Characterization of hFOB 1.19 Cell Line for Studying Zn-Based Degradable Metallic Biomaterials.

In vitro testing is the first important step in the development of new biomaterials. The human fetal osteoblast cell line hFOB 1.19 is a very promising cell model; however, there are vast discrepancies in cultivation protocols, especially in the cultivation temperature and the presence of the selection reagent, geneticin (G418). We intended to use hFOB 1.19 for the testing of Zn-based degradable metallic materials. However, the sensitivity of hFOB 1.19 to zinc ions has not yet been studied. Therefore, we compared the toxicity of zinc towards hFOB 1.19 under different conditions and compared it with that of the L929 mouse fibroblast cell line. We also tested the cytotoxicity of three types of Zn-based biomaterials in two types of media. The presence of G418 used as a selection reagent decreased the sensitivity of hFOB 1.19 to Zn2+. hFOB 1.19 cell line was more sensitive to Zn2+ at elevated (restrictive) temperatures. hFOB 1.19 cell line was less sensitive to Zn2+ than L929 cell line (both as ZnCl2 and extracts of alloys). Therefore, the appropriate cultivation conditions of hFOB 1.19 during biomaterial testing should be chosen with caution.

A detailed mechanism of degradation behaviour of biodegradable as-ECAPed Zn-0.8Mg-0.2Sr with emphasis on localized corrosion attack.

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.

Novel Ultrafine-Grain Mg-Gd/Nd-Y-Ca Alloys with an Increased Ignition Temperature.

Two novel ignition-resistant magnesium alloys, Mg-2Gd-2Y-1Ca and Mg-2Nd-1Y-1Ca, were prepared in the ultrafine-grain condition by equal channel angular pressing (ECAP). In addition, four commercial alloys-AZ31, AX41, AE42 and WE43-were prepared similarly as a reference. The microstructure, mechanical properties and ignition temperature were thoroughly investigated. Both novel alloys exhibited a mean grain size of ~1 µm and dense distribution of small secondary phase particles. The mechanical strength measured by the tensile deformation test showed that the novel alloys are much stronger (~290 MPa) than all commercial alloys except WE43. However, Ca segregation into the grain boundaries caused a significant decrease in ductility (<6%). The ignition temperature of the novel alloys (~950 °C) was considerably improved by the presence of Gd/Nd, Y and Ca. This study showed that both novel alloys exhibit high strength and high ignition temperature in the ultrafine-grain condition.

Ultrafine-Grained Zn-Mg-Sr Alloy Synthesized by Mechanical Alloying and Spark Plasma Sintering.

Zinc materials are considered promising candidates for bioabsorbable medical devices used for the fixation of broken bones or stents. Materials for these applications must meet high mechanical property requirements. One of the ways to fulfil these demands is related to microstructure refinement, particularly the decrease in grain size. In the present work, we combine two powder metallurgy techniques (mechanical alloying-MA, and spark plasma sintering-SPS) to prepare Zn-1Mg-0.5Sr nanograin material. The microstructure of compacted material consisted of Zn grains and particles of Mg2Zn11 intermetallic phases from 100 to 500 nm in size, which resulted in high values of hardness and a compressive strength equal to 86 HV1 and 327 MPa, respectively. In this relation, the combination of the suggested techniques provides an innovative way to form extremely fine microstructures without significant coarsening during powder compaction at increased temperatures.

Microstructural and Mechanical Characterization of Newly Developed Zn-Mg-CaO Composite.

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 slips. The properties of intermetallic particles and pores were determined in material volume using micro-computed tomography (µCT), enhancing the precision of our assumptions compared with commonly applied methods. Based on that, and the analysis after the compressive tests, we were able to determine the influence of aspect ratio, feret diameters, and volume content of intermetallic phases and pores on mechanical behavior. The influence of the aspects on mechanical behavior is described and discussed.

Advanced Zinc-Magnesium Alloys Prepared by Mechanical Alloying and Spark Plasma Sintering.

