This study examines the effect of electron beam treatment (EBT) of Co–Cr substrate on the film growth mechanism, mechanical properties, and surface topography of TiN/TiO2 coatings deposited by reactive magnetron sputtering. The obtained results and processes that occurred during the deposition are discussed in the context of crystallographic principles, and special attention is paid to the crystallographic orientation and growth mechanism studied by X-ray diffraction (XRD). The mechanical properties were investigated by means of nanoindentation and wear tests. The surface topography was evaluated using atomic force microscopy (AFM). The results obtained in the present study showed that polycrystalline TiN and anatase TiO2 phases were present in all cases. Electron beam treatment of Co–Cr substrate tended to form a reorientation of the microvolumes from (111) to (200) of TiN, leading to a change in the growth mechanism from three-dimensional (Volmer–Weber) to layer-by-layer (Frank–van der Merwe). It was found that the electron beam treatment process did not significantly affect the thickness of the coatings and the deposition rate. The treatment process led to an increase in surface roughness. The higher surface roughness after the EBT process should be appropriate to support cell growth and adhesion on the surface of the deposited bilayer coating. It was demonstrated that EBT of the substrate caused a decrease in hardness of the deposited coatings from 10 to 5 GPa. The observed decrease in hardness was attributed to the change in the preferred crystallographic orientation and film growth mechanism. The hardness of the bilayer coating after the application of EBT of the Co–Cr substrate was much closer to that of human bones, which means that severe stress shielding effect could not be expected. The evaluated coefficient of friction (COF) exhibited significantly lower values in the case of EBT of the substrate compared to the untreated Co–Cr material.
This work presents results on the influence of thickness on the structure and biological response of Cu-O coatings deposited on commercially pure titanium (cpTi) substrates using direct current (DC) magnetron sputtering. The deposition times were 5, 10, and 15 min to obtain coatings with different thicknesses. The results show that the films deposited for 5, 10, and 15 min correspond to thicknesses of 41, 74, and 125 nm, respectively. The phase composition of the coatings is in the form of a double-phase structure of CuO and Cu2O in all considered cases. The roughness is on the nanometric scale and no obvious trend as a function of the thickness can be observed for the deposited films. Also, it was found that, with an increase in the thickness of the films, the distribution of the heights becomes closer to symmetrical. The antimicrobial efficacy of different Cu-O-coated cpTi substrates was examined using a direct contact experiment. A possible bactericidal effect was investigated by inoculating a 200 μL bacterial suspension on CuO-coated cpTi and cpTi (control) for 24 h at 37 °C. The results showed that Cu-O-coated cpTi substrates have a 50%–60% higher antimicrobial activity than the substrate. At the same time, human osteosarcoma (MG-63) cells growing on Cu-O-coated cpTi substrates showed 80% viability following 24 h incubation. Depending on magnetron sputtering process parameters, a different coating thickness, various crystallite phase compositions, and diverse biocompatibility were obtained.
One of the primary risk factors for implant failure is thought to be implant-related infections during the early healing phase. Developing coatings with cell stimulatory behaviour and bacterial adhesion control is still difficult for bone implants. This study proposes an approach for one-step deposition of biocompatible and antimicrobial Cu-doped TiO2 coatings via glow-discharge sputtering of a mosaic target. During the deposition, the bias of the Ti6Al4V substrates was changed. Structure examination, phase analysis, and surface morphology were carried out using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The hardness values and hydrophilic and corrosion performance were also evaluated together with cytocompatible and antibacterial examinations against E. coli and S. aureus. The results show great chemical and phase control of the bias identifying rutile, anatase, CuO, or ternary oxide phases. It was found that by increasing the substrate bias from 0 to −50 V the Cu content increased from 15.3 up to 20.7 at% while at a high bias of −100 V, the copper content reduced to 3 at%. Simultaneously, apart from the Cu2+ state, Cu1+ is also found in the biased samples. Compared with the bare alloy, the hardness, the water contact angle and corrosion resistance of the biased coatings increased. According to an assessment of in vitro cytocompatibility, all coatings were found to be nontoxic to MG-63 osteoblast cells over the time studied. Copper release and cell-surface interactions generated an antibacterial effect against E. coli and S. aureus strains. The −50 V biased coating combined the most successful results in inhibiting bacterial growth and eliciting the proper responses from osteoblastic cells because of its phase composition, electrochemical stability, hydrophilicity, improved substrate adhesion, and surface roughness. Using this novel surface modification approach, we achieved multifunctionality through controlled copper content and oxide phase composition in the sputtered films.
