Advanced surface characterization of silver nanocluster segregation in Ag-TiCN bioactive coatings by RBS, GDOES and ARXPS

Surface modification by means of wear protective and antibacterial coatings represents, nowadays, a crucial challenge in the biomaterials field in order to enhance the lifetime of bio-devices. It is possible to tailor the properties of the material by using an appropriate combination of high wear resistance (e.g., nitride or carbide coatings) and biocide agents (e.g., noble metals as silver) to fulfill its final application. This behavior is controlled at last by the outmost surface of the coating. Therefore, the analytical characterization of these new materials requires high-resolution analytical techniques able to provide information about surface and depth composition down to the nanometric level. Among these techniques are Rutherford backscattering spectrometry (RBS), glow discharge optical emission spectroscopy (GDOES), and angle resolved X-ray photoelectron spectroscopy (ARXPS). In this work, we present a comparative RBS–GDOES–ARXPS study of the surface characterization of Ag–TiCN coatings with Ag/Ti atomic ratios varying from 0 to 1.49, deposited at room temperature and 200 °C. RBS analysis allowed a precise quantification of the silver content along the coating with a non-uniform Ag depth distribution for the samples with higher Ag content. GDOES surface profiling revealed that the samples with higher Ag content as well as the samples deposited at 200 °C showed an ultrathin (1–10 nm) Ag-rich layer on the coating surface followed by a silver depletion zone (20–30 nm), being the thickness of both layers enhanced with Ag content and deposition temperature. ARXPS analysis confirmed these observations after applying general algorithm involving regularization in addition to singular value decomposition techniques to obtain the concentration depth profiles. Finally, ARXPS measurements were used to provide further information on the surface morphology of the samples obtaining an excellent agreement with SEM observations when a growth model of silver islands with a height d = 1.5 nm and coverage θ = 0.20 was applied to the sample with Ag/Ti = 1.49 and deposited at room temperature.This work was financially supported by the Spanish Ministry of Science and Innovation (projects FUNCOAT CSD2008-00023 and RyC2007-0026). This research is sponsored by FEDER funds through the program COMPETE "Programa Operacional Factores de Competitividade" and by national funds through FCT "Fundacao para a Ciencia e a Tecnologia", in the framework of the Strategic Projects PEST-C/FIS/UI607/2011, and PEST-C/EME/UI0285/2011 and under the project PTDC/CTM/102853/2008. The authors would like to acknowledge I. Caretti and R. Velasco for the fruitful discussions and the proofreading of the manuscript

Ag+ release and corrosion behavior of zirconium carbonitride coatings with silver nanoparticles for biomedical devices

Zirconium carbonitride coatings with silver nanoparticles were produced by DC unbalanced dual magnetron sputtering system, using two targets, Zr and Zr/Ag in an Ar, C2H2 and N2 atmosphere. Stainless steel 316L and silicon (100) substrates were used for electrochemical and structural characterization, respectively. Silver was found to be well distributed throughout the coatings, maintaining the films' composition in depth, while its diffusion to the electrolyte decreases as immersion time increases, stopping its release after 7 to 8 days of immersion. Electrochemical characterization revealed very stable films that have improved base material, without any diminished corrosion resistance due to the silver content.The authors are grateful to 3B's Research Group in Biomaterials, Biodegradables and Biomimetics for the ICP measurements and Prof. Isabel Leonor, PhD for her assistance. This research is partially sponsored by FEDER funds through the program COMPETE-Programa Operacional Factores de Competitividade and by Portuguese national funds through FCT-Fundacao para a Ciencia e a Tecnologia, under the project ANTIMICROBCOAT-PTDC/CTM/102853/2008. This work has also been supported by the Ministerio de Ciencia e Innovacion of Spain through the Consolider-Ingenio 2010 program (CSD2008-00023) and through the project RyC2007-0026

Advanced structural characterization of biocompatible Ag-TiCN coatings

One of the main reasons for biomedical implants failure is the generation of wear debris together with microbial infection. To overcome this problem it has been proposed the use of very low wear coatings as diamond-like carbon (DLC), transitionmetal carbides (MeCx) or nitrides (MeNx) in combination with antibacterial elements such silver, gold or copper. The present work explores the potentialities of silver-containing carbon/nitride (Ag-TiCN) based coatings to be used as protective thin films for biomedical implants. Samples were prepared by DC unbalanced reactive magnetron sputtering with contents of Ag ranging from 0 to 20 at.% and Ti from 35 to 15 at.% while keeping C, N and O content constant. The coatings were fully characterized in terms of structure (XRD, Raman) and depth profiling composition by GDOES and RBS (using the nitrogen resonance at 3.70 MeV He+ ions). In particular, we have selected three samples with different Ag contents (0, 6 and 20%) and carried out and advanced surface characterization using XPS, ARXPS and HR-SEM to study the segregation of silver towards the surface. We have correlated the structure and composition of the films with their biological properties. Microbial adhesion was assessed for both bacteria (Staphylococcus epidermidis) and yeast (Candida albicans)