Zinc and its alloys are considered as promising materials for the preparation of biodegradable medical devices (stents and bone fixation screws) due to their enhanced biocompatibility. These materials must achieve an ideal combination of mechanical and corrosion properties that can be influenced by alloying or thermomechanical processes. This paper presents the effects of different mechanical alloying (MA) parameters on the composition of Zn-1Mg powder. At the same time, this study describes the influence of preparation by MA on Zn-6Mg and Zn-16Mg alloys. The selected powders were compacted by the spark plasma sintering (SPS) method. Subsequently, their microstructures were studied and their mechanical properties were tested. The overall process led to a significant grain refinement (629 ± 274 nm for Zn-1Mg) and the formation of new intermetallic phases (Mg2Zn11, MgZn2). The compressive properties of the sintered samples were mainly related to the concentration of the alloying elements, where an increase in concentration led to an improvement in strength but a deterioration in ductility. According to the obtained results, the best properties were obtained for the Zn-1Mg alloy.

Annealing Response of Additively Manufactured High-Strength 1.2709 Maraging Steel Depending on Elevated Temperatures.

The present work describes the influence of different temperatures on mechanical properties and microstructure of additively manufactured high-strength 1.2709 maraging steel. For this purpose, samples produced by selective laser melting technology were used in their as-printed as well as their heat-treated state. Both samples were than exposed to temperatures ranging between 100 °C to 900 °C with a total dwell time of 2 h followed by water-cooling. The microhardness of the as-printed material reached its maximum (561 ± 6 HV0.1) at 500 °C, which corresponded to the microstructural changes. However, the heat-treated material retained its initial mechanical properties up to 500 °C. As the temperature increased, the microhardness of both the materials reduced, reaching their minimum at 900 °C. This phenomenon was accompanied by a change in the microstructure by forming coarse-grained martensite. This also resulted in a significant decrease in the ultimate tensile strength and an increase in the plasticity. TEM analysis confirmed the formation of Ni3Mo intermetallic phases in the as-printed material when exposed to a temperature of 500 °C. It was found that the same phase was present in the heat-treated sample and it remained stable up to a temperature of 500 °C.

Microstructure and Mechanical Properties of Ti-25Nb-4Ta-8Sn Alloy Prepared by Spark Plasma Sintering.

As the commercially most-used Ti-6Al-4V alloy has a different modulus of elasticity compared to the modulus of elasticity of bone and contains allergenic elements, ß-Ti alloy could be a suitable substitution in orthopedics. The spark plasma sintering (SPS) method is feasible for the preparation of materials, with very low porosity and fine-grained structure, leading to higher mechanical properties. In this study, we prepared quaternary Ti-25Nb-4Ta-8Sn alloy using the spark plasma sintering method. The material was also heat-treated in order to homogenize the structure and compare the microstructure and properties in as-sintered and annealed states. The SPS sample had a modulus of elasticity of about 63 ± 1 GPa, which, after annealing, increased to the value of 73 ± 1 GPa. The tensile yield strength (TYS) of the SPS sample was 730 ± 52 MPa, ultimate tensile strength (UTS) 764 ± 10 MPa, and ductility 22 ± 9%. Annealed samples reached higher values of TYS and UTS (831 ± 60 MPa and 954 ± 48 MPa), but the ductility decreased to the value of 3 ± 1%. The obtained results are discussed considering the observed microstructure of the alloy.

Hydrogen Embrittlement of the Additively Manufactured High-Strength X3NiCoMoTi 18-9-5 Maraging Steel.

The main aim of this study was to determine the susceptibility of the additively manufactured high strength X3NiCoMoTi 18-9-5 maraging steel to hydrogen embrittlement. For this purpose, samples produced by selective laser melting technology, before and after heat treatment, were used. The examined samples were electrochemically charged with hydrogen in NaCl + NH4SCN solution at a current density of 50 mA/cm2 for 24 h. The H content increased from about 1 to 15 ppm. Heat treatment did not affect the amount of H trapped in the maraging steel. Tensile testing revealed that the tensile strength of the H-charged samples was much lower than that of the uncharged samples. Moreover, the material became brittle after charging compared to the ductile as-printed and heat-treated samples with elongation values of 7% and 2%, respectively. The loss of plasticity was confirmed by fractography, which revealed transformation of the fracture surface morphology from dimple-like in the as-produced state to a brittle one with smooth facets in the H-charged state.

Phase Composition of Al-Si Coating from the Initial State to the Hot-Stamped Condition.

