Nanocontainers with controlled permeability for feedback active coatings

Transcription

1 Nanocontainers with controlled permeability for feedback active coatings

2 Contents: 1. Self-healing coatings based on nanocontainers for corrosion protection: - with ph-triggered release, - triggered by mechanic rupture, - with light-triggered release. 2. Polyelectrolyte coatings for corrosion protection: - inhibitor-free coatings, - sandwich-like structures with controlled release of the inhibitor. 3. Ultrasonic fabrication of oil- or gas-filled containers: - gas-filled containers, - oil-filled carriers. 4. Bioactive coatings based on oil-filled containers.

3 Nanocontainer-based coatings To use the nanocontainers loaded with corrosion inhibitors Advantages Reduction of negative effect of the inhibitor on coating Prevention of inhibitor deactivation due to interaction with coating components Controllable release of inhibitor on demand Prevention of the inhibitor leakage Triggers: ph shift, light, pressure, corrosion products, etc. Shchukin, D.G., Möhwald, H. (27): SMALL, 3, Shchukin, D.G., Möhwald, H. (27): Hollow Micro- and Nanoscale Containers, "Advanced Materials Research" Ed. by L.V. Basbanes. 27, Nova Science Publishers, Inc. Andreeva, A.V.; Shchukin, D.G. (28): Materials Today, 11, 24-3.

4 Corrosion inhibitor (INH) loading into mesoporous containers PEI INH INH INH INH INH PSS Polyelectrolyte shell Skorb, E.V.; Fix, D.; Möhwald, H.; Shchukin, D.G. (29): Adv. Funct. Mater., in print.

5 Inhibitor release from nanocontainers OH - neutral alkaline OH - OH - controllable permeability of the polyelectrolyte shell the release of the inhibitor starts only after the begin of the corrosion

6 ph-controlled release of the inhibitor from containers in solution (A) scheme; Zeta Potential (mv) (B) changes of zeta potential during the procedure of polyelectrolyte shell formation; INH content mg/1 g of silica Deposition step % remained Layer number Time, min (C) loading of the interior of titania containers with 2-(benzothiazol-2- ylsulfanyl)- succinic acid under vacuum; (D) the release of inhibitor from nanocontainers at ph=1.1(a), and neutral ph (b)

7 The incorporation of the inhibitor-loaded containers with controlled release Coating Precursor sonication substrate curing Shchukin, D.G., Zheludkevich, M.L., Möhwald, H. (27): J. Mater. Chem. 16,

8 Incorporated containers θ=65 R=1,8

9 Release of the inhibitor from directly-impregnated impregnated coatings and coatings with containers. Conditions: under deaerated Milli-Q Q water (no oxygen, no ions). Coating directly doped with benzotriazole 1 8 3µm % remained Coating with the same amount of benzotriazole in nanocontainers with PE shell for controlled release 1 Days 8 3µm % remained Days

10 Incorporated containers

11 Self-healing effect on coatings with mesoporous containers without containers,.5 M NaCl, 14 days inhibitor-loaded containers with polyelectrolyte shell

12 Structure.5 Halloysite nanotubes Dimensions D V [1-3 cm 3 *Å -1 *g -1 ] nm 15 nm Pore size distribution d max = 17.8 ±.7 nm Pore diameter [nm] 1 µm Lvov, Y.M.; Shchukin, D.G.; Möhwald, H., Price, R.R. (28): ACS Nano 2,

13 Loading of halloysite nanotubes Nanotube lumen Molybdate-loaded nanotube Shchukin, D.G., Lvov, Y. (29): ACS Appl. Mater. and Interfaces, in print.

14 Halloysite-based feedback active anti-corrosive coatings aggressive medium mechanical damage + changed ph locally triggered release of inhibitor! homogeneous distribution metal Fix, D.; Andreeva, D.V.; Lvov, Y.M.; Shchukin, D.G.; Möhwald, H. (29): Adv. Funct. Mater., 11,

15 Halloysite-based coatings Current density observations (SVET) pure sol-gel coating min x [mm] y [mm] min x [mm] y [mm] -3-1 x [mm] 12 min y [mm] with inhibitor 9 loaded halloysite x [mm] y [mm] -3-1 x [mm] y [mm] -3-1 x [mm] y [mm]

16 Visual observations Halloysite-based coatings pure sol-gel coating 1 h in.1 NaCl with inhibitor loaded halloysite 1 h in.1 NaCl

17 Light triggered release Kinetics of benzotriazole release from the containers meso-tio 2 /(PEI/PSS) 2 and meso-tio 2 :Ag/(PEI/PSS) 2 under ph change and under UV and IR irradiation, respectively. remainder, % ph=7,2+ UV UV ph=1, ph=7, time, min time, min light stimulated release (UV, IR) is much faster in comparison with ph stimulate release of incorporated into the container pore chemicals. remainder, % Skorb, E.V.; Skirtach, A.; Möhwald, H.; Shchukin, D.G. (29): ACS Nano, in print IR 3 ph=7,2 1 ph=1,1 2 ph=7,2 + IR

18 Release of the inhibitor by light h.1 M NaCl 12 h 1 min UV irradiation corrosion UV-healing Benzotriazole-loaded mesoporous TiO 2 containers with polyelectrolyte shell in SiO x /ZrO x sol-gel coating on Al E. V. Skorb, D. G. Shchukin, H. Möhwald and D. V. Sviridov, J. Mater. Chem., 29, 19, 4931

