R. Escobar Galindo

Ag+ release inhibition from ZrCN–Ag coatings by surface agglomeration mechanism : structural characterization

New multifunctional materials based on well-established materials to which functional properties are added, such as antibacterial performance, have become a relevant research topic, in order to meet the requirements of today’s technological advances. This paper reports the results of a detailed structural and chemical characterization study of ZrCN–Ag coatings produced by reactive magnetron sputtering, as well as the release of silver after immersion in a simulated body fluid (Hank’s balanced salt solution), which mimic the material behaviour within the human body. The chemical composition was evaluated by electron probe microanalysis, x-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy, whereas the structure was assessed by Raman spectroscopy and x-ray diffraction. The material exhibits a homogeneous distribution of the elements throughout the films, with a (C + N)/Zr ratio of around 1.3 and 15 at% of silver. A mixture of amorphous (a-C and CNx) and crystalline phases (ZrCN) was identified. In addition, the silver was detected to be released in less than 0.7% of the total silver in the films, occurring during the first two hours of immersion; no further release was evidenced after this period of time. (Some figures may appear in colour only in the online journal)

Ag-Ti(C,N)-based coatings for biomedical applications : influence of silver content on the structural properties

Ag–TiCN coatings were deposited by dc reactive magnetron sputtering and their structural and morphological properties were evaluated. Compositional analysis showed the existence of Ag–TiCN coatings with different Ag/Ti atomic ratios (ranging from 0 to 1.49). The structural and morphological properties are well correlated with the evolution of Ag/Ti atomic ratio. For the samples with low Ag/Ti atomic ratio (below 0.20) the coatings crystallize in a B1-NaCl crystal structure typical of TiC0.3N0.7. The increase in Ag/Ti atomic ratio promoted the formation of Ag crystalline phases as well as amorphous CNx phases detected in both x-ray photoelectron spectroscopy and Raman spectroscopy analysis. Simultaneously to the formation of Ag crystalline phases and amorphous carbon-based phases, a decrease in TiC0.3N0.7 grain size was observed as well as the densification of coatings.

Silver activation on thin films of Ag–ZrCN coatings for antimicrobial activity

Nowadays, with the increase of elderly population and related health problems, knee and hip joint prosthesis are being widely used worldwide. However, failure of these invasive devices occurs in a high percentage thus demanding the revision of the chirurgical procedure. Within the reasons of failure, microbial infections, either hospital or subsequently-acquired, contribute in high number to the statistics. Staphylococcus epidermidis (S. epidermidis) has emerged as one of the major nosocomial pathogens associated with these infections. Silver has a historic performance in medicine due to its potent antimicrobial activity, with a broad-spectrum on the activity of different types of microorganisms. Consequently, the main goal of this work was to produce Ag-ZrCN coatings with antimicrobial activity, for the surface modification of hip prostheses. Thin films of ZrCN with several silver concentrations were deposited onto stainless steel 316 L, by DC reactive magnetron sputtering, using two targets, Zr and Zr with silver pellets (Zr+Ag target), in an atmosphere containing Ar, C2H2 and N2. The antimicrobial activity of the modified surfaces was tested against S. epidermidis and the influence of an activation step of silver was assessed by testing samples after immersion in a 5% (w/v) NaClO solution for 5 min. The activation procedure revealed to be essential for the antimicrobial activity, as observed by the presence of an inhibition halo on the surface with 11 at.% of Ag. The morphology analysis of the surface before and after the activation procedure revealed differences in silver distribution indicating segregation/diffusion of the metallic element to the films surface. Thus, the results indicate that the silver activation step is responsible for an antimicrobial effect of the coatings, due to silver oxidation and silver ion release.

Compositional and structural properties of nanostructured ZnO thin films grown by oblique angle reactive sputtering deposition: effect on the refractive index

In this work, we report the successful growth of ZnO nanostructured films by oblique angle magnetron sputtering deposition (OAD) from a Zn target in a mixture gas of Ar/O2. The film microstructure and the surface morphology of the samples were explored by HRSEM. The crystalline structure and the composition were determined by XRD and RBS, respectively. The optical properties of the ZnO films (refractive index, n, and extinction coefficient, k) were also studied by spectroscopic ellipsometry. Films were found to be porous and consisting of an inclined columnar structure, with columns tilting in the direction of the incident flux. The experimental results reveal that the deposition angle, the Ar/O2 gas ratio and the distance between the target and the substrate play a significant role in the composition, crystalline structure and optical and electrical properties of the ZnO thin films. In particular, it has been found that using different deposition angles in the range 0°–85° it is possible to control the refractive index varying from 1.9 to 1.5, due to the high porosity of the films as a result of the self-shadowing columnar structure produced during the process.

