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

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Abstract

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.

SEM micrograph of silver nanocluster surface segregation on bioactive AgTiCN coatings as analyzed by a) GDOES, b) RBS, and c) ARXPS depth profiles

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Acknowledgments

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 “Fundação para a Ciência 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.

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Authors and Affiliations

  1. Instituto de Ciencia de Materiales de Madrid (ICMM–CSIC), Cantoblanco, 28049, Madrid, Spain

    R. Escobar Galindo

  2. GRF–CFUM, Physics Department, University of Minho, Campus of Azurém, 4800-058, Guimarães, Portugal

    N. K. Manninen & S. Carvalho

  3. SEG–CEMUC, Department of Mechanical Engineering, University of Coimbra, Rua Luís Reis Santos, 3030 788, Coimbra, Portugal

    N. K. Manninen & S. Carvalho

  4. Departamento de Física Aplicada (CXII), Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain

    C. Palacio

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  1. R. Escobar Galindo
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  2. N. K. Manninen
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  4. S. Carvalho
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Correspondence to R. Escobar Galindo.

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Escobar Galindo, R., Manninen, N.K., Palacio, C. et al. Advanced surface characterization of silver nanocluster segregation in Ag–TiCN bioactive coatings by RBS, GDOES, and ARXPS. Anal Bioanal Chem 405, 6259–6269 (2013). https://doi.org/10.1007/s00216-013-7058-z

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  • DOI: https://doi.org/10.1007/s00216-013-7058-z

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