19 Anticorrosion activity of polyelectrolyte multilayers ph buffering activity Carrier for corrosion inhibitor Release of inhibitor on demand Stabilization of ph change Regeneration of coating defects Good adhesion to the substrate and sealing the surface defects Barrier for aggressive ions Mobility of the swollen polyelectrolyte complex Andreeva, D.V.; Fix, D.; Möhwald, H., Shchukin, D.G. (28): J. Mater. Chem. 18,

20 Anticorrosion behavior of PE coating with buffer activity 1 bilayers of weak strong PE PEI/PSS.1 M NaCl hr 1.5 hr 16 hr

21 Loading PE multilayers with corrosion inhibitor PSS Inhibitor 8-hydroxyquinoline PSS Prevention inhibitor leakage Release on demand Reduce negative effect of inhibitor on coatings

22 Surface passivation by 8-hydroxiquinoline8 Scanning vibration electrode technique,.1m NaCl A hr 6 hr 16 hr Y, µm X, µm Y, µm X, µm Y, µm X, µm B Andreeva, D.V.; Fix, D.; Möhwald, H., Shchukin, D.G. (28): Adv. Mater., 2,

23 Sealing effect of polyelectrolytes 1 µm Flow of the sealing polyelectrolyte

24 Visual corrosion & stability test in.5 M NaCl solution 12hr 4 days 7 days 21 days

25 Power of sonochemistry Frequencies from 2 khz to 1 GHz; acoustic wavelengths from 1 to 1-4 cm far above molecular and atomic dimensions. Sonochemical effects are derived from acoustic cavitation (negative/positive pressure cycles). The compression of bubbles during cavitation leads to the enormous concentration of energy: ~52 K, ~1 atm, heating and cooling rates ~ 1 1 K/s Potential of ultrasound: To perform chemistry and physics at high temperature but with a reactor near room temperature. Highly nonequilibrium structures can be made which meets the demands of technology as well as physical sciences. Surface energy is converted into chemical energy and its control can make rapid progress in interfacial science. Shchukin, D.G., Möhwald, H. (26): Phys. Chem. Chem. Phys. 8,

26 Surface of the cavitation microbubble ~52 K ~19 K Room temperature The work of evolution R(r) of a bubble with a radius r in metastable liquids is (thermodynamic nucleation theory): R r) = 4π r σ + π r ( P P v ) + ( μ μ ) m ( 1 v 1 3 The probability of the formation of microbubbles is: v * [ R( r ) k T ] ω, R (r*) ~ σ 3 n exp / For a typical surfactant concentration of c s = 1 mm and d= 1 µm the surfactant density is: c 14 Θ s v s = 1 2 mole/cm 2 πd A monolayer coverage and hence a reduction of σ may be expected! Surface active materials in the sonicated liquid will result in drastic reduction of the surface tension increasing the efficiency of the ultrasonic treatment. They decrease surface component of the evolution work and change the difference of the chemical potentials between liquid and gas phases, which is of special interest for sonochemical reactions. B

27 Cavitation microbubbles as templates Polymer/polyelectrolyte air-containing microbubbles heating, 45 ºC Intensity, a.u. PSS Span/Tween PSS Span/Tween H 2 O Shchukin, D.G., Köhler, K., Möhwald, H., Sukhorukov, G.B.: (25) Angew. Chem. Int. Ed., 44, Raman shift, cm -1 Raman confocal microscopy spectra from an aircontaining microbubbles (blue) and surrounding water solution (black).

28 Ultrasound in nanocontainer fabrication SiO 2 containers Grigoriev, D.; Miller, R.; Shchukin, D.; Möhwald, H. (27): SMALL, 3,

29 Containers with oil core and polymer shell Statistics Graph (1 measurements) Active material US generator Intensity (% ) Size (d.nm) polymer Son. LbL Coating General scheme: A. emulsification of active material presenting in oil phase in aqueous polymer solution by ultrasonication; B. shell functionalization (if necessary); C. embedding of nanocontainers into coating film.

30 Ultrasound in nanocontainer fabrication Oil-filled polymer containers Teng, X.; Shchukin, D.G.; Möhwald, H. (27): Adv. Funct. Mater., 17,

31 Containers with oil core and polymer shell Polystyrene shell Polyurithane shell Protein shell Teng, X.; Shchukin, D.G.; Möhwald, H. (28): Langmuir,24,

32 Containers with oil core and polymer shell AFM image of nanocontainers entrapped into polymer film Borodina T., unpublished results.

33 Containers with oil core and polymer shell 2 µm 2 µm 2 µm CLSM of the nanocontainers embedded into polymer coating 1µm 1µm SEM photographs

34 Release profile of VE from bioactive film in H 2 O/EtOH solution

35 Acknowledgements Max Planck Institute of Colloids and Interfaces: Prof. Dr. Helmuth Möhwald Dr. D. Grigoriev, Dr. X. Teng, Dr. E. Skorb, Dr. D. Andreeva, D. Fix, A. Praast, Dr. I. Dönch, Dr. T. Borodina, Dr. Y.-S. Han, M. Haase, Dr. J. Hartmann Institute for Micromanufacturing, Louisiana Tech: Prof. Dr. Y. Lvov