Study of the Effect of Anodic Oxidation on the Corrosion Properties of the Ti6Al4V Implant Produced from SLM.

Additive technologies allowed for the development of medicine and implantology, enabling the production of personalized and highly porous implants. Although implants of this type are used clinically, they are usually only heat treated. Surface modification using electrochemical methods can significantly improve the biocompatibility of biomaterials used for implants, including printed ones. The study examined the effect of anodizing oxidation on the biocompatibility of a porous implant made of Ti6Al4V by the SLM method. The study used a proprietary spinal implant intended for the treatment of discopathy in the c4-c5 section. As part of the work, the manufactured implant was assessed in terms of compliance with the requirements for implants (structure testing-metallography) and the accuracy of the pores produced (pore size and porosity). The samples were subjected to surface modification using anodic oxidation. The research was carried out for 6 weeks in in vitro conditions. Surface topographies and corrosion properties (corrosion potential, ion release) were compared for unmodified and anodically oxidized samples. The tests showed no effect of anodic oxidation on the surface topography and improved corrosion properties. Anodic oxidation stabilized the corrosion potential and limited the release of ions to the environment.

Modern methods of surface modification for new-generation titanium alloys.

The constantly growing need for the use of implants in osteotomy is mainly due to the aging population and the need for long-term use of this type of biomaterials. Improving implant materials requires the selection of appropriate functional properties. Currently used titanium (Ti) alloys, such as Ti6Al4V and Ti6Al7Nb, are being replaced by materials with better biocompatibility, such as vanadium (V) or niobium (Nb), allowing for creation of the so-called new generation alloys. These new alloys, with the incorporation of zirconium (Zr), iron, and tantalum, possess Young's modulus close to that of a bone, which further improves the improves the biomaterial's. biocompatibility. This article describes the atomic layer deposition (ALD) method and its possible applications in the new generation of titanium alloys for biomedical applications. Also, the exemplary results of tin oxide (SnO2) thin coatings deposited by ALD and physical vapor deposition (PVD) methods are presented. This study aimed to evaluate the physicochemical properties of a Ti13Nb13Zr alloy used for elements in the skeletal system. As the temperature and the number of cycles vary, the results demonstrate that the surface area of the samples changes. The uncoated Ti13Nb13Zr alloy exhibits hydrophilic properties. However, all coated specimens improve in this respect and provide improved clinical results. after the applied modification, the samples have a smaller contact angle, but still remain in the range of 0-90°, which makes it possible to conclude that their nature remains hydrophilic. Coating the specimens decreased the mineralization risk of postoperative complications. As a result, the biomaterials demonstrated improved effectiveness, decreased complication indicators, and improved patient well-being.

A study on the physicochemical properties of surface modified Ti13Nb13Zr alloy for skeletal implants.

As it is widely stated in the literature, biofilms are responsible for most chronic infections, which have grown exponentially over the past three decades. The use of so-called alloys, as a new generation of materials, enables us to find the golden mean in the arena widely known as implantology. The use of the surface layer, using the chosen Atomic Layer Deposition method, is to be the basis for minimizing the risk of an organism reactions. Therefore, the primary objective of this study was to observe the impact of physicochemical properties of the surface layers (bactericidal) on the processes that occur on the implants surface made of titanium biomaterials used in bone structures. The study also attempted to evaluate the physicochemical properties of the ZnO coatings, deposited on the substrate of one of the new generation Ti13Nb13Zr alloys, using the ALD method. Included in the assessment of the physicochemical properties of the surface layers formed in this manner, we perform pitting corrosion resistance tests, scratch tests, tribological tests and surface wettability tests. Based on the obtained data, the differing physicochemical properties of the alloy with ZnO coatings are found to be dependent on the applied surface modification. For the conducted tests, differences are determined for the tests on the corrosion resistance, surface wettability and the abrasion resistance for samples with and without the ZnO coating. In addition, tests show that the coating applied to the alloy, which is previously subjected to the sand-blasted process, is characterized by improved adhesion.

Physical Properties of Electropolished CoCrMo Alloy Coated with Biodegradable Polymeric Coatings Releasing Heparin after Prolonged Exposure to Artificial Urine.