Electrochemical vs antibacterial characterization of ZrCN-Ag coatings

Nowadays, antibacterial properties are becoming a viable feature to be introduced in biomaterials due to the possibility of modifying the materials' surface used in medical devices in a micro/nano metric scale. As a result, it is mandatory to understand the mechanisms of the antimicrobial agents currently used and their possible failures. In this work, the antibacterial activity of ZrCNAg films is studied, taking into consideration the ability of silver nanoparticles to be dissolved when embedded into a ceramic matrix. The study focuses on the silver release evaluated by glow discharge optical emission spectroscopy and the effect of the fluid composition on this release. The results revealed a very low silver release of the films, leading to non-antibacterial activity of such materials. The silver release was found to be dependent on the electrolyte composition. NaCl (8.9 g L? 1) showed the lowest spontaneously silver ionization, while introducing the sulfates in Hanks' balanced salt solution (HBSS) such ionization is increased; finally, the proteins incorporated to the (HBSS) showed a reduction of the silver release, which also explains the low ionization in the culture medium (tryptic soy broth) that contains high quantities of proteins.This research is partially sponsored by the FEDER funds through the program COMPETE - Programa Operacional Factores de Competitividade and by the Portuguese national funds through FCT-Fundacao para a Ciencia e a Tecnologia, under the projects ANTIMICROBCOAT - PTDC/CTM/102853/2008 and in the framework of the Strategic Projects PEST-C/FIS/UI607/2011, PEST-C/EME/UI0285/2011 and SFRH/BD/80947/2011.This work has also been supported by the Ministerio de Ciencia e Innovacion of Spain through the Consolider-Ingenio 2010 Programme (CSD2008-00023) and through project RyC2007-0026

Advanced characterization and optical simulation for the design of solar selective coatings based on carbon: transition metal carbide nanocomposites

Solar selective coatings based on carbon transition metal carbide nanocomposite absorber layers were designed. Pulsed filtered cathodic arc was used for depositing amorphous carbon:metal carbide (a-C:MeC, Me = V, Mo) thin films. Composition and structure of the samples were characterized by ion beam analysis, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. The optical properties were determined by ellipsometry and spectrophotometry. Three effective medium approximations (EMA), namely Maxwell-Garnett, Bruggeman, and Bergman, were applied to simulate the optical behaviour of the nanocomposite thin films. Excellent agreement was achieved between simulated and measured reflectance spectra in the entire wavelength range by using the Bergman approach, where in-depth knowledge of the nanocomposite thin film microstructure is included. The reflectance is shown to be a function of the metal carbide volume fraction and its degree of percolation, but not dependent on whether the nanocomposite microstructure is homogeneous or a self-organized multilayer. Solar selective coatings based on an optimized a-C:MeC absorber layer were designed exhibiting a maximum solar absorptance of 96% and a low thermal emittance of ~5% and 15% at 25 and 600 °C, respectively. The results of this study can be considered as a predictive design tool for nanomaterial-based optical coatings in general

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

Published 17 July 2013New 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.This research is partially sponsored by FEDER funds through the program COMPETE-Programa Operacional Factores de Competitividade and by Portuguese national funds through FCT-Fundacao para a Ciencia e a Tecnologia, under the projects ANTIMICROBCOAT-PTDC/CTM/102853/2008. This work has also been supported by the Ministerio de Ciencia e Innovacion of Spain through the Consolider-Ingenio 2010 programme (CSD2008-00023) and through project RyC2007-0026

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.Spanish Ministry of Science and InnovationFundação para a Ciência e Tecnologia (FCT)CRUP InstitutionMCIN

Structure-property relations in ZrCN coatings for tribologic applications

ZrCN coatings were deposited by dc reactive magnetron sputtering with N2 flows ranging from 2 to 10 sccm in order to investigate the influence of the nitrogen incorporation on structure and properties. Information about the chemical composition was obtained by glow discharge optical emission spectroscopy and Rutherford backscattering spectroscopy. The evolution of the crystal structure studied by X-ray diffraction revealed the formation of a face-centred cubic ZrCN phase for N2 flows greater than 4 sccm. Additionally, the presence of an amorphous phase in the coatings deposited with the highest N2 flows could be evidenced by Raman spectroscopy and X-ray photoelectron spectroscopy. This phase can act as a lubricant resulting in a low coefficient of friction as shown in the conducted ball-on-disc tests. Nanoindentation measurements showed that coatings deposited with a 6 sccm N2 flow had the maximum hardness which also revealed the best performance in the conducted dry cutting tests.CRUP InstitutionSpanish Ministry of Science and InnovationChristian Doppler Research Associatio

Surface characterization of Ti-Si-C-ON coatings for orthopedic devices : XPS and Raman spectroscopy

Ti–Si–C–ON films were deposited by DC reactive magnetron sputtering and their chemical properties, biofilm formation and toxicity were characterized. Based on the films composition three different growth regimes were identified on the films; (I) N/Ti = 2.11 (high atomic ratio) and low oxygen content; (II) 0.77 ≤ N/Ti ≤ 1.86 (intermediate atomic ratio) and (III) N/Ti ≤ 0.12 (low ratio) and high oxygen content. The phase composition varied from mainly TiN on regime I to TiCN on regime 2 and titanium oxides on regime III. Taking into account the results of biological characterization (biofilm formation and cytotoxicity), it was possible to conclude that samples with a high TiN content (regime I) presented more favorable biocompatibility, since it was less prone to microbial colonization and also displayed a low cytotoxicity.The authors are grateful to Dr. Alicia Andres, Institut de Ciencia de Materiales de Madrid (ICMM-CSIC), for his assistance in carrying out the Raman spectroscopic analysis. The work was financially supported by the CRUP Institution (project "Accao No E-1007/08), and the Spanish Ministry of Science and Innovation (projects FUN-COAT CSD2008-00023, MAT2008-06618-C02 and Integrated action HP016-2007). This research is partially sponsored by FEDER funds through the program COMPETE- Programa Operacional Factores de Competitividade and by Portuguese national funds through FCT-Fundacao para a Ciencia e a Tecnologia, under the project PTDC/CTM/102853/2008