Zinc-based subcuticular absorbable staples: An in vivo and in vitro study.

A zinc-nutrient element alloy (Zn-1.0Cu-0.5Ca) was developed into subcuticular absorbable staples (SAS) as a robust alternative to the commercially available poly(l-lactide-co-glycolide) (PLGA) SAS for the first time. The fixation properties of the Zn SAS were measured via pull-out tests and in-situ lap-shear pull-out test comparatively against the PLGA SAS. The Zn SAS exhibited fixation force of 18.9±0.2 N, which was over three times higher than that of PLGA SAS (5.5±0.1 N). The Zn SAS was used to close incision wounds in a SD rat model for biodegradability and biocompatibility characterisation at 1, 4 and 12 weeks. The Zn SAS showed uniform degradation behaviour after in vivo implantation at the average rate of 198±54, 112±28, and 70±24 µm/y after 1, 4, and 12 weeks, which reduced the fixation force to 16.8±1.1 N, 15.4±0.9 N, 12.7±0.7 N, respectively. These findings showed the potential of the Zn SAS for the closure of heavy loading and slowing healing tissues. The Zn SAS enabled successful closure and healing of the incision wound, similar to the PLGA staples. However, the slow long-term degradation rate of the Zn SAS may lead to unnecessary implant retention. In addition, the alloy SAS resulted in higher local foreign body responses due to their stiffness. Reducing the implant cross-section profile and applying low stiffness and a corrosion-accelerating coating are suggested as possible approaches to reduce post-service implant retention and improve the biocompatibility of the Zn SAS. STATEMENT OF SIGNIFICANCE: This work reports the fabrication of the first metallic subcuticular absorbable staples (SAS) made from ZnCuCa alloy for skin wound closure applications. The Zn-based SAS were characterised in vitro and in vivo (SD rat model) for biodegradability, fixation properties, biocompatibility and inflammatory responses, which were compared against the commercially available PLGA-based SAS. The Zn-based SAS provided a secure attachment of the full-thickness wounds on SD rats and allowed successful healing during the 12-week service period. In addition, the in vitro results showed that the Zn-based SAS provided more than three times higher fixation strength than the commercial PLGA, indicating the potential of the Zn-based SAS for load-bearing wound closure application.

Exploring the Influence of Biologically Relevant Ions on the Corrosion Behavior of Biodegradable Zinc in Physiological Fluids.

This work presents a study on the influence of biologically relevant ions on the corrosion of zinc (Zn) in physiological fluids. Electrochemical techniques were used to investigate the degradation of pure Zn exposed to different physiological electrolytes containing chlorides, carbonates, sulfates, and phosphates. The corrosion behavior of Zn in the solutions over a 7-day period was also assessed. SEM, EDS, and FTIR were used to analyze corrosion products. With respect to corrosion, the most aggressive ions are chlorides, which induce localized corrosion, while carbonates and phosphates reduce the corrosive attack of the chloride on Zn while inducing uniform corrosion. Sulfates reduce the corrosion rate by disrupting Zn's passive layer. The overall corrosion rate of Zn changed in each electrolyte depending on the nature of the solution and the corrosion product formed. These findings will be useful in predicting the in-service behavior of future biodegradable Zn medical implants.

Fabrication and Properties of Biodegradable Akermanite-Reinforced Fe35Mn Alloys for Temporary Orthopedic Implant Applications.

As a representative of the biodegradable iron (Fe)-manganese (Mn) alloys, Fe35Mn has been investigated as a promising biodegradable metal biomaterial for orthopedic applications. However, its slow degradation rate, though better than pure Fe, and poor bioactivity are concerns that retard its clinical applications. Akermanite (Ca2MgSi2O7, Ake) is a silicate-based bioceramic, showing desirable degradability and bioactivity for bone repair. In the present work, Fe35Mn/Ake composites were prepared via a powder metallurgy route. The effect of different contents of Ake (0, 10, 30, 50 vol %) on the microstructure, mechanical properties, degradation, and biocompatibility of the composites was investigated. The ceramic phases were found to be evenly distributed in the metal matrix. The Ake reacted with Fe35Mn and generated CaFeSiO4 during sintering. The addition of Ake increased the relative density of pure Fe35Mn from ∼90 to ∼94-97%. The compressive yield strength (CYS) and elastic modulus (Ec) increased with increasing Ake, with Fe35Mn/50Ake exhibiting the highest CYS of ∼403 MPa and Ec of ∼18 GPa. However, the ductility decreased at higher Ake concentrations (30 and 50%). Microhardness also showed an increasing trend with the addition of Ake. Electrochemical measurements indicated that higher concentrations of Ake (30 and 50%) could potentially increase the corrosion rate of Fe35Mn from ∼0.25 to ∼0.39 mm/year. However, all of the compositions tested did not show measurable weight loss after immersion in simulated body fluid (SBF) for 4 weeks, attributed to the use of prealloyed raw material, high sintered density of the fabricated composites, and the formation of a dense Ca-, P-, and O-rich layer on the surface. Human osteoblasts on Fe35Mn/Ake composites showed increasing viability with increasing Ake content, indicating improved in vitro biocompatibility. These preliminary results suggest that Fe35Mn/Ake can be a potential material for biodegradable bone implant applications, particularly Fe35Mn/30Ake, if the slow corrosion of the composite can be addressed.

