ICCG 12 -shortcourse -June l 11 l 2018 Chemical ... · ICCG 12 -shortcourse -June l 11 l 2018...

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ICCG short course 2018

ICCG 12 - short course - June l 11 l 2018Chemical nanotechnology and sol-gel coatingsDr. Karl-Heinz Haas

Source: Fh-ISCMitteilungen Wilhelm-Ostwald-Ges. zu Großbothen e.V. 12. Jg. (2007) Heft 2, S. 22

© Fraunhofer

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Overview:

� chemical nanotechnology and sol-gel processing

� historic development

� basic reactions: Inorganic and hybrid

� coating techniques and functionalities

� application areas, products and markets

� actual trends in SG coatings

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Solutions for industrial

partnersAnalytics

� Materials characterization

� Failure analysis

� Quality control

� In situ test equipment

� Human 3D in-vitro testing models

Processing� Micro-/Nanoparticles

� Fibers

� (Wet) coatings (R2R, Dip, Spin, etc.)

� 3D/2D structurization

� 3D printing

� Tissue engineering

� Clean room, GMP like facilities

� Demonstrators, pilot plants, automation

Materials

� Glass, Ceramics, ORMOCER®s

� Bioactive materials

� Battery materials

� Magnet materials

� Smart materials

� HT materials (fibers, CMC)

Fraunhofer ISC

Core competencies: materials and processing

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ORMOCER®s, developed by Fraunhofer ISC, trademark of Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., München

ORMOCER®

creative use of adjustable material properties generates new functions

Hybrid materialsORMOCER®s

Inorganic material Organic polymer

R2

R1

R2

ISC highlight: ORMOCER® Chemistry

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„The purposeful engineering of matter at scales of less than 100 nanometers (nm)to achieve size-dependent properties and functions“

source: \Lux research\

not nano „by accident“

not nano „by accident“

What is nanotechnology ?ISO/TS 80004-1 core terms

really smallreally small

not just small: small and different

not just small: small and different

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nanostructured materials

decreasingmelting pointthermal conductivity

E-moduluslight scattering

increasing

reactivity hardness, strength

thermal expansion coeff.diffusion coeff.

spezific surface areasolubility

Nanomaterials: size induced property changes

electronic, optical and magnetic properties are size dependent

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(Nano)-coatings: Processes

� Deposition from gasphase:� physical/chemical PVD/CVD� plasma(-polymerization), sometimes at atmospheric pressure� sputtering � atomic-layer-deposition (ALD) ->

� Liquid phase� galvanics� lacquering� sol-gel

� Structuring� lithography (electronics)� embossing, nanoimprint (NIL)� self-organization (SAM), Langmuir-Blodgett� ink-jet

Al2O3 coated LDPE (source: ALD Nanosolutions Whitepaper)

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Sol-Gel (SG)

� Sol: colloidal solution, particles in liquid/gas (lyosol, hydrosol, aerosol) no sedimentation i.e. Brownian movement is responsible for stability at small particles sizes, no Rayleigh-scattering, transparent

� Gel: 2-phase system, network structure filled with liquid/gas (hydrogel, aerogel/xerogel..), often transparent, inorganic/organic/hybrid

� Solution-Gelation-Process: Gel, network formation from liquids

� Formation of inorganic/organic networks via chemical processes in solution for synthesis of glasses, ceramics and inorganic-organic hybrid polymers

� The Sol-Gel-Process is part of chemical nanotechnology

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� inorganic and

hybrid materials from chemical precursors

liquid, molecular-disperse precursors(organically modifiedmetal-alkoxides)

sol gel

powder

coatings fibers “bulk“-materials

Wet-chemistry for nanomaterials: Sol-Gel-processing

Main advantages:• low T• high purity• molecular composites

→ transparency• easy forming

source: Fraunhofer ISC; Bulk-Materialien: NASA/JPL Caltech

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Gel formation

� Network types� via secondary valences (H-bonding, partially reversible)� chain entanglement (polymers)

� main valences e.g. ≡ Si-O-Si ≡� organic networks (irreversible) – e.g. hybrid polymers

Sol

Gel

source: Fraunhofer ISC

Start

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� 1789 Bergman: acidification ofwater glass: formation of viscoelastic solid,→ Sol-Gel-transition

� 1846 Ebelman: reaction of SiCl4 with alcohol → Si(OR)4,gelation with humidity

� 1923 Patrick: catalysts on SiO2-gels → high surface area

� 1932 Kistler: supercritical drying of gels → Aerogels

� 1939 Geffcken (Schott/Jena): spray pyrolysis on hot glas surfaces

sources: Qingdao Sinoglory Chemical Co.,Ltd http://www.webexhibits.org/causesofcolor/9.html

Sol-Gel-history - 1:

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� 1941 Bell Telephone: Insulator -> alkoxysilanes and organic fillers, the first technical hybrids !

