shall guide the future development of mitochondria-targeting materials in enhancing bone fracture healing.

Corrosion-Resistive ZrO2 Barrier Films on Selected Zn-Based Alloys.

This work presents the enhanced corrosion resistance of newly developed two-layer composite coatings deposited on low-carbon steel: electrodeposited zinc alloy coatings (Zn-Ni with 10 wt.% Ni (ZN) or Zn-Co with 3 wt.% Co (ZC), respectively) and a top ZrO2 sol-gel layer. Surface morphology peculiarities and anti-corrosion characteristics were examined using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX), atomic force microscopy (AFM), water contact angle (WCA) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analyses, potentiodynamic polarization (PDP) curves, corrosion potential (Ecorr), polarization resistance (Rp) measurements (for a prolonged period of 25 days) and open-circuit potential (OCP). The results were compared with the corrosion peculiarities of usual zinc coating. The zirconia top coatings in both systems were amorphous and dense, possessing hydrophobic nature. The experimental data revealed an increased corrosion resistance and protective ability of the ZC system in comparison to that of ZN due to its smooth, homogeneous surface and the presence of poorly crystallized oxides (ZnO and Co3O4), both later playing the role of a barrier for corrosive agents.

Numerical Simulation of Dynamic Degradation and Fatigue Damage of Degradable Zinc Alloy Stents.

Current research on the fatigue properties of degradable zinc alloy stents has not yet considered the issue of the fatigue life changing with material properties during the dynamic degradation process. Therefore, in this paper, we established a fatigue damage algorithm to study the fatigue problem affected by the changing of material properties during the dynamic degradation process of the stent under the action of pulsating cyclic loading. Three models: the dynamic degradation model, the dynamic degradation model under pulsating cyclic loading, and the coupled model of fatigue damage and dynamic degradation, were developed to verify the effect of fatigue damage on stent life. The results show that fatigue damage leads to a deeper degree of inhomogeneous degradation of the stent, which affects the service life of the stent. Fatigue damage is a factor that cannot be ignored. Therefore, when studying the mechanical properties and lifetime of degradable stents, incorporating fatigue damage into the study can help more accurately assess the lifetime of the stents.

Corrosion Studies of Temperature-Resistant Zinc Alloy Sacrificial Anodes and Casing Pipe at Different Temperatures.

In order to solve the problem of external corrosion of deep well casing in oil and gas fields, a new type of high-temperature-resistant zinc alloy sacrificial anode material was used. The temperature and corrosion resistance of the new anode material and TP140 casing were investigated by simulating the high-temperature working conditions of a deep well in an oil field using high-temperature and high-pressure corrosion tests and electrochemical tests. The results showed that at 100-120 °C, the corrosion rate of TP140 protected by a sacrificial anode was only one-tenth of that under unprotected conditions, and the minimum corrosion rate of TP140 protected by a sacrificial anode at 100 °C was 0.0089 mm/a. The results of the dynamic potential polarization curve showed that the corresponding corrosion current density of TP140 first increased and then decreased with the increase in temperature. The self-corrosion potential in sacrificial anode materials first increased and then decreased with the increase in temperature, and the potential difference with TP140 gradually decreased.

Biocompatibility Assessment of Zinc Alloys as a New Potential Material for Bioabsorbable Implants for Osteosynthesis.

In the last several years, zinc and its alloys have come into focus as bioabsorbable materials by qualifying themselves with an excellent corrosion rate, mechanical properties, anti-bacterial effects. and considerable biocompatibility. In this study, the biocompatibility of zinc-silver alloys containing 3.3 wt% silver (ZnAg3) was assessed by evaluating their cell viability, the proliferation rate, and the cell toxicity. Two alloys were investigated in which one was phosphated and the other was non-phosphated. The alloys were tested on human osteoblasts (hOb), which are, to a large extent, responsible for bone formation and healing processes. The performance of the phosphated alloy did not differ significantly from the non-phosphated alloy. The results showed a promising biocompatibility with hOb for both alloys equally in all conducted assays, qualifying ZnAg3 for further investigations such as in vivo studies.

Evolution from Bioinert to Bioresorbable: In Vivo Comparative Study of Additively Manufactured Metal Bone Scaffolds.

