Nanolaminates have been reported to have applications in different areas, such as the preparation of multilayer films, coating biomedical appliances or multilayer edible coatings with enhanced properties for applications in the food industry. This work aims at characterizing the surface properties, water vapor permeability, and thermal and mechanical properties of a nanolayered film. The film was produced using two polysaccharides with opposite charges, chitosan and sodium alginate deposited on to aminolyzed/charged PET. Contact angle measurements showed differences in the films with a successively higher number of layers. SEM images allowed the measurement of the thickness of the layers. The nanolayered film had a water vapor permeability of (0.85 ± 0.04) × 10 −11 g m −1 s −1 Pa −1 and a hardness increase of 0.245 ± 0.06 GPa. DSC and TG analyses of the nanolayered film showed increases of 39.2% in the melting energy when compared with the PET film used as support, and a decrease in the decomposition temperature from 386 to 331 • C.
Ag-DLC coatings with Ag contents ranging from 1.3 at.% to 13.1 at.% were deposited by DC magnetron sputtering. The coatings were characterized with respect to their structure (by means of XRD and Raman Spectroscopy), mechanical and tribological properties (by scratch test, nanoindentation, residual stress measurements and pin-on-disk test). The incorporation of 13.1 at.% Ag resulted in the formation of Ag grains with 2-3 nm which promoted the increase of graphite like bonds organized in rings. Regarding the mechanical properties, no variations were found for films with Ag contents lower than 13 at.%; a reduction of both hardness and compressive residual stress were then observed for higher values. Pin-on-disk tests were performed at two different contact pressures (690 MPa and 1180 MPa) in dry sliding conditions against a zirconia counterpart. For the lower contact pressure the variations in the wear rate are well correlated with the coatings structure and mechanical properties, while for higher contact pressure the presence of Ag is relevant, Ag-DLC coatings showing higher wear rate than DLC one. SEM analysis revealed the formation of Ag aggregates on the wear track and adhesion of silver to the counterpart.
ZrCN coatings were deposited by dc reactive magnetron sputtering with N 2 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 N 2 flows greater than 4 sccm. Additionally, the presence of an amorphous phase in the coatings deposited with the highest N 2 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 N 2 flow had the maximum hardness which also revealed the best performance in the conducted dry cutting tests.
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 film's 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.
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 TiC 0.3 N 0.7. The increase in Ag/Ti atomic ratio promoted the formation of Ag crystalline phases as well as amorphous CN x 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 TiC 0.3 N 0.7 grain size was observed as well as the densification of coatings.
Surface modification of bulk materials used in biomedical applications has become an important prerequisite for better biocompatibility. In particular, to overcome the particle generation, low-wear coatings based on carbon (nitrogen) and containing antimicrobial elements such as silver are promising candidates. Thus, the present work explores the potentialities of silver-containing carbonitride-based (Ag-TiCN) thin films prepared by direct current unbalanced reactive magnetron sputtering. The silver content in the coatings was varied from 0 to 26.7 at.% by changing the targets and the fraction of C 2 H 2 and N 2 in the gas mixture with Ar. The obtained Ag-TiCN based coatings were characterized in terms of composition and microstructure. Mechanical and tribological properties of the films were studied by nanoindentation and reciprocating pin-on disk *Manuscript changes highlighted Click here to view linked References 2 testing in a fetal bovinum serum solution, respectively. Raman, SEM and energy dispersive X-ray (EDX) analysis was carried out in the contact region after tribological tests to obtain information about the friction mechanism. The cytotoxicity of the coatings was assessed by in vitro tests using fibroblast cells. The coatings comprised a mixture of TiC x N 1-x , Ag and a-C(N) x phases whose relative proportion varied depending on the Ag/Ti ratio. The mechanical, tribological and cytotoxicity were correlated with the chemical and phase composition. When the Ag/Ti ratios were below 0.20 (Ag contents < 6.3 at.%) the films resulted harder (18 GPa) with higher wear resistance (10 -6 mm 3 /Nm), showing similar friction coefficient (0.3) and good biocompatibility.
In recent years, the use of nanocomposite materials to functionalize surfaces has been investigated, taking advantage of the complementary properties of the nanocomposite constituents. Among this family of materials, ceramic-Ag coatings have been widely studied due to the large variety of functionalities that silver possesses and the possibility of tuning the coating's practical features by selecting the proper matrix to support this noble metal. Therefore, this review focuses on the effects of silver nanoparticles on the functional properties of ceramic-Ag nanocomposites. The chemistry, structure, morphology and topography of the coatings are analyzed with respect to the changes produced by the silver nanoparticles' distribution, amount and sizes and by altering production process variables. To offer a clear understanding of the functionalities of these materials, the optical, electrical, mechanical, tribological, electrochemical and biological properties reported in the last decade are reviewed, focusing on the ability to tune such properties by modifying the silver distribution, morphology and composition. In particular, the surface plasmon resonance, self-lubricating ability and antibacterial effect of silver are covered in detail, establishing their correlation with factors such as silver diffusion, segregation and ionization.
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