In this study, we aimed to determine the effect of long-term exposure to artificial urine on the physical properties of CoCrMo alloy with biodegradable heparin-releasing polymeric coatings. Variants of polymer coatings of poly(L,L-lactide-ɛ-caprolactone) (P(L,L-L/CL)) and poly(D,L-lactide-ɛ-caprolactone) (P(D,L-L/CL)) constituting the base for heparin-releasing (HEP) polyvinyl alcohol (PVA) coatings were analyzed. The coatings were applied by the dip-coating method. Heparin was used to counteract the incrustation process in the artificial urine. The study included tests of wettability, resistance to pitting and crevice corrosion, determination of the mass density of metal ions penetrating into the artificial urine, and the kinetics of heparin release. In addition, microscopic observations of surface roughness and adhesion to the metal substrate were performed. Electrolytically polished CoCrMo samples (as a reference level) and samples with polymer coatings were used for the tests. The tests were conducted on samples in the initial state and after 30, 60, and 90 days of exposure to artificial urine. The analysis of the test results shows that the polymer coatings contribute by improving the resistance of the metal substrate to pitting and crevice corrosion in the initial state and reducing (as compared with the metal substrate) the mass density of metal ion release into the artificial urine. Moreover, the PVA + HEP coating, regardless of the base polymer coatings used, contributes to a reduction in the incrustation process in the first 30 days of exposure to the artificial urine.

Effects of the sources of calcium and phosphorus on the structural and functional properties of ceramic coatings on titanium dental implants produced by plasma electrolytic oxidation.

Plasma Electrolytic Oxidation (PEO) is as a promising technique to modify metal surfaces by application of oxide ceramic coatings with appropriate physical, chemical and biological characteristics. Therefore, objective of this research was to find the simplest settings, yet able to produce relevant bioactive implant surfaces layers on Ti implants by means of PEO. We show that an electrolyte containing potassium dihydrogen phosphate as a source of P and either calcium hydroxide or calcium formate as a source of Ca in combination with a chelating agent, ethylenediamine tetraacetic acid (EDTA), is suitable for PEO to deliver coatings with desired properties. We determined surface morphology, roughness, wettability, chemical and phase composition of titanium after the PEO process. To investigate biocompatibility and bacterial properties of the PEO oxide coatings we used microbial and cell culture tests. The electrolyte based on Ca(OH)2 and EDTA promotes active crystallization of apatites after PEO processing of the Ti implants. The PEO layers can increase electrochemical corrosion resistance. The PEO can be potentially used for development of bioactive surfaces with increased support of eukaryotic cells while inhibiting attachment and growth of bacteria without use of antibacterial agents.

Selected Physicochemical Properties of Diamond Like Carbon (DLC) Coating on Ti-13Nb-13Zr Alloy Used for Blood Contacting Implants.

Despite high interest in the issues of hemocompatibility of titanium implants, particularly those made of the Ti-13Nb-13Zr alloy, the applied methods of surface modification still do not always guarantee the physicochemical properties required for their safe operation. The factors that reduce the efficiency of the application of titanium alloys in the treatment of conditions of the cardiovascular system include blood coagulation and fibrous proliferation within the vessel's internal walls. They result from their surfaces' physicochemical properties not being fully adapted to the specifics of the circulatory system. Until now, the generation and development mechanics of these adverse processes are not fully known. Thus, the fundamental problem in this work is to determine the correlation between the physicochemical properties of the diamond like carbon (DLC) coating (shaped by the technological conditions of the process) applied onto the Ti-13Nb-13Zr alloy designed for contact with blood and its hemocompatibility. In the paper, microscopic metallographic, surface roughness, wettability, free surface energy, hardness, coating adhesion to the substrate, impendence, and potentiodynamic studies in artificial plasma were carried out. The surface layer with the DLC coating ensures the required surface roughness and hydrophobic character and sufficient pitting corrosion resistance in artificial plasma. On the other hand, the proposed CrN interlayer results in better adhesion of the coating to the Ti-13Nb-13Zr alloy. This type of coating is an alternative to the modification of titanium alloy surfaces using various elements to improve the blood environment's hemocompatibility.