Additively manufactured scaffolds offer significant potential for treating bone defects, owing to their porous, customizable architecture and functionalization capabilities. Although various biomaterials have been investigated, metals - the most successful orthopedic material - have yet to yield satisfactory results. Conventional bio-inert metals, such as titanium (Ti) and its alloys, are widely used for fixation devices and reconstructive implants, but their non-bioresorbable nature and the mechanical property mismatch with human bones limit their application as porous scaffolds for bone regeneration. Advancements in additive manufacturing have facilitated the use of bioresorbable metals, including magnesium (Mg), zinc (Zn), and their alloys, as porous scaffolds via Laser Powder Bed Fusion (L-PBF) technology. This in vivo study presents a comprehensive, side-by-side comparative analysis of the interactions between bone regeneration and additively manufactured bio-inert/bioresorbable metal scaffolds, as well as their therapeutic outcomes. The research offers an in-depth understanding of the metal scaffold-assisted bone healing process, illustrating that Mg and Zn scaffolds contribute to the bone healing process in distinct ways, but ultimately deliver superior therapeutic outcomes compared to Ti scaffolds. These findings suggest that bioresorbable metal scaffolds hold considerable promise for the clinical treatment of bone defects in the near future.

Microstructure and Texture Evolution of the Magnesium Alloy ZMX210 during Rolling and Annealing.

The processability during massive deformation of magnesium-wrought products is hampered by the low formability of magnesium alloys. The research results of recent years demonstrate that rare earth elements as alloying elements improve the properties of magnesium sheets, such as formability, strength and corrosion resistance. The substitution of rare earth elements by Ca in Mg-Zn-based alloys results in a similar texture evolution and mechanical behaviour as RE-containing alloys. This work is an approach to understanding the influence of Mn as an alloying element to increase the strength of a Mg-Zn-Ca alloy. For this aim, a Mg-Zn-Mn-Ca alloy is used to investigate how Mn affects the process parameters during rolling and the subsequent heat treatment. The microstructure, texture and mechanical properties of rolled sheets and heat treatment at different temperatures are compared. The outcome of casting and the thermo-mechanical treatment are used to discuss how to adapt the mechanical properties of magnesium alloy ZMX210. The alloy ZMX210 behaves very similarly to the ternary Mg-Zn-Ca alloys. The influence of the process parameter rolling temperature on the properties of the ZMX210 sheets was investigated. The rolling experiments show that the ZMX210 alloy has a relatively narrow process window.

[Research status and development of biodegradable zinc alloy as orthopedics implant].

Znic (Zn) alloys with good cytocompatibility and suitable degradation rate have been a kind of biodegradable metal with great potential for clinical applications. This paper summarizes the biological role of degradable Zn alloy as bone implant materials, discusses the mechanical properties of different Zn alloys and their advantages and disadvantages as bone implant materials, and analyzes the influence of different processing strategies (such as alloying and additive manufacturing) on the mechanical properties of Zn alloys. This paper provides systematic design approaches for biodegradable Zn alloys as bone implant materials in terms of the material selection, product processing, structural topology optimization, and assesses their application prospects with a view to better serve the clinic.

Cytotoxicity of Biodegradable Zinc and Its Alloys: A Systematic Review.

Zinc-based biodegradable metals (BMs) have been developed for biomedical implant materials. However, the cytotoxicity of Zn and its alloys has caused controversy. This work aims to investigate whether Zn and its alloys possess cytotoxic effects and the corresponding influence factors. According to the guidelines of the PRISMA statement, an electronic combined hand search was conducted to retrieve articles published in PubMed, Web of Science, and Scopus (2013.1-2023.2) following the PICOS strategy. Eighty-six eligible articles were included. The quality of the included toxicity studies was assessed utilizing the ToxRTool. Among the included articles, extract tests were performed in 83 studies, and direct contact tests were conducted in 18 studies. According to the results of this review, the cytotoxicity of Zn-based BMs is mainly determined by three factors, namely, Zn-based materials, tested cells, and test system. Notably, Zn and its alloys did not exhibit cytotoxic effects under certain test conditions, but significant heterogeneity existed in the implementation of the cytotoxicity evaluation. Furthermore, there is currently a relatively lower quality of current cytotoxicity evaluation in Zn-based BMs owing to the adoption of nonuniform standards. Establishing a standardized in vitro toxicity assessment system for Zn-based BMs is required for future investigations.

The determination of zinc using flow injection and continuous flow analysis combined with a polymer inclusion film-coated column: Application to the determination of zinc in alloys and commercial lithium chloride.