� 1943 Moulton (American Optical Company): Si-/Ti-alkoxide for interference filter

� 1946 Corning: Oxide powders by emulsion process

� 1958 Schott Glas: IROXTM & CalorexTM

Interference filters commercialized

� 1960 DuPont (Iler): Industrial processing of silica colloids

� 1967 DuPont: Al-Oxide fibers

� 1969 3M: Multicomponent fibers

� 1973 Yoldas: Monolithic ceramics from gels

� .......source: “Sol-Gel Chemistry“ J. Livage, Uni Rennes Nov 2005

Sol-Gel-history - 2:

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Industrial applications: fibers and abrasives

3M (1981)Al-Oxid, Ce-Oxid

source: “Sol-Gel Chemistry“ J. Livage, Uni Rennes Nov 2005

Saffil-fibers Al2O3-SiO2 (95-5%)

© Fraunhofer

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Industrial applications: Aerogels – inorganic and hybrid

source: Sanchez et al 2011

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Industrial applications: oxidic coatings

source: left: “Sol-Gel Chemistry“ J. Livage, Uni Rennes Nov 2005; right: Erlus Dachziegel

� Antireflective on glass (TiO2/SiO2) Schott

� Antireflective with nanoporous SiO2

� Heat shielding

� Photocatalysis for glazing and construction materials

Erlus Lotus (TM)

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SG: Industrial implementation

Source: Wet chemical coating technologies Aegerter ISGS Summerschool 2012

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Example: reactions/structures tetraalkoxysilane

� condensation starts immediately after hydrolysis

� formation of rings, branches, chainsdepending on pH, solvent, water, catalyst,substitution (R)

� ≡ Si-OH and ≡ Si-OR containingintermediates

source: Kickelbick “Hybrid Materials“ 2007

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Basic steps of hybrid polymer formation

1st step: formation of inorganic network

hydrolysis

≡ Si-OR + H2O → ≡ Si-OH + ROH

polycondensation

≡Si-OH + HO-Si≡ → ≡Si-O-Si≡ + H2O

≡Si-OR + HO-Si≡ → ≡Si-O-Si≡ + ROH

(possible cocondensation with other metal alkoxides – Ti, Al, Zr)

2nd step: formation of organic network

≡Si-O-Si-X + X-Si-O-Si≡ → ≡Si-O-Si----Si-O-Si≡

crosslinking reactions of Si-bound monomers

addition of non-Si bound monomers also possible

X: acrylate-, vinyl-, epoxy-, isocyanat-, etc.

curing: thermal, UV, redox, plasma

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inorganic network(glass,ceramic)

modified inorganic network(silicone)

organic crosslinking, inorganic-organic network (hybrid polymer)

precursors type I

precursors type II

precursors type III

CH2 C C C

O

M

O

O

O

Si

O

OSi

O

O

O O

M OO

O

M OO

O

O Si

O

SiR

O

O

O

Si RR

O

O Si

O

O

O Si

O

O

CH2 CH2

Si

Si CH2

O

O

Si

O

O CH2 CH2 SiSi OO

O

Si CH2Si

O

INORGANIC ORGANIC

organic network (organic polymer)

precursors type IV

ORMOCER® structural units

© Fraunhofer

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Multifunctional precursors: type II and IIIfunctional groups

O CH2 CH CH2

O

R = H, CH

O R

O C C CH2

CH CH2

R’Si

RO

RO

(R)RO

(CH2)n

sol-gel-process

+H2O- ROH

- H2O

O OO

O

R'R'

Si Si

R'

inorganic backbone

organic crosslinking by UV- or

thermally inducedpolymerisation (curing reaction)

3(CH2)n

(CH2)n(CH2)n

CH3

MeN 3 Cl+ -CF2)5C F3(

NH2

SH

C H6 5

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SG coating functionalities/applications:

� optical: antireflective, heat insulation, optical fiber coatings, optical filters, UV-protection, LED-displays, optical waveguides, electrochromics see short course U. Posset

� electronic properties:

� (transparent) electron conductive

� ion conductive: batteries, fuel cells

� semiconducting: solar cells, photocatalysis

� dielectric layers, ferro-/piezoelectrics

� protection: corrosion (metals, construction materials), thermal and permeation barriers, scratch/abrasion resistance, low friction

