3D Printed Metal Oxide-Polymer Composite Materials for Antifouling Applications

Abstract

Current technology to prevent biofouling usually relies on the use of toxic, biocide-containing materials, which can become a serious threat to marine ecosystems, affecting both targeted and nontargeted organisms. Therefore, the development of broad-spectrum, less toxic antifouling materials is a challenge for researchers; such materials would be quite important in applications like aquaculture. In this respect, surface chemistry, physical properties, durability and attachment scheme can play a vital role in the performance of the materials. In this work, acrylonitrile butadiene styrene (ABS)/micro ZnO or nano ZnO composite lattices with different metal oxide contents were developed using 3D printing. Their antifouling behavior was examined with respect to aquaculture applications by monitoring growth on them of the diatoms Navicula sp. and the monocellular algae Chlorella sp. with image analysis techniques. As shown, the presence of metal oxides in the composite materials can bring about antifouling ability at particular concentrations. The present study showed promising results, but further improvements are needed.

Keywords: 3D printing; ZnO based ABS composites; antifouling properties; aquaculture.

Figure 1

The used printing system and the growth conditions.

Figure 2

Schematic presentation of experiments for the investigation of the antifouling action.

Figure 3

XRD patterns of micro- (a) and nano-ZnO-ABS (b) filaments, micro- (c) and nano-ZnO-ABS (d) printed materials, as well as for pure ABS.

Figure 4

High magnification FESEM for the 5% ZnO nano- and micro- samples; 5% nano ZnO-ABS × 80,000; 5% micro ZnO-ABS × 40,000.

Figure 5

SEM images presenting examples of the structures of the 0.5%, 5% and 20% nano- and micro-ZnO-ABS filaments and printed composite materials. Magnification ×20,000. Scale is 4 µm for all images.

Figure 5

SEM images presenting examples of the structures of the 0.5%, 5% and 20% nano- and micro-ZnO-ABS filaments and printed composite materials. Magnification ×20,000. Scale is 4 µm for all images.

Figure 6

(a) Raman spectra of 20% micro- and nano-ZnO-ABS printed composite materials; (b) Peak analysis of Raman spectrum for 20% micro-ZnO-ABS; and (c) Raman spectrum for micro-ZnO-ABS composites as a function of ZnO concentration.

Figure 6

(a) Raman spectra of 20% micro- and nano-ZnO-ABS printed composite materials; (b) Peak analysis of Raman spectrum for 20% micro-ZnO-ABS; and (c) Raman spectrum for micro-ZnO-ABS composites as a function of ZnO concentration.

Figure 7

Raman mapping and spectra of nano-ZnO-ABS printed composite materials. (A) Example of Raman spectrum corresponding to mauve-blue dark color regions in the maps; (B) example of a Raman spectrum corresponding to blue color regions in the maps.

Figure 8

Raman mapping and spectra of micro-ZnO-ABS printed composite materials. (C) Example of a Raman spectrum corresponding to yellow-green color regions in the maps; (D) example of Raman spectrum corresponding to red color regions in the maps.

Figure 9

Percentage of coverage of composite material with Chlorella.

Figure 10

Percentage of coverage of composite material with Navicula.

Figure 11

XRD patterns of micro- (a–d) and nano-ZnO-ABS (e–h) for the initial printed 3D grid (black) exposed to Navicula (red) and Chlorella (blue), respectively.

Figure 12

SEM images of Chlorella and Navicula biofilms on the 0.5%, 5% and 20% nano- and micro-ZnO-ABS 3D printed composites, respectively.

Figure 13

Higher magnification SEM images of (a) Chlorella biofilm on the 5% nano-ZnO-ABS and (b) Navicula biofilms on the 5% micro-ZnO-ABS, 3D printed composites.

Figure 14

EDX elemental mapping of 10% nano-ZnO-ABS and 0.5% micro-ZnO-ABS, 3D printed composites (reference and after plankton exposure). Large image-composite elemental map followed by individual element mapping bellow.