Evolution of degradation mechanism and fixation strength of biodegradable Zn-Cu wire as sternum closure suture: An in vitro study.

This work reports the first in vitro study on the in-situ biodegradation behaviour and the evolution of fixation strength of Zn-Cu alloy wires in a simulated sternum closure environment. Zn-Cu wires were used to reapproximate the partial bisected sternum models, and their fixation effect was compared with traditional surgical grade 316 L stainless steel (SS) wires in terms of fixation rigidity, critical load, first/ultimate failure characteristics. The metal sutures were then immersed in Hank's balanced salt solution for 12 weeks immersion period, and their corrosion behaviours assessed. Zn-Cu wires showed similar fixation rigidity at 70.89 ± 6.97 N/mm as SS, but the critical load, first failure and ultimate failure characteristics were inferior to SS. The key challenges that limited the fixation effect of the Zn-Cu wires were poor mechanical strength, short elastic region, and strain softening behaviours, which resulted in poor load-bearing capabilities and reduced the knot security of the sutures. The in-situ biodegradation of the Zn-Cu suture was accompanied by the early onset of localised corrosion within the twisted knot and the section located next to the incision line. Crevice corrosion and strain-induced corrosion were the dominant mechanisms in the observed localised corrosion. The localised corrosion on the Zn-Cu sutures did not lead to a significant shift in fixation rigidity, critical load and the first failure characteristics. The findings suggest that the Zn-based biodegradable metallic wires could be a promising sternum closure suture material once the limitations in mechanical characteristics are addressed.

Expedient secondary functions of flexible piezoelectrics for biomedical energy harvesting.

Flexible piezoelectrics realise the conversion between mechanical movements and electrical power by conformally attaching onto curvilinear surfaces, which are promising for energy harvesting of biomedical devices due to their sustainable body movements and/or deformations. Developing secondary functions of flexible piezoelectric energy harvesters is becoming increasingly significant in recent years via aiming at issues that cannot be addressed or mitigated by merely increasing piezoelectric efficiencies. These issues include loose interfacial contact and pucker generation by stretching, power shortage or instability induced by inadequate mechanical energy, and premature function degeneration or failure caused by fatigue fracture after cyclic deformations. Herein, the expedient secondary functions of flexible piezoelectrics to mitigate above issues are reviewed, including stretchability, hybrid energy harvesting, and self-healing. Efforts have been devoted to understanding the state-of-the-art strategies and their mechanisms of achieving secondary functions based on piezoelectric fundamentals. The link between structural characteristic and function performance is unravelled by providing insights into carefully selected progresses. The remaining challenges of developing secondary functions are proposed in the end with corresponding outlooks. The current work hopes to help and inspire future research in this promising field focusing on developing the secondary functions of flexible piezoelectric energy harvesters.

An overview and critical assessment of the mechanisms of microstructural refinement during ultrasonic solidification of metals.

A refined, equiaxed grain structure and the formation of finer primary intermetallic phases are some of the notable benefits of ultrasonic processing of liquid/solidifying melts. Ultrasonic treatment (UST) has been widely explored in Al and Mg-based alloys due to its operational versatility and scalability. During UST, the refinement of grain and primary intermetallic phases occurs via cavitation-induced fragmentation mechanisms. In addition, UST improves the efficiency (activation of particles) of the conventional grain refinement process when potent particles are added through master alloys. Though the UST's ability to produce refined as-cast structures is well recognized, the understanding of the refinement mechanisms is still debated and unresolved. Significant efforts have been devoted to understanding these mechanisms through the use of sophisticated techniques such as in-situ/ real-time observation, lab-scale and commercial-scale casting processes. All these studies aim to demonstrate the significance of cavitation, fragmentation modes, and alloy chemistry in microstructure refinement. Although the physical effects of cavitation and acoustic streaming (fluid flow) are primary factors influencing the refinement, the dominant grain refinement mechanisms are affected by several solidification variables and casting conditions. Some of these include melt volume, solute, cooling rate, potent particles, grain growth (equiaxed, columnar or dendritic), and the cold zones of the casting where the onset of nucleation occurs. This review aims to provide a better insight into solidification variables emphasizing the importance of cold zones in generating fine structures for small- and large-volume (direct chill) castings. Another important highlight of this review is to present the relatively less explored mechanism of (acoustic) vibration-induced crystallization and discuss the role of cavitation in achieving a refined ingot structure.