Impact of Surface Treatment on the Functional Properties Stainless Steel for Biomedical Applications.

The main goal of the carried out tests was to analyze the influence of the surface modification of a substrate by depositing composite ZnO layers by the Atomic Layer Deposition (ALD) method. The samples were subjected to preliminary surface modification consisting of being sandblasted and electropolished. A ZnO layer was applied to the prepared substrates by the ALD method. As a precursor of ZnO, diethylzinc (DEZ) was used, which reacted with water, enabling the deposition of the thin films. The chamber temperature was as follows: T = 100-300 °C. The number of cycles was 500 and 1500. As part of the assessment of the physicochemical properties of the resulting surface layers, the tests of chemical composition of the layer, pitting corrosion, impedance corrosion, adhesion to the metal substrate, morphology surface, and wettability were carried out. On the basis of the obtained research, it was found that a composite ZnO layer deposited onto a substrate previously subjected to the electrochemical polishing process has more favorable physicochemical properties. Moreover, an influence of temperature and the number of cycles of the deposition process on the obtained properties was observed, where the ZnO layer was characterized by more favorable properties at a temperature of 200-300 °C at 1500 cycles of the deposition process.

Structure and Properties of ZnO Coatings Obtained by Atomic Layer Deposition (ALD) Method on a Cr-Ni-Mo Steel Substrate Type.

This paper aimed to investigate the structure and physicochemical and tribological properties of ZnO coatings deposited by ALD on 316L stainless steel for biomedical applications. To obtain ZnO films, diethylzinc (DEZ) and water were used as ALD precursors. Zinc oxide layers were deposited at the same temperature of 200 °C using three types of ALD cycles: 500, 1000 and 1500. The structure and morphology of ZnO coatings were examined using SEM and AFM microscopes. The XRD and GIXRD methods were used for the phase analysis of the obtained coatings. To determine the resistance to pitting corrosion, potentiodynamic investigations and impedance spectroscopy were conducted in a Ringer solution at a temperature of 37 °C. The obtained results showed that the number of ALD cycles had a significant impact on the structure, morphology and corrosion resistance of the ZnO layers. It was found that after increasing the coating thickness of the ZnO on the material, its electrochemical properties determining the corrosion resistance also increased. Moreover, on the basis of the ball-on-plate tribological investigations, we found a significant reduction in the friction coefficient of the samples with the investigated coatings in relation to the noncoated substrates.

Electrochemical and Biological Performance of Biodegradable Polymer Coatings on Ti6Al7Nb Alloy.

The inhibition of the corrosion of metal implants is still a challenge. This study aimed to increase the corrosion resistance of Ti6Al7Nb alloy implants through surface modification, including grinding, sandblasting, and anodic oxidation followed by the deposition of a polymer coating. The aim of the work was to determine the influence of biodegradable polymer coatings on the physico-chemical properties of a Ti6Al7Nb alloy used for short-term implants. Biodegradable coatings prepared from poly(glycolide-caprolactone) (P(GCap)), poly(glycolide ε-caprolactone-lactide) (P(GCapL)), and poly(lactide-glycolide) (PLGA) were applied in the studies. The dip-coating method with three cycles of dipping was applied. Corrosion resistance was assessed on the basis of potentiodynamic studies. The studies were carried out on samples after 30, 60, and 90 days of exposure to Ringer's solution. Surface topography, wettability, and cytotoxicity studies were also carried out. The degradation process of the base material was evaluated on the basis of the mass density of the metal ions released to the solution. The results indicated the influence of the coating type on corrosion resistance. In addition, a beneficial effect of the polymer coating on the reduction of the density of the released metal ions was found, as compared to the samples without polymer coatings. The obtained results provide basic knowledge for the development of polymer coatings enriched with an active substance. The presence of ciprofloxacin in the coating did not reduce the corrosion resistance of the metal substrate. Moreover, the cytotoxicity test using the extract dilution method demonstrated that the implants' coatings are promising for further in vitro and in vivo studies.

Study of the Morphology and Properties of Biocompatible Ca-P Coatings on Mg Alloy.

