Anodic Production and Characterization of Biomimetic Oxide Layers on Grade 4 Titanium for Medical Applications.

Biomaterials are the basis for the development of medicine because they allow safe contact with a living organism. The aim of this work was to produce innovative oxide layers with a microporous structure on the surface of commercially pure titanium Grade 4 (CpTi G4) and to characterize their properties as drug carriers. The anodization of the CpTi G4 subjected to mechanical grinding and electrochemical polishing was carried out in a solution of 1M ethylene glycol with the addition of 40 g of ammonium fluoride at a voltage of 20 V for 2, 18, 24, and 48 h at room temperature. It was found that the longer the anodization time, the greater the number of pores formed on the CpTi G4 surface as revealed using the FE-SEM method, and the greater the surface roughness determined in profilometric tests. As the anodizing time increases, the amount of the drug in the form of gentamicin sulfate incorporated into the resulting pores decreases. The most favorable drug release kinetics profile determined via UV-VIS absorption spectroscopy was found for the CpTi G4 anodized for 2 h.

Electrophoretic Deposition of Multi-Walled Carbon Nanotube Coatings on CoCrMo Alloy for Biomedical Applications.

Carbon nanotubes are a promising material for use in innovative biomedical solutions due to their unique chemical, mechanical, electrical, and magnetic properties. This work provides a method for the development of ultrasonically assisted electrophoretic deposition of multi-walled carbon nanotubes on a CoCrMo dental alloy. Functionalization of multi-walled carbon nanotubes was carried out by chemical oxidation in a mixture of nitric and sulfuric acids. The modified and unmodified multi-walled carbon nanotubes were anaphoretically deposited on the CoCrMo alloy in an aqueous solution. Chemical composition was studied by Fourier transform infrared spectroscopy. Surface morphology was examined by scanning electron microscopy. The mechanism and kinetics of the electrochemical corrosion of the obtained coatings in artificial saliva at 37 °C were determined using the open-circuit potential method, electrochemical impedance spectroscopy, and anodic polarization curves. The capacitive behavior and high corrosion resistance of the tested electrodes were revealed. It was found that the kinetics of electrochemical corrosion of the CoCrMo electrode significantly decreased in the presence of the functionalized multi-walled carbon nanotube coating. Electrophoretic deposition was shown to be an effective, low-cost, and fast method of producing nanotubes with controlled thickness, homogeneity, and packing density.

Effect of Artificial Saliva Modification on Pitting Corrosion and Mechanical Properties of the Remanium®-Type Orthodontic Archwire.

The pitting corrosion of orthodontic apparatus elements in the oral environment is an interest of both clinicians and scientists dealing with the assessment of the biocompatibility of medical materials. This work presents a study on the effect of ready-to-use Listerine® and Meridol® mouthwashes and sodium fluoride on the resistance of the commercial Remanium®-type orthodontic archwire to pitting corrosion in artificial saliva at 37 °C. XRD, SEM, EDS, mechanical properties, and microhardness measurements were used to characterize the archwire. The in vitro corrosion resistance of the archwire was examined using the open-circuit potential method, electrochemical impedance spectroscopy, and anodic polarization curves. The physicochemical characteristics confirmed the presence of a bi-phase alloy with a mixed austenite/ferrite structure containing Fe 74.4(7) at.%, Cr 18.4(4) at.%, and Ni 7.2(4) at.%. The Fe-Cr-Ni alloy was characterized by high tensile strength and Vickers microhardness. EIS revealed the capacitive behavior with high corrosion resistance. It was found that the kinetics of pitting corrosion in the artificial saliva decreased in the presence of NaF and mouthwashes. The potentiodynamic characteristics confirmed the decrease in susceptibility to pitting corrosion after the modification of artificial saliva. The pitting corrosion mechanism of the self-passive oxide layer on the surface of the Fe-Cr-Ni electrode in the biological environment containing chloride ions was discussed in detail. Mechanical properties after corrosion tests were weakened.

Biological Activity and Thrombogenic Properties of Oxide Nanotubes on the Ti-13Nb-13Zr Biomedical Alloy.