Optical properties and refractive index sensitivity of reactive sputtered oxide coatings with embedded Au clusters

In the present study, nanocomposite coatings of Au clusters embedded in two different oxides, TiO2 and Al2O3, were synthesized using pulsed DC magnetron sputtering. The depositions were carried out in three steps, by depositing the oxide, the Au clusters, and again the oxide. The deposition time of the Au clusters was varied in order to achieve different cluster sizes, morphologies, and nanocomposite topographies. The structure, microstructure, morphology, and the optical properties of the coatings were studied. With the increase in Au content, red-shifted surface plasmon resonance (SPR) peaks with higher intensity and increased widths were observed due to changes in the metal clusters sizes and morphology and due to interparticle effects. In order to relate the peculiar SPR extinction bands with the different clusters shapes and distributions, a simulation of the optical properties of the nanocomposites was performed making use of the Renormalized Maxwell-Garnett approach. A theoretical study concerning the refractive index sensitivity was made in order to predict the optimal coatings parameters for sensing experiments. The increased surface area and the strong SPR extinction bands make these coatings suitable for gas sensing and also catalysis, albeit many other application fields can be envisaged.

Calibration of nitrogen content for GDOES depth profiling of complex nitride coatings

Quantitative GDOES studies in protective coating materials (oxides, nitrides, oxynitrides, etc.) are severely limited by the lack of certified standards containing known amounts of oxygen and/or nitrogen. In this work, we propose an alternative method for nitrogen quantification using as calibration samples, a series of deposited nitride coatings whose composition is pre-established by absolute quantitative measurements with Rutherford backscattering spectrometry. This calibration approach was successfully applied to the study of different complex nitride systems as nanometric multilayers or nanocomposite, and to enlarge the application of GDOES to a wider range of practical applications.

Beneficial silver: antibacterial nanocomposite Ag-DLC coating to reduce osteolysis of orthopaedic implants

Silver-containing diamond-like-carbon (DLC) is a promising material for biomedical implants due to its excellent combination of antibacterial and mechanical properties. In this work, a dual-cathode pulsed filtered cathodic arc source containing silver and graphite rods was employed in order to obtain DLC samples with various silver contents. Chemical composition of the samples was analyzed by acquiring their compositional depth-profiles using radio-frequency Glow Discharge Optical Emission Spectroscopy (rf-GDOES), while the microstructural properties were analyzed by X-ray diffraction and Raman spectroscopy. Tribological studies carried out against UHMWPE balls in fetal bovine serum indicate that the presence of silver in DLC could be beneficial to reduce the wear of the polymeric surfaces.

Determination of Boron Diffusion Coefficients in Borided Tool Steels

The boron diffusion in the Fe2B and FeB borided phases formed at the surface of AISI H13 tool steels during the paste boriding process was estimated. The treatment was carried out at temperatures of 1173, 1223 and 1273 K with 2, 4, 6 and 8 h exposure times for each temperature using a 4 mm layer thickness of boron carbide paste over the material surface. The boride layers were characterized by the GDOES technique to determine in quantitative form the presence of the alloying elements on the borided phases. The boron diffusion coefficients and were determined by the mass balance equation and the boride incubation time assuming that the boride layers obey the parabolic growth law. Also, the mass gain produced by both boride layers at the surface of the tool steels was determined. Finally, the boron diffusion coefficients were interpreted as a function of the treatment temperature, obtaining the activation energy values for the diffusion controlled growth of Fe2B and FeB hard coatings.

STUDY OF POLYMER/METAL COATING UNDER STRESS USING POSITRON ANNIHILATION SPECTROSCOPY

Positron annihilation spectroscopy (PAS) has proven to be a very useful technique for, e.g., the study of defects in materials and the characterization of polymer free-volume. Positron lifetime, Doppler broadening of the annihilation radiation (characterized by the so-called S parameter) and angular correlation of annihilation radiation (ACAR) are the techniques used mostly. In the last few years these techniques have been extended to the study of physical defects at the atomic level of coating systems. These studies show that positron lifetime and the S parameter can monitor the degradation of the coating due to environmental changes (water or UV exposure). The present work is focused on the behavior of coatings under external stresses as studied by PAS. Results of positron annihilation measurements (before and after stretching) on interstitial free (IF) steel coated with epoxy using the Delft variable energy positron (VEP) beam facility are discussed.

Positron beam analysis of structurally ordered porosity in mesoporous silica thin films

Positron beam techniques have been employed to characterise low-k dielectric silica based films, which have two or three dimensional structures of nanometre size pores. Pore fractions vary from 5 to 50%. Positrons implanted in the layer slow down and eventually annihilate with the electrons from the layer. However, in pores of the dielectric films positronium (Ps) is formed before annihilation takes place. The two states of Ps (para-positronium (p-Ps) and ortho-positronium (o-Ps)) are formed with rather different life times of 125 ps and 142 ns, respectively. The behaviour of Ps in the porous material can be described as hot particles with 1 eV initial kinetic energy, which lose their energy by frequent collisions with the atoms of the pore walls. When the pores are interconnected or separated by thin walls allowing permeation of the Ps some of the Ps will effuse from the film into the vacuum. The 2D-ACAR technique enables one to monitor the velocity distribution of the annihilating p-Ps and shows an increasing fraction of surface emitted p-Ps when positrons are implanted closer to the film surface. Measurements of Doppler broadening of 2-gamma annihilation and detection of 3-gamma events (o-Ps) give insight into the frequency of other annihilation events. Combining the results, a complete picture can be obtained of the interactions and transport of the Ps particles in the material. By modelling the Ps behaviour information is obtained on structural parameters of the porous material. A transport model based on multi energy group diffusion of particles describes the results well.