Dr. Nikos Kehagias. Catalan Institute of Nanoscience and Nanotechnology, CSIC and The Barcelona Institute of Science and Technology, Barcelona, Spain

Transcription

1 Euronanoforum June Malta Dr. Nikos Kehagias Catalan Institute of Nanoscience and Nanotechnology, CSIC and The Barcelona Institute of Science and Technology, Barcelona, Spain

2 Nanotechnology Value Chain Materials Nanofabrication Nanometrology A B C D Courtesy of:

3 Advanced Nanomanufacturing Hybrid Hierarchical Nanopatterning Micro/Nano Injection Molding R2R Large Area Functional Surfaces

4 ICN2 NIL Platform Self assembly templates Au nanoparticles Photonic applications 56 nm Multi level patterning 3 dimensional polymer structuring Sub 100 nm Chirped gratings 4 mm Colloidal crystal growth 35 nm gap Phononic Crystals 400 nm wide nanochannels 2D PhC 500 nm 200 nm

5 MARKET OUTLOOK Global nano-patterinng market is estimated as US$ 1.9 billion in projected to reach US$ 19.1 billion by 2020 NIL represents 82.9% of the total nano-patterning market NIL is estimated as US$ 1.6 billion in projected to reach US$ 13.9 billion by 2020 UVNIL fastest growing NIL technology representing 72.8% share of the market in 2015 UV-NIL market is estimated at US$ 1.4 billion in projected to reach US$ 12.4 billion in 2020 Hot embossing market is estimated at US$ million in projected to reach US$ 1.3 billion in 2020 Data acquired from Nanopatterning A global market report- 09/15

6 Intelligent Surfaces

7 Process Flow Design Master orgination NIL Applications + + d a Value chain

8 as evolved objects with high performance using commonly found ale to the nanoscale. The understanding of the functions provided by n guide us to imitate and produce nanomaterials, nanodevices, and of objects (bacteria, plants, land and aquatic animals, seashells etc.) Self- Cleaning Surfaces ng, low adhesion, and drag reduction surfaces n various commercial applications. These include transportation vehicles pplications [3]. To reduce pressure drop and volume loss in luidics, it is desirable to minimize the drag force at the solid liquid phobicity, self-cleaning and low adhesion is the leaves of water-repellent 2,4-11]. The leaf surface is very rough due to so-called papillose icroasperities. In addition to the microscale roughness, the surface of the erities composed of three-dimensional epicuticular waxes which are c. The waxes on lotus leaves exist as tubules [10,11]. Water droplets on dily sit on the apex of the nanostructures because air bubbles fill the (Figure 1a). Therefore, these leaves exhibit considerable and contact angle hysteresis of a lotus leaf are about 164 and 3, n the leaves remove any contaminant particles from their surfaces when nd show low adhesive force [14-16]. Wetting is a multiscale phenomenon Lotus leaf Rose petal Lotus effect [12], and (b) scale structure of shark reducing drag [21]., and drag reduction surfaces nd self-cleaning is provided by fish which are known to be well protected gh they are wetted by water [15,17]. Fish scales have a hierarchical with diameters of 4 5 mm covered by papillae µm in length and is a model from nature for a low drag surface, is covered by very small denticles (little skin teeth), ribbed with longitudinal grooves (aligned ater) (Figure 1b). These grooved scales reduce vortice formation

9 Alternative NIL REVERSE NIL

10 Hierarchical patterning Reverse nanoimprint lithography over pre/patterned surfaces Inking mode Microstructures UV-NIL Nanostructures RNIL Intact mode Inking mode Intact mode A. Fernández et.al., Design of hierarchical surfaces for tuning wetting characteristics, B. ACS Applied Materials & Interfaces, (2017) Accepted- Manuscript ID: am t.r1

11 Self- Cleaning Surfaces Towards 3D hiearchical surfaces + Micro structures Nano structures 3D structures

12 Hydrophobic Surfaces 2D surfaces Contact angles [ o ] Theoretical Experimental Surface Structure Wenzel Cassie-Baxter Static Sliding Hysteresis Microstructure ± 4 35 ± 5 16 ± 6 Honeycomb pillars ± 5 Pinned 30 ± 4 Honeycomb lines ± 9 Pinned 21 ± 10 Nano pillars ± 2 Pinned 23 ± 4 Nano spikes 146 ± 3 Pinned 45 ± 5

13 Self- Cleaning Surfaces 3D-Hierarchical surfaces Contact angles [ o ] Theoretical Experimental Surface Structure Wenzel Cassie-Baxter Static Sliding Hysteresis Honeycomb pillars + Micropillars Honeycomb lines + Micropillars Nano pillars + Micropillars Nano spikes + Micropillars ± 3 18 ± 3 12 ± ± 5 17 ± 2 10 ± ± 1 11 ± 4 7 ± ± 2 7 ± 2 4 ± 2

14 Self- Cleaning Surfaces

15 Self- Cleaning Surfaces

16 Plast4Future Technology Enabeling Functional Plastic Surfaces Mold Nano-Patterning Steel Mold Injection Molding Plastic Functional products

17 NANO-Injection moulding Courtesy of NILT Aps.

18 Indusrtial Applicsations Colour effects Easy to paint Superhydrophobic

19 Injection moulding PP Flat WCA 90 ± 3 WCA 150 ± 3 Sliding 16 ± 3 Hysteresis 15 ± 4 TOPAS Flat WCA 92 ± 2 WCA 152 ± 2 Sliding 13 ± 3 Hysteresis 10 ± 3 66 % WCA Increasing 65 % WCA Increasing

