Introduction to the RSC Advances themed collection on nano and microscale modifications of biomaterials.

Andrzej Zielinski and Beata Majkowska-Marzec introduce the RSC Advances themed collection on nano and microscale modifications of biomaterials.

Evaluation of adhesion strength, corrosion, and biological properties of the MWCNT/TiO2 coating intended for medical applications.

Multi-wall carbon nanotube (MWCNT) coatings are gaining increasing interest because of their special properties used in many science fields. The titania coatings are known for their improvement of osteoblast adhesion, thus changing the surface architecture. Bi-layer coatings comprising 0.25 wt% of the MWCNTs and 0.30 wt% of titania (anatase structure) were synthesized in a two-stage procedure using the electrophoretic deposition method (EPD). The MWCNT and TiO2 coatings were deposited with voltage and time parameters, respectively, of 20 V and 0.5 min, and 50 V and 4 min. EDS, AFM, SEM, Raman spectroscopy, nano-scratch test, potentiodynamic corrosion tests, wettability studies, and cytotoxicity determined with MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) test on human dermal fibroblasts (HDF) and mouse osteoblast precursors (MC3T3), and lactate dehydrogenase (LDH) activity test were carried out on examined surfaces. The prepared MWCNT/TiO2 coating is uniformly distributed by MWCNTs and agglomerated by TiO2 particles of size ranging from 0.1 to 3 µm. Raman spectroscopy confirmed the anatase structure of the TiO2 addition and showed typical peaks of the MWCNTs. The MWCNT/TiO2 coating had higher roughness, higher adhesion strength, and improved corrosion resistance compared to the MWCNT basic coating. The results of biological tests proved that physicochemical properties of the surface, such as high porosity and wettability of MWCNT/TiO2-coated material, would support cell adhesion, but toxic species could be released to the culture medium, thus resulting in a decrease in proliferation.

Mechanical Properties and Wear Susceptibility Determined by Nanoindentation Technique of Ti13Nb13Zr Titanium Alloy after "Direct Laser Writing".

Laser treatment has often been applied to rebuild the surface layer of titanium and its alloys destined for long-term implants. Such treatment has always been associated with forming melted and re-solidified thin surface layers. The process parameters of such laser treatment can be different, including the patterning of a surface by so-called direct writing. In this research, pulse laser treatment was performed on the Ti13Nb13Zr alloy surface, with the distance between adjacent laser paths ranging between 20 and 50 µm. The obtained periodic structures were tested to examine the effects of the scan distance on the microstructure using SEM, the roughness and chemical and phase composition using EDS and XRD, and the mechanical properties using the nanoindentation technique. After direct laser writing, the thickness of the melted layers was between 547 and 123 µm, and the surface roughness varied between 1.74 and 0.69 µm. An increase in hardness was observed after laser treatment. The highest hardness, 5.44 GPa, was obtained for the sample modified with a laser beam spacing of 50 µm. The value of the distance has been shown to be important for several properties and related to a complex microstructure of the thin surface layer close to and far from the laser path.

Effect of pulse laser treatment at different process variables on mechanical behavior of carbon nanotubes electrophoretically deposited on titanium alloy.

PURPOSE: Titanium and its alloys are widely used as biomaterials for long-term implants, but they are usually surface-modified due to their weak bioactivity and wear resistance. Laser processing was used to modify the surface layer, and elemental carbon was a component of the deposited coatings. This research aims to use a combination of both methods based on preliminary electrophoretic deposition of multi-wall carbon nanotubes (MWNCTs) followed by pulse laser treatment. Carbon nanotubes were chosen due to their mechanical and chemical stability as well as their tubular shape, resulting in enhanced mechanical properties of laser-modified layers. METHODS: The pulse laser power and laser scanning speed were defined as variable process parameters. The microstructure, roughness Ra, nanohardness H, Young's modulus E, and indent depth values were measured, and the H/E, H 3/E2, and relative changes of all these values in comparison to MWCNTs-coated and non-coated surfaces, were calculated. RESULTS: The obtained results show that the best mechanical properties of MWCNTs-coated and laser-treated specimens are obtained at a laser power of 900 W and laser feed of 6 mm/s. The observed relations can be explained considering processes occurring on the surface such as deposition of carbon nanotubes, melting and re-crystallization of the surface layer, formation and possible partial decomposition of titanium carbides, and associated changes in local chemical composition, phase composition, and a level of residual stresses beneath the surface. CONCLUSIONS: The developed process can substitute the time and money-consuming carbonization of titanium and its alloys.

Influence of Surface Modification of Titanium and Its Alloys for Medical Implants on Their Corrosion Behavior.