Design, mechanical and degradation requirements of biodegradable metal mesh for pelvic floor reconstruction.

Pelvic organ prolapse is the herniation of surrounding tissue and organs into the vagina and/or rectum and is a result of the weakening of pelvic floor muscles, connective tissue, and fascia. It is widely accepted that 50% of women will develop prolapse, with the prevalence increasing with age, and up to 10-20% of those seek evaluation for their condition. Suture repairs of pelvic floor defects are associated with a high failure rate, and permanent meshes were introduced to reduce the recurrence rate. The meshes were successful in reducing the rate of recurrence but were also associated with a higher rate of complications (pain or erosion into surrounding organs) and as such have been banned in many countries. New materials that are able to provide tissue support without complications are urgently required. A promising new material may be a biodegradable metal, which provides support during healing and subsequently completely degrades. We summarise pelvic mesh usage, and evaluate the use of a biodegradable metal, which has advantages of biocompatibility, antibacterial properties, and mechanical properties. The remaining challenges are discussed as follows: (1) degradation rate, (2) stiffness, (3) corrosion fatigue, (4) zinc aging, and (5) MRI artifacts.

In vivo performance of a rare earth free Mg-Zn-Ca alloy manufactured using twin roll casting for potential applications in the cranial and maxillofacial fixation devices.

A magnesium alloy containing essential, non-toxic, biodegradable elements such as Ca and Zn has been fabricated using a novel twin-roll casting process (TRC). Microstructure, mechanical properties, in vivo corrosion and biocompatibility have been assessed and compared to the properties of the rare earth (RE) element containing WE43 alloy. TRC Mg-0.5 wt% Zn- 0.5 wt% Ca exhibited fine grains with an average grain size ranging from 70 to 150 µm. Mechanical properties of a TRC Mg-0.5Zn-0.5Ca alloy showed an ultimate tensile strength of 220 MPa and ductility of 9.3%. The TRC Mg-0.5Zn-0.5Ca alloy showed a degradation rate of 0.51 ± 0.07 mm/y similar to that of the WE43 alloy (0.47 ± 0.09 mm/y) in the rat model after 1 week of implantation. By week 4 the biodegradation rates of both alloys studied were lowered and stabilized with fewer gas pockets around the implant. The histological analysis shows that both WE43 and TRC Mg-0.5Zn-0.5Ca alloy triggered comparable tissue healing responses at respective times of implantation. The presence of more organized scarring tissue around the TRC Mg-0.5Zn-0.5Ca alloys suggests that the biodegradation of the RE-free alloy may be more conducive to the tissue proliferation and remodelling process.

Zinc-nutrient element based alloys for absorbable wound closure devices fabrication: Current status, challenges, and future prospects.

The need for the development of load-bearing, absorbable wound closure devices is driving the research for novel materials that possess both good biodegradability and superior mechanical characteristics. Biodegradable metals (BMs), namely: magnesium (Mg), zinc (Zn) and iron (Fe), which are currently being investigated for absorbable vascular stent and orthopaedic implant applications, are slowly gaining research interest for the fabrication of wound closure devices. The current review presents an overview of the traditional and novel BM-based intracutaneous and transcutaneous wound closure devices, and identifies Zn as a promising substitute for the traditional materials used in the fabrication of absorbable load-bearing sutures, internal staples, and subcuticular staples. In order to further strengthen Zn to be used in highly stressed situations, nutrient elements (NEs), including calcium (Ca), Mg, Fe, and copper (Cu), are identified as promising alloying elements for the strengthening of Zn-based wound closure device material that simultaneously provide potential therapeutic benefit to the wound healing process during implant biodegradation process. The influence of NEs on the fundamental characteristics of biodegradable Zn are reviewed and critically assessed with regard to the mechanical properties and biodegradability requirements of different wound closure devices. The opportunities and challenges in the development of Zn-based wound closure device materials are presented to inspire future research on this rapidly growing field.