The success of implant treatment is dependent on the osseointegration of the implant. The main goal of this work was to improve the biofunctionality of the Ti-13Nb-13Zr implant alloy by the production of oxide nanotubes (ONTs) layers for better anchoring in the bone and use as an intelligent carrier in drug delivery systems. Anodization of the Ti-13Nb-13Zr alloy was carried out in 0.5% HF, 1 M (NH4)2SO4 + 2% NH4F, and 1 M ethylene glycol + 4 wt.% NH4F electrolytes. Physicochemical characteristics of ONTs were performed by high-resolution electron microscopy (HREM), X-ray photoelectron spectroscopy (XPS), and scanning Kelvin probe (SKP). Water contact angle studies were conducted using the sitting airdrop method. In vitro biological properties and release kinetics of ibuprofen were investigated. The results of TEM and XPS studies confirmed the formation of the single-walled ONTs of three generations on the bi-phase (α + ß) Ti-13Nb-13Zr alloy. The ONTs were composed of oxides of the alloying elements. The proposed surface modification method ensured good hemolytic properties, no cytotoxity for L-929 mouse cells, good adhesion, increased surface wettability, and improved athrombogenic properties of the Ti-13Nb-13Zr alloy. Nanotubular surfaces allowed ibuprofen to be released from the polymer matrix according to the Gallagher-Corrigan model.

In Vitro Bioelectrochemical Properties of Second-Generation Oxide Nanotubes on Ti-13Zr-13Nb Biomedical Alloy.

Surface charge and in vitro corrosion resistance are some of the key parameters characterizing biomaterials in the interaction of the implant with the biological environment. Hence, this work investigates the in vitro bioelectrochemical behavior of newly developed oxide nanotubes (ONTs) layers of second-generation (2G) on a Ti-13Zr-13Nb alloy. The 2G ONTs were produced by anodization in 1 M (NH4)2SO4 solution with 2 wt.% of NH4F. The physical and chemical properties of the obtained bamboo-inspired 2G ONTs were characterized using scanning electron microscopy with field emission and energy dispersive spectroscopy. Zeta potential measurements for the examined materials were carried out using an electrokinetic analyzer in aqueous electrolytes of potassium chloride, phosphate-buffered saline and artificial blood. It was found that the electrolyte type and the ionic strength affect the bioelectrochemical properties of 2G ONTs layers. Open circuit potential and anodic polarization curve results proved the influence of anodizing on the improvement of in vitro corrosion resistance of the Ti-13Zr-13Nb alloy in PBS solution. The anodizing conditions used can be proposed for the production of long-term implants, which are not susceptible to pitting corrosion up to 9.4 V.

Influence of Anodizing Conditions on Biotribological and Micromechanical Properties of Ti-13Zr-13Nb Alloy.

The biomedical Ti-13Zr-13Nb bi-phase (α + ß) alloy for long-term applications in implantology has recently been developed. The porous oxide nanotubes' (ONTs) layers of various geometries and lengths on the Ti-13Zr-13Nb alloy surface can be produced by anodizing to improve osseointegration. This work was aimed at how anodizing conditions determinatine the micromechanical and biotribological properties of the Ti-13Zr-13Nb alloy. First-generation (1G), second-generation (2G), and third-generation (3G) ONT layers were produced on the Ti-13Zr-13Nb alloy surface by anodizing. The microstructure was characterized using SEM. Micromechanical properties were investigated by the Vickers microhardness test under variable loads. Biotribological properties were examined in Ringer's solution in a reciprocating motion in the ball-on-flat system. The 2D roughness profiles method was used to assess the wear tracks of the tested materials. Wear scars' analysis of the ZrO2 ball was performed using optical microscopy. It was found that the composition of the electrolyte with the presence of fluoride ions was an essential factor influencing the micromechanical and biotribological properties of the obtained ONT layers. The three-body abrasion wear mechanism was proposed to explain the biotribological wear in Ringer's solution for the Ti-13Zr-13Nb alloy before and after anodizing.

Production and Characterization of the Third-Generation Oxide Nanotubes on Ti-13Zr-13Nb Alloy.

In the group of vanadium-free titanium alloys used for applications for long-term implants, the Ti-13Zr-13Nb alloy has recently been proposed. The production of a porous layer of oxide nanotubes (ONTs) with a wide range of geometries and lengths on the Ti-13Zr-13Nb alloy surface can increase its osteoinductive properties and enable intelligent drug delivery. This work concerns developing a method of electrochemical modification of the Ti-13Zr-13Nb alloy surface to obtain third-generation ONTs. The effect of the anodizing voltage on the microstructure and thickness of the obtained oxide layers was conducted in 1 M C2H6O2 + 4 wt% NH4F electrolyte in the voltage range 5-35 V for 120 min at room temperature. The obtained third-generation ONTs were characterized using SEM, EDS, SKP, and 2D roughness profiles methods. The preliminary assessment of corrosion resistance carried out in accelerated corrosion tests in the artificial atmosphere showed the high quality of the newly developed ONTs and the slight influence of neutral salt spray on their micromechanical properties.