Magnesium alloys are considered as potential biomaterials for use in orthopedic implantology. The main barrier to the use of Mg alloys in medicine is their overly fast and irregular degradation in body fluids. The use of protective calcium phosphate coatings to increase the corrosion resistance of Mg alloy (AM50 alloy: 4 wt.% Al, 0.3 wt.% Mn, 0.2 wt.% Zn, rest Mg) was examined in this study. The scientific goal of the study was the assessment of the influence of calcium phosphate layer morphology on the corrosion process in Ringer's solution. Modification of the coating morphology was obtained by changing the chemical composition of the phosphatizing bath using NaOH (NaAM50 sample) or ZnSO4 (ZnAM50 sample). In practice, a more dense and uniform coating could be obtained by the immersion of AM50 alloy in a solution containing ZnSO4 (ZnAM50 sample). In this study, an adhesion test performed on the ZnAM50 sample indicated that the critical load was 1.35 N. XRD phase analysis confirmed that the obtained coatings included dicalcium phosphate dihydrate (CaHPO4*2H2O). The coatings prepared on the NaAM50 and ZnAM50 samples are effective barriers against the progress of corrosion deeper into the substrate. After 120 h immersion in Ringer's solution, the volume of the evolved hydrogen was 5.6 mL/cm2 for the NaAM50 and 3.4 mL/cm2 for the ZnAM50 sample.

Biodegradable polymer coatings on Ti6Al7Nb alloy.

The aim of the study was to determine the influence of long term exposure to Ringer's solution of biodegradable polymer coatings containing an active substance on the Ti6Al7Nb alloy substrate on the physical and chemical properties of the coatings and the degradation process of the metal substrate. The studies used poly(L-lactide-co-trimethylene carbonate) P(L/TMC), poly(L-lactide-co-trimethylene carbonate-glycolide) P(L/TMC/G) and poly(D,L-lactide-glycolide) (PLGA) coatings applied to the anodically oxidized Ti6Al7Nb alloy by means of dipping method (1, 2 and 3 dips). The polymer coatings contained ciprofloxacin. Roughness and wettability tests were carried out on the substrate and polymer coatings, the pitting corrosion resistance of the substrate and samples with polymer coating was determined, the number of metallic ions released to the solution from the coated and uncoated samples was determined as well as the adhesion of polymer coatings. The research was supplemented by microscopic observations. The results of the research indicate different influence of exposure to Ringer's solution on the physical and chemical properties of biodegradable polymer coatings containing ciprofloxacin and the course of the degradation process of the metal substrate.

Phase composition and morphology characteristics of ceria-stabilized zirconia powders obtained via sol-gel method with various pH conditions.

PURPOSE: High purity, fine crystalline, degradation-free at low temperature powders have attracted special interest in CAD/CAM prosthetic dentistry full ceramic restorations. This study reports the preparation and characterisation of zirconia-ceria (0.9 ZrO2 0.1 CeO2) powders. Materials were obtained from zirconium-n-alkoxide and cerium nitrate hexahydrate in the pH 2-4 and 8-10. METHODS: Zirconia- ceria powders were obtained with the sol-gel method in a humid-free environment. Thermal analysis (TGA/DTA) of the as-prepared materials was made for an assessment of its behaviour at elevated temperatures. Specimens were dried at 80 °C and calcinated in two stages: at 300 °C with soaking time 2.5 h and 850 °C with holding time 2.5 h, in order to evaluate the phase transformations. Thermal analyses of the as-dried powders were made for an assessment of its thermal behaviour during heat treatment up to 1000 °C. By X-ray diffraction (XRD), polymorphs of ZrO2 were identified. Additionally, scanning electron microscopy (SEM) and laser particle size distribution (PSD) were involved for characterisation of morphology of the powders. RESULTS: A correlation between the pH of the colloidal system and the morphology of the as-obtained powders were found. Based on analysis (SEM, PSD), structures were identified known as soft and hard agglomerates. CONCLUSIONS: It can be stated that differences found between powder morphology were dependent on the value pH used, which can be crucial for powder densification during sintering and compacting green bodies which, as a consequence, may be crucial for the lifetime of zirconia prostheses. Correlations between phase composition and pH are difficult to grasp, and require further, more sophisticated, studies.

