MULTIFUNCTIONAL COATINGS

WITH ANTIBIOFOULING
PROPERTIES
José D. Castro*1, Isabel Carvalho1,2,3, Mariana Henriques2, S. Carvalho1,3
1CFUM-UP, Centro de Física das Universidades do Minho e do Porto, University of Minho, Campus of Azurém, 4800-058
Guimarães, Portugal.
2CEB, Center of Biological Engineering, LIBRO – Laboratório de Investigação em Biofilmes Rosário Oliveira, University

of Minho, Campus of Gualtar, 4710-057 Braga, Portugal.

3SEG-CEMMPRE Mechanical Engineering Department, University of Coimbra, 3030-788 Coimbra, Portugal

1- Abstract
Biofouling is “the accumulation of microorganisms, plants, algae, or small animals on wetted surfaces that have a mechanical function, causing structural or other functional
deficiencies”. Biofouling process has enjoyed a special attention for its affectation to a big number of different pieces from different applications: offshore platforms, vessels,
biomedical devices, architectural pieces, decorative pieces... All applications mentioned before have a common need, achieve a multifunctionality in order to accomplish its main
function, avoiding biofouling formation. Focusing in this issue, doped metallic oxynitrides are a plausible solution, bringing to the board an interesting viewpoint of multifunctionality in
surfaces: aesthetics and antibacterial. The present study developed Ti(O)N and Zr(O)N films doped with two different biocides agents, silver and copper. Reactive direct current
magnetron sputtering with reactive gas pulsed process was used in order to obtain the films over metallic samples. Physical, chemical and morphology characteristics were assessed,
as well as functional properties like colour variation, wettability, roughness and antibacterial resistance. Comparing the colour palette, Zr(O)N got a wider variation than Ti(O)N
system. Blue, rose-gold, golden, purple and black tones were obtained. Antibacterial and antibiofouling tests proved that the biocidal agents inhibited S. epidermidis and microalgae
growth. The coatings developed by the present study can be easily tunable to the desirable decorative purposes with antibacterial and antibiofouling.

2- Experimental details

Reactive Oxygen applied by pulses

atmosphere Duty cycle
(Ar+N2+O2) Top layer Top layer O2 flow
time
Ag-TiN X X
Set 1
(MeN) interlayer Ag-Ti(O)N Ag-TiON-DC40
Ag-TiON-DC80
✓ (1.2 sccm)
✓ (1.2 sccm)
18 s
36 s
(Me) interlayer Set 2
Cu-ZrN X X
Unbalanced Cu-ZrON-DC40 ✓ (1.5 sccm) 18 s
magnetron co- Substrate Cu-Zr(O)N
Cu-ZrON ✓ (1.5 sccm) 36 s
sputtering
system

3- Results
3.1- Structural and morphological analysis (SEM-EDS & XRD) 3.2- Color, wettability and roughness measurements
Oxygen incorporation Cross-section
Ag-TiN Ag-TiON-DC80 Ag-TiN
Ag-Ti(O)N

TiN TiON-DC40 TiON-DC80 Ag-TiN Ag-TiON-DC40 Ag-TiON-DC80

2 µm 1 µm
ZrN ZrON-DC40 ZrON-DC80 Cu-ZrN Cu-ZrON-DC40 Cu-ZrON

Cu-ZrN Cu-ZrON Cu-ZrON

Cu-ZrN Cu-ZrON Ag-TiN Ag-TiON-DC80
2 µm
Cu-Zr(O)N

2 µm 2 µm 2 µm

- More compact films with oxygen incorporation in Ag-Ti(O)N system, unlike Cu-Zr(O)N
system where oxygen promoted voids into structure.
More
- Ag crystal form was present in all Ag-Ti(O)N films, meanwhile Cu crystal form solely
appeared in Cu-ZrON film after chemical treatment with NaOCl solution (5% v/v). This
hydrophilic
behaviour
= Higher
roughness
activation was crucial in order to obtain the antibacterial behave in Cu-ZrON film.

3.2- Antibacterial and Antibiofouling

Sample Ti or Zr N O Ag or Cu Microalgae exposure

name (at. %) (at. %) (at. %) (at. %)
TiN TiON-DC80 Control
Ag-TiN 52 45 - 3
Ag-TiON-
44 17 38 1
DC80
Cu-ZrN 42 47 - 11

Cu-ZrON 29 21 43 7 TiN Ag-TiN Ag-TiON-DC80

Ag-TiN Ag-TiON-DC80 Control detail

Halo test
(S. epidermidis) ZrN Cu-ZrN Cu-ZrON

Less diatoms were attached in Ag doped films

4- Conclusions
• Ag-Ti(O)N and Cu-Zr(O)N films with oxygen variation through duty cycle were performed with reactive
DC magnetron sputtering technique obtaining a large range of thicknesses (1.70∼3.10 µm).
• SEM micrographs revealed the influence of oxygen in densification exhibited by Ag-Ti(O)N films and the
appearance of voids in Cu-Zr(O)N coatings. While Ag nanoparticles appeared on the surface or embedded
in the coating, Cu did not display any shape. Cross-section micrographs displayed columnar growth profile
in all systems.
Acknowledgements
The authors acknowledge to Physics center of University of Minho and University of Porto (CF-
UM-UP) by its support though the strategical project (UID/FIS/04650/2019). This study was
supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of
the strategic funding of UID/FIS/04650/2019 and UID/BIO/04469/2019 unit and BioTecNorte
operation (NORTE-01-0145-FEDER-000004) funded by the European Regional Development Fund
under the scope of Norte2020 - Programa Operacional Regional do Norte and in the framework of
the On-SURF (co-financed via FEDER (PT2020) POCI-01-0247-FEDER-024521) project.

• Oxygen incorporation in all coatings influenced the shifting to darker tones on films, passing through a
wide variety of colours with aesthetical interest.
• Antibacterial and antibiofouling tests proved that Ag and Cu doped systems inhibited S. epidermidis and
microalgae growth.