The Influence of the Gradient Infill of PLA Samples Produced with the FDM Technique on Their Mechanical Properties.

Three-dimensional printing is a dynamically developing field of industry. Its main advantage is the small amount of waste, no need to use specialized tools, and easy control of the mechanical properties of the printed model. One of the most popular techniques of 3D printing is FDM. The main factor influencing the mechanical properties of 3D-printed materials is the filling density. The aim of this study was to determine the mechanical properties of porous structures with a porosity gradient of PLA samples printed using the FDM technique. The accuracy of mapping the structures by computed tomography was assessed, and then a static compression test was performed. It has been shown that the strength properties increased with the increase in the filling density. The highest value of compression strength, amounting to 41.2 MPa, was observed for samples made of PLA with an 80% filling degree, whereas the lowest value of compression strength was found in PLA-T samples with a filling degree of 10%, reaching only 0.6 MPa. It was found that not only the core filling density, but also the outer layers, influences the mechanical properties. The assessment of spatial architecture allowed for a qualitative and quantitative assessment. The obtained images from the computed tomograph showed that the designed sample models were correctly reproduced in the entire volume.

Influence of Sandblasting Process on Tribological Properties of Titanium Grade 4 in Artificial Saliva for Dentistry Applications.

Titanium Grade 4 (Ti G4) is widely used in medicine for dental implants. The failure-free life of implants depends on their properties such as resistance to wear and friction processes. This paper presents an analysis of the influence of sandblasting on tribological wear of commercial dental implants made of TiG4 in artificial saliva. Tribological wear measurements were performed in a reciprocating motion in the ball-on-disc system. The scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS) method was used to characterize the surface of the implants before and after the tribological wear test. The microhardness of Ti G4 was measured before and after sandblasting by the Vickers method. The contact angle was determined by the method of sitting drop in air. The residual stress test using the X-Ray Diffraction (XRD) single-{hkl} sin2ψ method was carried out. The compressive residual stress of 324(7) MPa and surface hardening of Ti G4 was revealed after sandblasting with Al2O3 particles of 53-75 µm in diameter. It was found that sandblasting changes the surface wettability of Ti G4. The intermediate wettability of the mechanically polished surface and the hydrophobicity of the sandblasted surface was revealed. Sandblasting reduces the tribological wear and friction coefficient of Ti G4 surface in saliva. The three-body abrasion wear mechanism was proposed to explain the tribological wear of Ti G4 in saliva.

Production, Characterization and Application of Oxide Nanotubes on Ti-6Al-7Nb Alloy as a Potential Drug Carrier.

This work concerns the development of a method of functionalization of the surface of the biomedical Ti-6Al-7Nb alloy by producing oxide nanotubes (ONTs) with drug-eluting properties. Shaping of the morphology, microstructure, and thickness of the oxide layer was carried out by anodization in an aqueous solution of 1 M ethylene glycol with the addition of 0.2 M NH4F in the voltage range 5-100 V for 15-60 min at room temperature. The characterization of the physicochemical properties of the obtained ONTs was performed using SEM, XPS, and EDAX methods. ONTs have been shown to be composed mainly of TiO2, Al2O3, and Nb2O5. Single-walled ONTs with the largest specific surface area of 600 cm2 cm-2 can be obtained by anodization at 50 V for 60 min. The mechanism of ONT formation on the Ti-6Al-7Nb alloy was studied in detail. Gentamicin sulfate loaded into ONTs was studied using FTIR, TG, DTA, and DTG methods. Drug release kinetics was determined by UV-Vis spectrophotometry. The obtained ONTs can be proposed for use in modern implantology as carriers for drugs delivered locally in inflammatory conditions.

Effect of Temperature on Electrochemically Assisted Deposition and Bioactivity of CaP Coatings on CpTi Grade 4.

Calcium phosphate (CaP) coatings are able to improve the osseointegration process due to their chemical composition similar to that of bone tissues. Among the methods of producing CaP coatings, the electrochemically assisted deposition (ECAD) is particularly important due to high repeatability and the possibility of deposition at room temperature and neutral pH, which allows for the co-deposition of inorganic and organic components. In this work, the ECAD of CaP coatings from an acetate bath with a Ca:P ratio of 1.67, was developed. The effect of the ECAD conditions on CaP coatings deposited on commercially pure titanium grade 4 (CpTi G4) subjected to sandblasting and autoclaving was presented. The physicochemical characteristics of the ECAD-derived coatings was carried out using SEM, EDS, FTIR, 2D roughness profiles, and amplitude sensitive eddy current method. It was showed that amorphous calcium phosphate (ACP) coatings can be obtained at a potential -1.5 to -10 V for 10 to 60 min at 20 to 70 °C. The thickness and surface roughness of the ACP coatings were an increasing function of potential, time, and temperature. The obtained ACP coatings are a precursor in the process of apatite formation in a simulated body fluid. The optimal ACP coating for use in dentistry was deposited at a potential of -3 V for 30 min at 20 °C.