Evaluation of physicochemical properties of surface modified Ti6Al4V and Ti6Al7Nb alloys used for orthopedic implants.

The paper presents the results of selected functional properties of TiO2 layers deposited by ALD method on the surface of Ti6Al4V and Ti6Al7Nb alloys intended for implants in bone surgery. TiO2 layer was applied at the constant temperature of the ALD process at T=200°C at a variable number of cycles, which resulted in a different layer thickness. Different process cycles of 500, 1250, and 2500 were analyzed. The application of experimental methods (AFM, SEM, wettability, potentiodynamic test, EIS, scratch test, nanohardness and layer thickness) enabled to select the optimal number of cycles, and thus the thickness of the TiO2 layer of the most favorable functional properties. The obtained results clearly showed that regardless of the type of titanium substrate, the TiO2 layer applied in a 2500cycle ALD process has the best physicochemical and electrochemical properties. These properties have major impact on biocompatibility, and therefore the quality of the final product. The information obtained can be useful for manufacturers of medical devices involved in the production of implants used in reconstructive surgery of skeletal system.

Evaluation of physicochemical properties of SiO2-coated stainless steel after sterilization.

The study of most of the literature devoted to the use of coronary stents indicates that their efficiency is determined by the physicochemical properties of the implant surface. Therefore, the authors of this study suggested conditions for the formation of SiO2 layers obtained with the use of sol-gel methodology showing physicochemical properties adequate to the specific conditions of the cardio-vascular system. Previous experience of authors helped them much to optimize the coating of 316LVM steel surface with SiO2. The values of parameters that determine the usefulness of the coating in medical applications have been determined. In order to identify the phenomena taking place at the boundary of phases and to evaluate the usefulness of the proposed surface modification, taking into consideration the medical sterilization (steam or ethylene oxide (EO)), the potentiodynamic, impedance, adhesion, surface morphology and biological assessment characterizations were performed. Regardless of the usage of the sterilizing agent (steam, EO) the study showed the reduction of critical force causing layer's delamination. The research results of corrosion resistance study also confirmed a slight decrease of SiO2 barrier properties of the samples after sterilization in contact with the artificial plasma. SiO2 layers after the sterilization process did not show significant features of cytotoxicity and had no negative influence on blood cell counts, which confirmed the results of quantitative and qualitative studies.

Comparative characteristics of endodontic drills.

The work concerns the analysis of influence of the wear process of endodontic instruments on the mechanical and physico-chemical properties of the materials from which they are made. A detailed study of the microstructure, mechanical properties and corrosion resistance in the environment simulating work of the tool was conducted. The research was done for the new Mtwo endodontic files and after six times of use. In addition, the observations with a scanning electron microscope in order to reveal possible damage caused by the impact of a corrosive environment were carried out. The results showed that use of the tool by six times revealed damage at the edges of the blades and may cause a lack of continuity of the cutting line resulting in the uneven distribution of the resistive force which acts on the tool during operation.

Technological capabilities of surface layers formation on implant made of Ti-6Al-4V ELI alloy.

PURPOSE: The aim of the presented research was to find a combination of surface modification methods of implants made of the Ti-6Al-4V ELI alloy, that lead to formation of effective barrier for metallic ions that may infiltrate into solution. METHODS: To this end, the following tests were carried out: roughness measurement, the voltamperometric tests (potentiodynamic and potentiostatic), and the ion infiltration test. RESULTS: The electropolishing process resulted in the lowering of surface roughness in comparison with mechanical treatment of the surface layer. The anodization process and steam sterilization increased corrosion resistance regardless of the mechanical treatment or electropolishing. The crevice corrosion tests revealed that independent of the modification method applied, the Ti-6Al-4V ELI alloy has excellent crevice corrosion resistance. The smallest quantity of ions infiltrated to the solution was observed for surface modification consisting in the mechanical treatment and anodization with the potential of 97 V. CONCLUSIONS: Electric parameters deter- mined during studies were the basis for effectiveness estimation of particular surface treatment methods. The research has shown that the anodization process significantly influences the pitting corrosion resistance of the Ti-6Al-4V ELI alloy independent of the previous surface treatment methods (mechanical and electrochemical). The surface layer after such modification is a protective barrier for metallic ions infiltrated to solution and protects titanium alloy against corrosive environment influence.