� antifouling, antimicrobial, bioactive, biodegradable

� antisoiling, anti-icing, anti-fogging, easy-to-clean, photocatalysis

� gas and liquid sensors, catalysis

� flame retardancy

� encapsulation, controlled release

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SG/coatings: Papers per year Scopus, all fields, total: 117 T

Around 40% ofall SG-papers are dealing with coatings

All SG

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SG/coatings: Patents – No. families/ytotal SG 11500, coatings 4500 (Patbase; /TA)

Around 40% ofall SG-patents are dealing with coatings

All SG

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0

500

1000

1500

2000

2500

3000

2001 2011 2013 2014 estim. 2019-estim.

Mio. US $(BCC-reports)

� around 1/3 in US, Germany is leading in Europe

� high number of coating applications

� high growth rates: electronics, biomaterials and hybrids

Sol-Gel world market (conservative estimate):

Source: BCC-Report “Sol-Gel Processing of Ceramics and Glass” 2014

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Nanocoatings and SG-coatings are sometimes not well separatedMain application areas: Construction, medical, household, electronics

Recent drivers: automotive and aerospace

Source: SG nanocoatings 2016, Future markets

© Fraunhofer

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SG typical coating techniques

dip-coating

spin-coating

spray-coating

Sources: Wikipedia-Sol-Gel

© Fraunhofer

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SG coatings:

� typical thickness (one coat):inorganic: few hundert nm; hybrid: 4-10 µm

� curing: thermal, UV, plasma

� substrates:

� metals and ceramics: inorganic/hybrid

� polymers, paper, wood, textiles: hybrid

� including of (nano)-fillers, pigments, dyestuffs possible

� dense and porous films

� organic functionalities with covalent bonding to hybrid network -> stability

© Fraunhofer

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original PV-glass

ISC anti-dust

up to – 30%

typical– 5%

transmission losses :

vs.

� nanotechnology: antireflective and anti-dust functions

� self-cleaning through wind/humidity due to 3D-surface structure

� low transmission losses in dry or urban areas

Example: Antireflective/antidust coatings - nanoporous SiO2

sources: Fraunhofer-ISC

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catalytic particles

Photoactivity

Self cleaning roof tiles

TiO2

nanoparticles

Application: Photocatalytic active surfaces

Erlus Lotus (TM)

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Example of commercialization: temperature resistant inorganic glass-like coatingson metal

Under-surfaces of steam irons Exhaust pipes

http://www.e-p-g.de/en/surface-finishing/#Temperatureresistance-2

© Fraunhofer

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Hybrid polymer coatings: Comparison with organic lacquers and glass-like oxidic surfaces

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0

5

10

15

20

25

30

35

40

45

0 100 200 300 500

abrasion cycles

% haze

ORMOCER®-coating plane

glass

polycarbonate

in use for eyeglass lenses, mobile phone displays, optical polymer parts

O

O

O

O

O

O

O

O

O

OO

OO

O

O

O

Hybrid polymers as transparent hardcoats: Wet coatings

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Hard and abrasion resistantcoatings on PC/PMMA

Ima

ge

:sR

H &

Esc

he

nb

ach

Examples of commercialization: Transparent hybrid polymer hardcoat

fast UV-curing

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Examples of commercialization: automotive clearcoat i-Gloss TM BASF in-situ fillersiGloss combines two kinds of materials in a nanostructured hybrid.

https://www.basf.com/no/en/company/news-and-media/science-around-us/car-finish-higher-gloss-and-fewer-scratches.html

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PET 1 µm

SEM of hybrid flexible barrier film

POLO concept: Inorganic vacuum-coated layers combined with barrier coatings based on hybrid poly-mers to close the pinholes from sputtering

inorganic layer (SiOx)

hybrid polymer: ORMOCER®

Roll to roll magneton sputteringFh-FEP

ORMOCER® coating by Reverse Gravure Application Fh-IVV

1

250nm

Hybrid materials as barrier systems

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Ultrabarrier foils: Encapsulation of organic solar cells/OLED-displays on flexible substrates using hybrid polymer coatings

© Fraunhofer ISC/IAP

inorganic coating, 20-60 nm

ORMOCER© (< 0,5 µm)

inorganic layer, 20-60 nm

carrier film (PET)

Ultra barrier films2. generation

Barrier values: H2O: ca. 10-5 g/m2 dO2: ca. 10-5 cm3/m2 d bar

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Hybrid multifunctional coatings for packaging materialssee also presentation S. Amberg-Schwab