Biodegradable shape memory alloys: Progress and prospects.

Shape memory alloys (SMAs) have a wide range of potential novel medical applications due to their superelastic properties and ability to restore and retain a 'memorised' shape. However, most SMAs are permanent and do not degrade in the body when used in implantable devices. The use of non-degrading metals may lead to the requirement for secondary removal surgery and this in turn may introduce both short and long-term health risks, or additional waste disposal requirements. Biodegradable SMAs can effectively eliminate these issues by gradually degrading inside the human body while providing the necessary support for healing purposes, therefore significantly alleviating patient discomfort and improving healing efficiency. This paper reviews the current progress in biodegradable SMAs from the perspective of biodegradability, mechanical properties, and biocompatibility. By providing insights into the status of SMAs and biodegradation mechanisms, the prospects for Mg- and Fe-based biodegradable SMAs to advance biodegradable SMA-based medical devices are explored. Finally, the remaining challenges and potential solutions in the biodegradable SMAs area are discussed, providing suggestions and research frameworks for future studies on this topic.

In Vivo Evaluation of Bioabsorbable Fe-35Mn-1Ag: First Reports on In Vivo Hydrogen Gas Evolution in Fe-Based Implants.

This work investigates the influence of Ag (1 wt%) on the mechanical properties, in vitro and in vivo corrosion, and biocompatibility of Fe-35Mn. The microstructure of Fe-35Mn-1Ag possesses a uniform dispersion of discrete silver particles. Slight improvements in compressive properties are attributed to enhanced density and low porosity volume. Fe-35Mn-1Ag exhibits good in vitro and in vivo corrosion rate of Fe-35Mn due to an increase in microgalvanic corrosion. Gas pockets, which originate from an inflammatory response to the implants, are observed in the rats after 4 weeks implantation but are undetectable after 12 weeks. No chronic toxicity is observed with the Fe-35Mn-1Ag, suggesting acceptable in vivo biocompatibility. The high corrosion rate of the alloy triggers an increased level of nonadverse tissue inflammatory responses 4 weeks after implantation, which subsequently subsides at 12 weeks. The Fe-35Mn-1Ag displays properties that are suitable for orthopedic applications.

The influence of Ca and Cu additions on the microstructure, mechanical and degradation properties of Zn-Ca-Cu alloys for absorbable wound closure device applications.

Novel ternary Zn-Ca-Cu alloys were studied for the development of absorbable wound closure device material due to Ca and Cu's therapeutic values to wound healing. The influence of Ca and Cu on the microstructure, mechanical and degradation properties of Zn were investigated in the as-cast state to establish the fundamental understanding on the Zn-Ca-Cu alloy system. The microstructure of Zn-0.5Ca-0.5Cu, Zn-1.0Ca-0.5Cu, and Zn0.5Ca-1.0Cu is composed of intermetallic phase CaZn13 distributed within the Zn-Cu solid solution. The presence of CaZn13 phase and Cu as solute within the Zn matrix, on the one hand, exhibited a synergistic effect on the grain refinement of Zn, reducing the grain size of pure Zn by 96%; on the other hand, improved the mechanical properties of the ternary alloys through solid solution strengthening, second phase strengthening, and grain refinement. The degradation properties of Zn-Ca-Cu alloys are primarily influenced by the micro-galvanic corrosion between Zn-Cu matrix and CaZn13 phase, where the 0.5% and 1.0% Ca addition increased the corrosion rate of Zn from 11.5 µm/y to 19.8 µm/y and 29.6 µm/y during 4 weeks immersion test.

Additively manufactured iron-manganese for biodegradable porous load-bearing bone scaffold applications.