The effects of a SiO2 coating on the corrosion parameters cpTi and Ti-6Al-7Nb alloy.

The aim of this paper was to evaluate the usefulness of the sol-gel method application, to modificate the surface of the Ti6Al7Nb alloy and the cpTi titanium (Grade 4) with SiO2 oxide, applied on the vascular implants to improve their hemocompatibility. Mechanical treatment was followed by film deposition on surface of the titanium samples. An appropriate selection of the process parameters was verified in the studies of corrosion, using potentiodynamic and impedance method. A test was conducted in the solution simulating blood vessels environment, in simulated body fluid at t = 37.0 ± 1 °C and pH = 7.0 ± 0.2. Results showed varied electrochemical properties of the SiO2 film, depending on its deposition parameters. Correlations between corrosion resistance and layer adhesion to the substrate were observed, depending on annealing temperature.

Biomechanical analysis of limited-contact plate used for osteosynthesis.

This paper presents the results of numerical analysis aimed at determining the state of stresses and displacements of compression plate used in osteosynthesis of tibia, carried out by applying finite element method using the ANSYS program. The analysis took into account two variants of the osteosynthesis. Variant I included the osteosynthesis in which plate was attached directly to the bone, in variant II, the plate was moved away from the bones by about 5 mm. Biomechanical characteristics of the corrective osteotomy plate-tibia was determined for implants made of Ti-6Al-4V alloy. The boundary conditions adopted for the analysis reflect phenomena occurring in a real system. Based on the results of the analysis relative displacements and reduced stresses in various components were determined as a function of the applied load within the range of F = 500-1500 N. The maximum forces, both variant I and variant II determined during analysis, ensure that the generated stress does not exceed yield strength of the material and compressive strength of the bone, and do not exceed safety movement in the fracture gap. In addition, it was found that the locking of the compressive plate to the bone has a little effect on the distribution of displacements and stresses on the plate-tibia system in the case of a simple fracture.

Influence of surgical drills wear on thermal process generated in bones.

The influence of the wear rate of drills used in bone surgery on the temperature distribution in the femur models (Sawbones) is presented in the paper. Surgical drills of diameter d = 4.5 mm and diverse edge geometry (90° and 120°) were selected for the study. In order to carry out thermal analysis with the use of finite element, experimental studies of wear process were necessary. These studies, among others, consisted in determination of average values of axial forces and cutting torques as a function of the number of drilled holes. The study showed an impact of the drill geometry on values that describe cutting process. It was found that the greatest values of torques and axial cutting forces occur in drills of point angle of 120°. Next, in order to determine the effect of wear rate on the generation of temperature in the cutting zone, thermal analysis of the drilling process using the finite element method was carried out. It was found that higher temperatures in the bone are observed for drilling with the use of the drill of point angle equal to 120°, as in the experimental study. For the tools of such edge geometry the wear of cutting edge is more intensive and the generated temperature in femur for the wear land VBB = 0.32 mm has reached the critical value associated with the process of thermal necrosis.

Numerical and experimental analyses of drills used in osteosynthesis.

This paper presents the results of numerical analysis and experimental studies of the process of bone drilling using drills applied in osteosynthesis procedures. In the studies, two surgical drills with a diameter d = 4.5 mm and varying in drill point geometry 2κ were used. Thermal analysis based on FEM allowed determining the distribution of temperatures generated in the bone as a function of rotational speed of the drill. The results indicate that both drill point geometry and rotational speed of the drill have influence on temperatures generated in bone tissue. Additionally, the range was determined for possible values of rotational speed, which does not initiate the process of thermal necrosis of bone. The experimental studies of the process of drilling in a femur model showed the impact of drill point geometry on the values describing the cutting process. It was concluded that the highest values of torques and axial forces during cutting occur in the tools with angle 2κ2 = 120°.