Titanium and its alloys are often used for long-term implants after their surface treatment. Such surface modification is usually performed to improve biological properties but seldom to increase corrosion resistance. This paper presents research results performed on such metallic materials modified by a variety of techniques: direct voltage anodic oxidation in the presence of fluorides, micro-arc oxidation (MAO), pulse laser treatment, deposition of chitosan, biodegradable Eudragit 100 and poly(4-vinylpyridine (P4VP), carbon nanotubes, nanoparticles of TiO2, and chitosan with Pt (nano Pt) and polymeric dispersant. The open circuit potential, corrosion current density, and potential values were determined by potentiodynamic technique, and microstructures of the surface layers and coatings were characterized by scanning electron microscopy. The results show that despite the applied modifications, the corrosion current density still appears in the region of very low values of some nA/cm2. However, almost all surface modifications, designed principally for the improvement of biological properties, negatively influence corrosion resistance. The reasons for observed effects can vary, such as imperfections and permeability of some coatings or accelerated degradation of biodegradable deposits in simulated body fluids during electrochemical testing. Despite that, all coatings can be accepted for biological applications, and such corrosion testing results are presumed not to be of major importance for their applications in medicine.

Mechanical Behavior of Bi-Layer and Dispersion Coatings Composed of Several Nanostructures on Ti13Nb13Zr Alloy.

Titanium implants are commonly used because of several advantages, but their surface modification is necessary to enhance bioactivity. Recently, their surface coatings were developed to induce local antibacterial properties. The aim of this research was to investigate and compare mechanical properties of three coatings: multi-wall carbon nanotubes (MWCNTs), bi-layer composed of an inner MWCNTs layer and an outer TiO2 layer, and dispersion coatings comprised of simultaneously deposited MWCNTs and nanoCu, each electrophoretically deposited on the Ti13Nb13Zr alloy. Optical microscopy, scanning electron microscopy, X-ray electron diffraction spectroscopy, and nanoindentation technique were applied to study topography, chemical composition, hardness, plastic and elastic properties. The results demonstrate that the addition of nanocopper or titanium dioxide to MWCNTs coating increases hardness, lowers Young's modulus, improves plastic and elastic properties, wear resistance under deflection, and plastic deformation resistance. The results can be attributed to different properties, structure and geometry of applied particles, various deposition techniques, and the possible appearance of porous structures. These innovative coatings of simultaneously high strength and elasticity are promising to apply for deposition on long-term titanium implants.

Mechanical and Corrosion Properties of Laser Surface-Treated Ti13Nb13Zr Alloy with MWCNTs Coatings.

Titanium and its alloys is the main group of materials used in prosthetics and implantology. Despite their popularity and many advantages associated with their biocompatibility, these materials have a few significant disadvantages. These include low biologic activity-which reduces the growth of fibrous tissue and allows loosening of the prosthesis-the possibility of metallosis and related inflammation or other allergic reactions, as well as abrasion of the material during operation. Searching for the best combinations of material properties for implants in today's world is not only associated with research on new alloys, but primarily with the modification of their surface layers. The proposed laser modification of the Ti13Nb13Zr alloy with a carbon nanotube coating is aimed at eliminating most of the problems mentioned above. The carbon coating was carried out by electrophoretic deposition (EPD) onto ground and etched substrates. This form of carbon was used due to the confirmed biocompatibility with the human body and the ability to create titanium carbides after laser treatment. The EPD-deposited carbon nanotube coating was subjected to laser treatment. Due to high power densities applied to the material during laser treatment, non-equilibrium structures were observed while improving mechanical and anti-corrosive properties. An electrophoretically deposited coating of carbon nanotubes further improved the effects of laser processing through greater strengthening, hardness or Young's modulus similar to that required, as well as led to an increase in corrosion resistance. The advantage of the presented laser modification of the Ti13Nb13Zr alloy with a carbon coating is the lack of surface cracks, which are difficult to eliminate with traditional laser treatment of Ti alloys. All samples tested showed contact angles between 46° and 82° and thus, based on the literature reports, they have hydrophilic surfaces suitable for cell adhesion.

Hydrogen Embrittlement and Oxide Layer Effect in the Cathodically Charged Zircaloy-2.

The present paper is aimed at determining the less investigated effects of hydrogen uptake on the microstructure and the mechanical behavior of the oxidized Zircaloy-2 alloy. The specimens were oxidized and charged with hydrogen. The different oxidation temperatures and cathodic current densities were applied. The scanning electron microscopy, X-ray electron diffraction spectroscopy, hydrogen absorption assessment, tensile, and nanoindentation tests were performed. At low oxidation temperatures, an appearance of numerous hydrides and cracks, and a slight change of mechanical properties were noticed. At high-temperature oxidation, the oxide layer prevented the hydrogen deterioration of the alloy. For nonoxidized samples, charged at different current density, nanoindentation tests showed that both hardness and Young's modulus revealed the minims at specific current value and the stepwise decrease in hardness during hydrogen desorption. The obtained results are explained by the barrier effect of the oxide layer against hydrogen uptake, softening due to the interaction of hydrogen and dislocations nucleated by indentation test, and hardening caused by the decomposition of hydrides. The last phenomena may appear together and result in hydrogen embrittlement in forms of simultaneous hydrogen-enhanced localized plasticity and delayed hydride cracking.