A column coated with a polymer inclusion film (PIF) containing Aliquat 336 as carrier cast on glass beads packed in a glass tube is described for the separation, preconcentration, and determination of zinc(II) in flow injection analysis (FIA) and continuous flow analysis (CFA) systems. In the FIA method, 200 µL of a sample solution containing 2 mol/L lithium chloride is injected into a 2 mol/L lithium chloride stream. This converts zinc(II) ion into its anionic chlorocomplexes which are then extracted into the Aliquat 336-based PIF by anion exchange. The extracted zinc(II) is then back-extracted into a stream of 1 mol/L sodium nitrate solution and determined spectrophotometrically using 4-(2-pyridylazo)resorcinol as the color reagent. The limit of detection (LOD, S/N = 2) was determined as 0.017 mg/L. The usability of the PIF-based FIA method was demonstrated by the determination of zinc in alloys. The PIF-coated column was also employed successfully in the CFA determination of zinc(II) as an impurity in commercial lithium chloride samples. For this, 2 mol/L commercial lithium chloride solution was passed through the column for a predetermined time period followed by stripping in a stream of 1 mol/L sodium nitrate solution.

Progress and Prospect of Zn Anode Modification in Aqueous Zinc-Ion Batteries: Experimental and Theoretical Aspects.

Aqueous zinc-ion batteries (AZIBs), the favorite of next-generation energy storage devices, are popular among researchers owing to their environmental friendliness, low cost, and safety. However, AZIBs still face problems of low cathode capacity, fast attenuation, slow ion migration rate, and irregular dendrite growth on anodes. In recent years, many researchers have focused on Zn anode modification to restrain dendrite growth. This review introduces the energy storage mechanism and current challenges of AZIBs, and then some modifying strategies for zinc anodes are elucidated from the perspectives of experiments and theoretical calculations. From the experimental point of view, the modification strategy is mainly to construct a dense artificial interface layer or porous framework on the anode surface, with some research teams directly using zinc alloys as anodes. On the other hand, theoretical research is mainly based on adsorption energy, differential charge density, and molecular dynamics. Finally, this paper summarizes the research progress on AZIBs and puts forward some prospects.

Bioabsorbable zinc alloys for use in urological surgery.

PURPOSE: Non-absorbable clips are widely used in urologic surgery and they may come in contact with an open urinary tract intraoperatively. As a result, stray clips in the urinary tract and associated intractable infections have been reported. We developed a bioabsorbable metal and evaluated whether it would dissolve if it strayed into the urinary tract. METHODS: We prepared four types of alloys mainly comprising zinc (Zn) with small amounts of magnesium (Mg) and strontium (Sr), and the biological effects, degradability, strength, and ductility were investigated. Each alloy was implanted in the bladder of five rats for 4, 8, and 12 weeks. The alloys were removed and evaluated for degradability, stone adhesion, and tissue changes. The Zn-Mg-Sr alloy had degradability and no stone adhesion in the rat experiments, and it was implanted in the bladders of five pigs for 24 weeks. The Mg and Zn levels in the blood were measured, and staple changes were confirmed by cystoscopy. RESULTS: Zn-Mg-Sr alloys showed the best degradability of 6.51% at 12 weeks. In pig experiments, the degradation rate was 3.72% at 24 weeks. None of the pigs had changes in the Zn or Mg concentrations in the blood. Overall, the bladder incision was healed and the gross pathology showed wound healing. CONCLUSIONS: The Zn-Mg-Sr alloys were safely used in animal experiments. Furthermore, the alloys are easy to process and can be formed into various shapes, such as staples, making them useful in robotic surgery.

Highly efficient capture of mercury from complex water matrices by AlZn alloy reduction-amalgamation and in situ layered double hydroxide.

Mercury pollution is a critical, worldwide problem and the efficient, cost-effective removal of mercury from complex, contaminated water matrices in a wide pH range from strongly acidic to alkaline has been a challenge. Here, AlZn and AlFe alloys are investigated and a new process of synergistic reduction-amalgamation and in situ layered double hydroxide (SRA-iLDH) for highly efficient capture of aqueous Hg(II) is developed using AlZn alloys. The parameters include the pH values of 1-12, the Hg(II) concentrations of 10-1000 mg L-1, and the alloy's Zn concentrations of 20%, 50% and 70% and Fe concentrations of 10%, 20% and 50%. The initial rate of Hg(II) uptake by AlZn alloys decreases with increasing Zn concentration while the overall rate is not affected. Specifically, AlZn50 alloy removes >99.5% Hg(II) from 10 mg L-1 solutions at pH 1-12 in 5 min at a rate constant of 0.055 g mg-1 min-1 and achieves a capacity of 5000 mg g-1, being the highest value reported so far. The super-performance of AlZn alloy is attributed to multiple functions of chemical reduction, dual amalgamation, in situ LDH's surface complexation and adsorption, isomorphous substitution and intercalation. This study provides a simple and highly efficient approach for removing Hg(II) from complex water matrices.