AimBio-degradable packaging materials basedon renewable raw materials

Properties� Antimicrobial� Barrier (humidity, oxygen, oil/fat)� Indicator functionality (condition of

packaged goods)

Possible with multifunctionalbiodegradable coatings for biopolymers

Benefits� Lower environmental burden� Better CO2 footprint� Extension of functionality

© DIBBIOPACK

EU-Project DIBBIOPACK: 19 partners from 11 countries

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Source © K. Dobberke für Fraunhofer ISC

� avoiding corrosion using hybrid polymer coatings

� excellent adhesion on various substrates

� also useful as primer layer for subsequent coatings

Corrosion protection

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© BASF

Hybrid polymers as passivation for electronics

� electronic control units have to work in ever more severe conditions e.g. near the motor

� ORMOCER®s can be used as thin filmpassivation coating:

� chemical bonding to metallic surfaces ->suppressing ion migration

� low gas permeation (even for sulfur containing gases)

� low space requirement (thin film instead of bulk encapsulation)

© Fraunhofer

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Transparent hybrid polymer coating with TiO2 nanoparticles showing photocatalytic activity

Source: Fraunhofer-ISC

Hybrid polymers with TiO2-nanoparticles: Photocatalysis

© Fh-ISC Würzburg

© Fh-ISC Würzburg

© Fraunhofer

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� Bragg-grating in glass fiber is sensitive towards mechanical stresses � change of optical properties

� Coating is responsible for mechanical stress transfer towards fiber and also protects sensitive fiber

� Fast UV-curable coating

Protective hybrid polymer coatings for Bragg-grating fiber sensors

source: FBGS Technologies, Jena source: Fraunhofer-ISC

© Fraunhofer

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structure

Two-photon-absorption: TPA technology

[1]c

a

[1] S. Fessel et al J Sol-Gel Sci Technol (2012)

no solvent

voxel

lens

ORMOCER®

resin

substrate

development

with solvent

� organic crosslinking of ORMOCER® resins induced by 2-photon-absorption TPA

� high photon density necessary-> focused fs-pulses

� inherent 3D structuring possible

� scalable process (sub-100 nm…µm)

© Fraunhofer

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Elektroden-

partikel

electrode

particle

ORMOCER®

coating

electrode

particle

Electrochemistry: ORMOCER® coatings of/on active materials

Core-Shell� stability of electrode materials� high voltage possible

–> 5 V batteries� good current stability� better cycling stability

→ longlife→ energy density→ power density

© Fraunhofer

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ORMOCER®

50 nm

50 nm

ORMOCER®

50 nm

LMNO

ORMOCER®

LTO NCM

TEM: Ultrathin coatings on LTO: Li4Ti5O12, NCM: Li(Ni,Mn,Co)O2 and LMNO: LiNi1,6Mn0,4O4 particles

50 nm

Coating on electrode materials with Li-Ion conducting hybrid polymers

Source: Fraunhofer-ISC

© Fraunhofer

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ORMOCER® coating of active materials:voltage stability in a NCM-graphite cell

4,3 V

4,2 V; 4,3 V; 4,5 V

4,2 V

NCM with ORMOCER®

NCM uncoated/1

NCM uncoated/2

�Increased cycle stability and charging-end voltage

Number of cycles

Dis

charg

e c

ap

aci

ty/%

© Fraunhofer

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Bild © F. Frech

Si(100)

Li1+xAlxTi2-x(PO4)3

500 nm

>200 nm

� Ultrathin electrolyte layer as

key component in solid state batteries

� Dip coating or other printing processes

All solid-state-electrolytes: based on ceramics

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Conclusion

� Chemical nanotechnology and especially sol-gel processing are leading to more and more industrial applications especially due to the versatility of functionalities based on hybrid inorganic-organic systems and the relative ease of processing various forms (powders, coatings, fibers etc.)

� Scientific interest and also patenting activities are still increasing

� Areas like biomedical applications, additive manufacturing (2D -> 3D), battery materials and the possible use of biogenic precursors will widen the use of sol-gel materials even further

© Fraunhofer

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Dr. Karl-Heinz Haas

[email protected]

Fraunhofer Institute for Silicate Research ISC

Neunerplatz 2 | 97082 Würzburg | Germany

www.isc.fraunhofer.de

Thank you for your attention!

Prisms, 3D-micro-patterned by fs-laser-induced polymerization (2PP) © Fraunhofer ISC

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