Selective laser melting (SLM) can produce complex hierarchical architectures paving the way for highly customisable biodegradable load-bearing bone scaffolds. For the first time, an in-depth analysis on the performance of SLM-manufactured iron-manganese bone scaffolds suitable for load-bearing applications is presented. Microstructural, mechanical, corrosion and biological characterisations were performed on SLM-manufactured iron-manganese scaffolds. The microstructure of the scaffold consisted primarily of γ-austenite, leading to high ductility. The mechanical properties of the scaffold were sufficient for load-bearing applications even after 28 days immersion in simulated body fluids. Corrosion tests showed that the corrosion rate was much higher than bulk pure iron, attributed to a combination of the manufacturing method, the addition of Mn to the alloy and the design of the scaffold. In vitro cell testing showed that the scaffold had good biocompatibility and viability towards mammalian cells. Furthermore, the presence of filopodia showed good osteoblast adhesion. In vivo analysis showed successful bone integration with the scaffold, with new bone formation observed after 4 weeks of implantation. Overall the SLM manufactured porous Fe-35Mn implants showed promise for biodegradable load-bearing bone scaffold applications. STATEMENT OF SIGNIFICANCE: Biodegradable iron scaffolds are emerging as a promising treatment for critical bone defects. Within this field, selective laser melting (SLM) has become a popular method of manufacturing bespoke scaffolds. There is limited knowledge on SLM-manufactured iron bone scaffolds, and no knowledge on their application for load-bearing situations. The current manuscript is the first study to characterise SLM manufactured iron-manganese bone scaffolds for load-bearing applications and also the first study to perform In vivo testing on SLM produced biodegradable iron scaffolds. In this study, for the first time, the mechanical, corrosion and biological properties of an iron-manganese scaffold manufactured using SLM were investigated. In summary the SLM-manufactured porous iron-manganese implants displayed great potential for biodegradable load-bearing bone scaffolds.

In-Situ Observation of the Continuous Phase Transition in Determining the High Thermoelectric Performance of Polycrystalline Sn0.98Se.

We report a comprehensive in-situ phase-change study on polycrystalline Sn0.98Se via high-temperature X-ray diffraction and in-situ high-voltage transmission electron microscopy from room temperature to 843 K. The results clearly demonstrate a continuous phase transition from Pnma to Cmcm starting from 573 to 843 K, rather than a sudden transition at 800 K. We also find that the thermal-conductivity rise at high temperature after the phase transition, as commonly seen in pristine SnSe, does not occur in Sn0.98Se, leading to a high thermoelectric figure of merit. Density functional theory calculations reveal the origin to be the suppression of bipolar thermal conduction in the Cmcm phase of Sn0.98Se due to the enlarged bandgap. This work fills the gap of in-situ characterization on polycrystalline Sn0.98Se and provides new insights into the outstanding thermoelectric performance of polycrystalline Sn0.98Se.

The Prospects for Biodegradable Zinc in Wound Closure Applications.

Zinc is identified as a promising biodegradable metal along with magnesium and iron. In the last 5 years, considerable progress is made on understanding the mechanical properties, biodegradability, and biocompatibility of zinc and its alloys. A majority of these studies have focused on using zinc for absorbable cardiovascular and orthopedic device applications. However, it is likely that zinc is also suitable for other biomedical applications. In this work, the prospects for zinc in the fabrication of wound closure devices such as absorbable sutures, staples, and surgical tacks are critically assessed, with the aim of inspiring future research on biodegradable Zn for this medical application.

Exploring the Role of Manganese on the Microstructure, Mechanical Properties, Biodegradability, and Biocompatibility of Porous Iron-Based Scaffolds.

In this work, the role that manganese plays in determining the structure and performance of sintered biodegradable porous Fe-Mn alloys is described. Powder metallurgy processing was employed to produce a series of biodegradable porous Fe-xMn (x = 20, 30, and 35 wt %) alloys suitable for bone scaffold applications. Increasing manganese content increased the porosity volume in the sintered alloys and influenced the ensuing properties of the metal. The Fe-35Mn alloy possessed optimum properties for orthopedic application. X-ray diffraction analysis and magnetic characterization confirmed the predominance of the antiferromagnetic austenitic phase and ensured the magnetic resonance imaging (MRI) compatibility of this alloy. The porous Fe-35Mn alloy possessed mechanical properties (tensile strength of 144 MPa, elastic modulus of 53.3 GPa) comparable to human cortical bone. The alloy exhibited high degradation rates (0.306 mm year-1) in simulated physiological fluid, likely due to its considerable Mn content and the high surface area inherent to its porous structures, while cytotoxicity and morphometry tests using mammalian preosteoblast cells (MC3T3-E1) indicated good cell viability in the Fe-35Mn alloy.

Comparison of the Microstructure and Biocorrosion Properties of Additively Manufactured and Conventionally Fabricated near ß Ti-25Nb-3Zr-3Mo-2Sn Alloy.

The microstructure and biodegradability of a near ß Ti-25Nb-3Zr-3Mo-2Sn alloy produced by laser engineered net shaping have been compared to those of alloys produced via casting and cold rolling in order to identify the key effects of processing pathways on the development of microstructure and biocorrosion properties. Results confirm the significant influence of processing technique on microstructure and concomitant biocompatibility of the alloy. Tests using mesenchymal stem cells confirm the ability of the additively manufactured alloy to support cell adhesion and spreading.