The chemical and phase composition of the coating and the coating/substrate interface of an Al-Si-coated 22MnB5 hot stamped steel was investigated by means of SEM-EDS, XRD, micro-XRD and electron diffraction. Moreover, the surface profile was analyzed by XPS and roughness measurements. The XPS measurements showed that the thickness of the Si and Al oxide layers increased from 14 to 76 nm after die-quenching, and that the surface roughness increased as well as a result of volume changes caused by phase transformations. In addition to the FeAl(Si) and Fe2Al5 phases and the interdiffusion layer forming complex structures in the coating, electron diffraction confirmed the presence of an Fe2Al5 phase, and also revealed very thin layers of Fe3(Al,Si)C, Fe2(Al,Si)5 and Al-bearing rod-shaped particles in the immediate vicinity of the steel interface. Moreover, the scattered nonuniform layer of the Fe2Al8Si phase was identified in the outermost layer of the coating. Despite numerous studies devoted to researching the phase composition of the Al-Si coating applied to hot stamped steel, electron diffraction revealed very thin layers and particles on the coating/substrate interface and outermost layer, which have not been analyzed in detail.

Test conditions can significantly affect the results of in vitro cytotoxicity testing of degradable metallic biomaterials.

In vitro cytotoxicity testing is an indispensable part of the development of new biomaterials. However, the standard ISO 10993-5 enables variability in the testing conditions, which makes the results of the test incomparable. We studied the influence of media composition on the results of the cytotoxicity test. Solutions of ZnCl2 served as simulated extracts and we also used extracts of three types of Zn-based and Mg-based degradable metals. We incubated the cells with the solutions prepared in two types of media with two concentrations of serum (5 and 10%). We compared the toxic effect of the extracts on L929 murine fibroblast-derived cell line, which is recommended by ISO standard and on "osteoblast-like cells" U-2 OS. We also compared two methods of exposition: solutions were added either to a sub-confluent layer or to the cell suspension. We evaluated the metabolic activity of the cells using the resazurin test. We found out that in vitro cytotoxicity is dramatically influenced by the concentration of serum and by the type of the medium as well as by the type of exposition and type of cells. Therefore, when performing in vitro cytotoxicity testing of biomaterials, the authors should carefully specify the conditions of the test and comparison of different studies should be carried out with caution.

Development of TiAl-Si Alloys-A Review.

This paper describes the effect of silicon on the manufacturing process, structure, phase composition, and selected properties of titanium aluminide alloys. The experimental generation of TiAl-Si alloys is composed of titanium aluminide (TiAl, Ti3Al or TiAl3) matrix reinforced by hard and heat-resistant titanium silicides (especially Ti5Si3). The alloys are characterized by wear resistance comparable with tool steels, high hardness, and very good resistance to oxidation at high temperatures (up to 1000 °C), but also low room-temperature ductility, as is typical also for other intermetallic materials. These alloys had been successfully prepared by the means of powder metallurgical routes and melting metallurgy methods.

The Influence of Powder Milling on Properties of SPS Compacted FeAl.

The Fe-28 at.% Al alloy was studied in this article. The aim was to describe the influence of gas atomized powder pre-milling before SPS (Spark Plasma Sintering) sintering on the structure and properties of the bulk materials. The initial powder was milled for 0.5, 1, and 8 h. It was proven that 1 h milling leads to the change in size and morphology of the particles, B2→A2 phase transformation, and to the contamination with the material from a milling vessel. Powder materials were compacted by the SPS process at 900, 1000, and 1100 °C. The differences between the bulk materials were tested by LM, SEM, and TEM microscopy, XRD, and neutron diffraction methods. It was proven that, although the structures of initial powder (B2) and milled powder (A2) were different, both provide after-sintering material with the same structure (D03) with similar structural parameters. Higher hardness and improved ductility of the material sintered from the milled powder are likely caused by the change in chemical composition during the milling process.

Extrusion of the biodegradable ZnMg0.8Ca0.2 alloy - The influence of extrusion parameters on microstructure and mechanical characteristics.

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.

Characterization of Newly Developed Zinc Composite with the Content of 8 wt.% of Hydroxyapatite Particles Processed by Extrusion.

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.

Structure and Properties of High­Strength Ti Grade 4 Prepared by Severe Plastic Deformation and Subsequent Heat Treatment.