20 Dynamic Surfaces Nanospikes - Micropillars Nanopillars - Micropillars Impact velocity Wetting state Impact velocity Wetting state m/s Lotus State: 167 ± m/s Lotus State: 168 ± m/s Petal State: 151 ± m/s Petal State: 156 ± 3 > 0.9 m/s Wenzel State: 117 ± 5 > 1.7 m/s Wenzel State: 120 ± 6

21 Oleophobic Surfaces Liquids with lower surface tension than water Overhanging structures needed A stable Cassie-Baxter state results only when Concave structure Convex structure The traction on the liquid-air interface is downwards due to the capillary force.

22 FABRICATION STEPS Metal deposition Can be demolded Photolithography or RNIL Cannot be demolded Nickel up-plating Resist removal Imprinted overhanging structures Ormocomp UV-NIL Kinoshita et al., Rep. Prog. Phys. (2008) PDMS Replica N. Bogdanski et al. 3D-Hot embossing of undercut structures an approach to micro-zippers, Microelectronic Engineering 73 74, , (2004)

23 Oleophobic Surfaces Low density: µm Medium density: µm Water contact angles [⁰] High density: µm Surface Structure Static Sliding Hysteresis Flat surface 112 ± 3 35 ± 3 40 ± 6 Low density 148 ± 3 11 ± 4 10 ± 4 Medium density 155 ± 1 8 ± 2 6 ± 3 High density 147 ± 3 15 ± 3 12 ± 5

24 Roll-to-Roll Nanometrology InlineNano PET film Stamp Patterned film UV light source

25 Roll-to-Roll at ICN2 InlineNano PET film Stamp Patterned film UV light source

26 Schematics of Silicon Master - A Line Grating - Spacing: 6 µm; Height: 100 nm 2.5mm SEM of a line Line width: 470 nm 20 mm 470 nm 430 nm 80 mm 430 nm 380 nm 380 nm 320 nm 320 nm 500 nm

27 Intensity (a.u.) InlineNano in MOTION Variation in rolling speed: 1.0 m/min 2.0 m/min 3.0 m/min Line Width: 470nm 430nm 380nm 320nm Y (mm) -> The different line width of the grating can be identified up to a rolling speed of 3.0 m per min.

28 FLEXPOL project (721062) PILOTS Pilot Line Manufacturing of Nanostructured Antimicrobial Surfaces using Advanced Nanosurface Funtionalization Technologies" 10 partners 4 industrial partners 6 research partners 36 project months (1/ /2019) 5,678 Mio. EUR total costs

29 FLEXPOL project (721062) Materials processing & Nanostructuring Antimicrobial films Product validation in laboraty & hospital Blown-extruded polypropylene film with encapsulated antimicrobial essential oil Surfaces with hierarchical micro- and nanofeatures inhibiting microbes attachment and Investigation of product efficiacy in laboratory and real hospital environment

30 Partners ACKNOWLEDGMENTS Dr. Ariadna Fernández Dr. Achille Francone Prof. Clivia Sotomayor Torres

31 THANK YOU FOR YOUR ATTENTION

32 DYNAMIC SURFACES In the last years, several new wetting states have been experimentally observed. For a hierarchical surface, there can exist nine modes of wetting depending on whether water penetrates in micro and nanostructures. Rose petal effect has a very promising wetting state for different applications, such as microdroplet transport and localized chemical reactions. Lotus Rose Rose filled microstructure Cassie Wenzel Wenzel filled microstructure Cassie filled microstructure Wenzel filled nanostructure Wenzel filled micro/nanostructure Bhushan, B.; Nosonovsky, M., The rose petal effect and the modes of superhydrophobicity. Philosophical transactions. Series A 2010, 368 (1929),

33 DYNAMIC SURFACES Intact mode fabricated surfaces PMMA Ormocomp Static contact angle: 167 ± 3 Sliding angle: 7 ± 4 Hysteresis: 6 ± 3 Static contact angle: 168 ± 2 Sliding angle: 6 ± 2 Hysteresis: 4 ± 2

34 DYNAMIC SURFACES Dynamic effects on a superhydrophobic surface analyse energy barriers responsible of wetting transitions. These transitions are directly from a composite to a homogeneous state. Lotus state External stimuli Wenzel state Hierarchical surfaces open the pathway for intermediate transitions, which can be useful if one can get a precise control over them. Lotus state External stimuli Petal state External stimuli Wenzel state

35 Contact angle ( 0 ) Oleophobic Surfaces Olive oil Low density Medium density High density Ethylene glycol Density can induce sagging effect Liquid Bond number Extent of gravitational forces relative to capillary forces acting on the drop Diiodomethane Bo 2 gl LA Water Surface Tension (mn/m) Water Density (g/m 3 ) Diiodomethane Ethylene glycol Olive oil Surface Tension (mn/m) M. Nosonovsky et al., Philosophical Transactions of the Royal Society A 374 (2073) (2016).

36 Surface tension (mn/m) Contact angle ( 0 ) Oleophobic Surfaces Surface tension threshold for oleophobicity Wetting No wetting 29.7 mn/m Ethanol concentration (%) Surface tension (mn/m)