Long-Term Assessment of the In Vitro Corrosion Resistance of Biomimetic ACP Coatings Electrodeposited from an Acetate Bath.

Calcium phosphate coatings are able to improve the osseointegration process due to their chemical composition, which is similar to that of bone tissues. In this work, to increase the long-term corrosion resistance and to improve the osseointegration process of commercially pure titanium Grade 4 (CpTi G4), biomimetic amorphous calcium phosphate (ACP) coatings were electrodeposited for the first time from an acetate bath with a pH level of 7.0 and a Ca:P ratio of 1.67. ACP coatings were obtained on CpTi G4 substrate subjected to sandblasting and autoclaving using electrochemically assisted deposition at a potential of -3 V relative to the open circuit potential for 30 min at room temperature. SEM, EDS, 2D roughness profiles, amplitude-sensitive eddy current method, and Kelvin scanning probe were used for the surface characterization of the biomaterial under study. In vitro corrosion resistance tests were conducted for 21 days in artificial saliva using open circuit potential, polarization curves, and electrochemical impedance spectroscopy measurements. The passive-transpassive behavior was revealed for the obtained ACP coatings. The long-term corrosion resistance test showed a deterioration of the protective properties for CpTi G4 uncoated and coated with ACP with immersion time. The mechanism and kinetics of the pitting corrosion on the CpTi G4|TiO2|ACP coating system are discussed in detail.

Effect of Autoclaving Time on Corrosion Resistance of Sandblasted Ti G4 in Artificial Saliva.

Titanium Grade 4 (Ti G4) is the most commonly used material for dental implants due to its excellent mechanical properties, chemical stability and biocompatibility. A thin, self-passive oxide layer with protective properties to corrosion is formed on its surface. However, the spontaneous TiO2 layer is chemically unstable. In this work, the impact of autoclaving time on corrosion resistance of Ti G4 in artificial saliva solution with pH = 7.4 at 37 °C was studied. Ti G4 was sandblasted with white Al2O3 particles and autoclaved for 30-120 min. SEM, EDS, 2D roughness profiles, confocal laser scanning microscopy, and a Kelvin scanning probe were used for the surface characterization of the Ti G4 under study. In vitro corrosion resistance tests were conducted using open circuit potential, polarization curves, and electrochemical impedance spectroscopy measurements. It was found that Sa parameter, electron work function, and thickness of the oxide layers, determined based on impedance measurements, increased after autoclaving. The capacitive behavior and high corrosion resistance of tested materials were revealed. The improvement in the corrosion resistance after autoclaving was due to the presence of oxide layers with high chemical stability. The optimal Ti G4 surface for dentistry can be obtained by sandblasting with Al2O3 with an average grain size of 53 µm, followed by autoclaving for 90 min.

Effect of Hydrogen Electrosorption on Mechanical and Electronic Properties of Pd80Rh20 Alloy.

The interaction of hydrogen with Pt-group metals and alloys is at the center of research in the fields of electrochemistry, electrocatalysis, hydrogen technologies and fuel cells developed under the Hydrogen Economy. In this work, the material under study was Pd80Rh20 alloy (50 µm foil) subjected to hydrogen electrosorption at potentials corresponding to formation of α, α-ß and ß phase in 0.1 M H2SO4 at 25 °C. The total amount of hydrogen adsorbed at the surface and absorbed in octahedral interstitial positions of fcc Pd80Rh20 alloy, was determined from the oxidation charges. The H/(Pd+Rh) was 0.002, 0.4 and 0.8 for α, α-ß, and ß Pd80Rh20H, respectively. Microindentation hardness testing and nanoindentation showed weakening of mechanical properties of the Pd80Rh20 alloy after hydrogen electrosorption due to internal stresses. Decrease of work function with increasing amount of hydrogen absorbed occurred due to the surface roughness changes and the presence of electropositive hydrogen atoms absorbed in the crystal lattice responsible for the dipole interaction. The detailed mechanism of hydrogen absorption/diffusion in the Pd80Rh20 alloy structure is discussed. The obtained results give a new insight into the relationship between the amount of absorbed hydrogen and mechanical and electronic properties of the Pd80Rh20 alloy at the micro- and nanoscale.