Research status and development of biodegradable zinc alloy as orthopedics implant / 生物医学工程学杂志

Znic (Zn) alloys with good cytocompatibility and suitable degradation rate have been a kind of biodegradable metal with great potential for clinical applications. This paper summarizes the biological role of degradable Zn alloy as bone implant materials, discusses the mechanical properties of different Zn alloys and their advantages and disadvantages as bone implant materials, and analyzes the influence of different processing strategies (such as alloying and additive manufacturing) on the mechanical properties of Zn alloys. This paper provides systematic design approaches for biodegradable Zn alloys as bone implant materials in terms of the material selection, product processing, structural topology optimization, and assesses their application prospects with a view to better serve the clinic.

High Throughput Preparation of Ag-Zn Alloy Thin Films for the Electrocatalytic Reduction of CO2 to CO.

Ag-Zn alloys are identified as highly active and selective electrocatalysts for CO2 reduction reaction (CO2RR), while how the phase composition of the alloy affects the catalytic performances has not been systematically studied yet. In this study, we fabricated a series of Ag-Zn alloy catalysts by magnetron co-sputtering and further explored their activity and selectivity towards CO2 electroreduction in an aqueous KHCO3 electrolyte. The different Ag-Zn alloys involve one or more phases of Ag, AgZn, Ag5Zn8, AgZn3, and Zn. For all the catalysts, CO is the main product, likely due to the weak CO binding energy on the catalyst surface. The Ag5Zn8 and AgZn3 catalysts show a higher CO selectivity than that of pure Zn due to the synergistic effect of Ag and Zn, while the pure Ag catalyst exhibits the highest CO selectivity. Zn alloying improves the catalytic activity and reaction kinetics of CO2RR, and the AgZn3 catalyst shows the highest apparent electrocatalytic activity. This work found that the activity and selectivity of CO2RR are highly dependent on the element concentrations and phase compositions, which is inspiring to explore Ag-Zn alloy catalysts with promising CO2RR properties.

Effect of Substrates Performance on the Microstructure and Properties of Phosphate Chemical Conversion Coatings on Metal Surfaces.

Phosphate chemical conversion (PCC) technology has attracted extensive attention for its ability to regulate the surface properties of biomedical metals. However, titanium (Ti)-based alloys exhibit inertia because of the native passive layer, whereas zinc (Zn)-based alloys show high activity in acidic PCC solutions. The substrate performance affects the chemical reaction in the phosphating solution, which further leads to diversity in coating properties. In this work, the zinc-phosphate (ZnP) coatings are prepared on Ti alloy (TA) and Zn alloy (ZA) substrates using the PCC method, respectively. The coatings prepared herein are detected by a scanning electron microscope (SEM), X-ray diffractometer (XRD), laser scanning confocal microscope (LSCM), universal testing machine, contact angle goniometer, and electrochemical workstation system. The results show that the substrate performance has little effect on the phase composition but can significantly affect the crystal microstructure, thickness, and bonding strength of the coatings. In addition, the ZnP coatings improve the surface roughness of the substrates and show good hydrophilicity and electrochemical corrosion resistance. The formation mechanism of the ZnP coating is revealed using potential-time curves, indicating that the metal-solution interfacial reaction plays a dominant role in the deposition process.

Current status and outlook of potential applications of biodegradable materials in cerebral vascular stents.

The treatment of intracranial aneurysms (IAs) has undergone a very significant transformation in recent decades, and endovascular interventions have gradually become one of the most common treatments. As permanent metal stents can cause some degree of long-term damage to patients, biodegradable stent materials are emerging as attractive potential alternatives. By reviewing the current research status and the advantages and disadvantages of existing biodegradable biomaterials, this review expects to provide a valuable reference for subsequent research on biodegradable biomaterials.