Titanium alloys are widely used for biomedical implants, but their performance is limited by wear, corrosion, and susceptibility to bacterial colonisation. To overcome these drawbacks, multilayer Ti–Cu oxide coatings were deposited on Ti6Al4V substrates using direct current magnetron sputtering. Two multilayer architectures (6 × 2 and 12 × 2 TiO2/CuO bilayers) were fabricated and evaluated for their structural, mechanical, electrochemical, and biological properties. SEM/EDS and XRD confirmed well-adhered crystalline coatings consisting of rutile/anatase TiO2 and monoclinic CuO with uniform elemental distribution. The coatings increased surface roughness, improved adhesion, and enhanced hardness by up to ~180% compared to uncoated Ti6Al4V alloy. Compared to the bare substrate, electrochemical testing in simulated body fluid showed higher corrosion resistance of both coated samples, but particularly for the 12 × 2 multilayers. Both architectures provided sustained Cu2+ release over seven days without a burst effect. In vitro biological testing showed that both multilayer coatings achieved over 96% inhibition of Gram-positive bacteria such as Staphylococcus aureus and Bacillus subtilis, while exhibiting moderate antibacterial effects against Gram-negative strains (Escherichia coli, Pseudomonas aeruginosa). Despite the presence of copper, MG-63 osteoblast-like cells demonstrated sustained viability and successful extracellular matrix mineralisation, indicating excellent cytocompatibility of the coatings with bone-forming cells. These results demonstrate that multilayer Ti–Cu oxide coatings can effectively balance antibacterial performance, corrosion resistance, mechanical strength, and support bone cell integration, making them a promising strategy for the surface modification of titanium-based biomedical implants.
Nanostructured TiO2/Cu coatings were deposited on Ti6Al4V alloy by a two-step glow-discharge sputtering process and evaluated for their structural, electrochemical, and biological properties. Dual-acid etching produced microroughened substrates before TiO2 layer deposition, followed by surface Cu sputtering with varied deposition times. Characterisation by AFM, OM, SEM/EDS, and XRD confirmed the formation of TiO2 with Cu/Cu2O-containing hybrid coatings with good adhesion to the substrate. Increasing Cu deposition enhanced surface hydrophobicity and copper ion release. EIS measurements proved that the coatings retained stable protective behaviour in simulated body fluid (SBF). Antibacterial tests against Escherichia coli showed up to 98% improved efficacy compared to bare Ti6Al4V, confirming the strong antimicrobial role of copper. However, MG63 osteoblast-like cells exhibited reduced viability even after pre-immersion in PBS, suggesting that cytotoxicity was associated not only with excess Cu ion release but also with direct interaction between cells and surface Cu nanostructures. Overall, the results indicate that TiO2/Cu coatings provide excellent antimicrobial activity, good protection and strong adhesion, but their limited biocompatibility highlights the need for fine-tuned copper incorporation in future biomedical implant applications.
An experimental study of the lowest resonant mode of spherical and hemispherical pendant droplets with low Bond numbers (less than 0.1) is proposed. The resonant frequency was determined by Resonant Droplet Tensiometry (RDT), where the forced oscillations are driven by an electric field. The main aim of the study is to demonstrate the influence of the supporting surface radius as well as the droplet radius on the resonant frequencies of small pendant droplets. For that purpose, precisely crafted and polished metal and PTFE surfaces, different in radius, were used to support spherical or hemispherical droplets of deionized water driven in oscillations by a frequency modulated dielectrophoretic force. Experimentally obtained resonant frequencies of the lowest resonant mode were used to calculate the dimensionless eigenfrequencies with respect to the droplet radius. The results are compared with other theoretical studies.