Severe plastic deformation represented by three passes in Conform SPD and subsequent rotary swaging was applied on Ti grade 4. This process caused extreme strengthening of material, accompanied by reduction of ductility. Mechanical properties of such material were then tuned by a suitable heat treatment. Measurements of in situ electrical resistance, in situ XRD and hardness indicated the appropriate temperature to be 450 °C for the heat treatment required to obtain desired mechanical properties. The optimal duration of annealing was stated to be 3 h. As was verified by neutron diffraction, SEM and TEM microstructure observation, the material underwent recrystallization during this heat treatment. That was documented by changes of the grain shape and evaluation of crystallite size, as well as of the reduction of internal stresses. In annealed state, the yield stress and ultimate tensile stress decreased form 1205 to 871 MPa and 1224 to 950 MPa, respectively, while the ductility increased from 7.8% to 25.1%. This study also shows that mechanical properties of Ti grade 4 processed by continual industrially applicable process (Conform SPD) are comparable with those obtained by ECAP.

Zn-Mg Biodegradable Composite: Novel Material with Tailored Mechanical and Corrosion Properties.

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.

High Strength X3NiCoMoTi 18-9-5 Maraging Steel Prepared by Selective Laser Melting from Atomized Powder.

Maraging steels are generally characterized by excellent mechanical properties, which make them ideal for various industrial applications. The application field can be further extended by using selective laser melting (SLM) for additive manufacturing of shape complicated products. However, the final mechanical properties are strongly related to the microstructure conditions. The present work studies the effect of heat treatment on the microstructure and mechanical properties of 3D printed samples prepared from powder of high-strength X3NiCoMoTi 18-9-5 maraging steel. It was found that the as-printed material had quite low mechanical properties. After sufficient heat treatment, the hardness of the material increased from 350 to 620 HV0.1 and the tensile yield strength increased from 1000 MPa up to 2000 MPa. In addition, 3% ductility was maintained. This behavior was primarily affected by strong precipitation during processing.

The Fundamental Comparison of Zn-2Mg and Mg-4Y-3RE Alloys as a Perspective Biodegradable Materials.

Biodegradable materials are of interest for temporary medical implants like stents for restoring damaged blood vessels, plates, screws, nails for fixing fractured bones. In the present paper new biodegradable Zn-2Mg alloy prepared by conventional casting and hot extrusion was tested in in vitro and in vivo conditions. Structure characterization and mechanical properties in tension and compression have been evaluated. For in vivo tests, hemispherical implants were placed into a rat cranium. Visual observation of the living animals, an inspection of implant location and computed tomography CT imaging 12 weeks after implantation were performed. Extracted implants were studied using scanning electron microscopy (SEM) on perpendicular cuts through corrosion products. The behaviour of zinc alloy both in in vitro and in vivo conditions was compared with commercially used Mg-based alloy (Mg-4Y-3RE) prepared by conventional casting and hot extrusion. Both compressive and tensile yield strengths of Zn and Mg-based alloys were similar; however, the brittleness of Mg-4Y-3RE was lower. Zn and Mg-based implants have no adverse effects on the behaviour or physical condition of rats. Moreover, gas bubbles and the inflammatory reaction of the living tissue were not detected after the 12-week period.

Corrosion behaviour and cell interaction of Ti-6Al-4V alloy prepared by two techniques of 3D printing.

3D printing seems to be the technology of the future for the preparation of metallic implants. For such applications, corrosion behaviour is pivotal. However, little is published on this topic and with inconsistent results. Therefore, we carried out a complex study in which we compared two techniques of the 3D printing technology - selective laser melting and electron beam melting. The corrosion behaviour was studied in physiological solution by standard electrochemical techniques and susceptibility to localised corrosion was estimated too. All samples showed typical passive behaviour. Localised corrosion was shown to be possible on the original as-printed surfaces. Corrosion experiments were repeated tree times. To reveal possible negative effects of 3D printing on cytocompatibility, direct in vitro tests were performed with U-2 OS cells. The cells showed good viability and proliferation, but their growth was impeded by surface unevenness. Our results suggest that both techniques are suitable for implants production. Statistical evaluation was performed by ANOVA followed by Tukey's test.