Nano-Technologies VSchmidHannovermesseSurfaceTechnology15.Ppt, 1

Advances in Nano-Coatings to Achieve

Interesting Nano-Effects

Hannover Messe „Surface Technology“

Deutsche Messe AG, Messegelände, 30521 Hannover

13.-17.04.2015

Phone: +49 511 89-0, Mail: incoming@messe.de

Dipl.-Chem. Helmut Schmid

Fraunhofer-Institute Chemical Technology (ICT), Box 1240, D-76318 Pfinztal, Germany Web: www.ict.fhg.de, Phone: +49 721 4640-709, Mail: sd@ict.fhg.de

Multi-Functional Nano-Coatings 2

Index 1. Introduction / Motivation 3

2. Nature and Principles of the Effects 7

3. Cooperation within the Consortium 22

4. Sample Examples / Final Applications 23

5. Summary / Conclusion 31

6. Outlook 33

Introduction / Motivation 3

Why nano effects as wire coatings for architectural applications? The topic of "nanotechnology" has caused high expectations in public perception that were not always met. Therefore, it is interesting to clarify the question what can be realized by relatively simple means of chemical nanotechnology: -Create interesting optical effects -Achieve functional effects -Unique features for partner companies -The competitiveness is improved -Basics for perspective product applications -Companies will be stabilized and thus developed -Securing the future of jobs

Nanotechnology 4 Sources: Fotocommunity, Pons, Wikipedia

Natural NT „Artifical“ Nanotechnology

Nano-Products

Non-Release-Syst. Release-Systems

Inorganic Nanoparticles

Organic Nanoparticles (CNT´s)

Polymer-Binder

Sol/Gel-Technology

Physical Chemical

Classification, our Understanding of Nanotechnology 5

Figure 5.1 Size classification of well known objects. Interesting Nano-Region: 5 – 50 nm.

0,1 nm 1 nm 10 nm 100 nm

0,1 μm

1 μm

1000 nm

0,01 mm

10 μ

Atoms,

Molecules

DNA Viruses

Proteins

Oligomers, Polymers

Bacteria

Biolog.

Cells

Human

Hair

Crystallites

Macroscopic Dimension

Atomar, Molecular

Chemistry

Nano Dimension

VIS

Classification, how you can imagine the dimension of 1 nm 6 Sources: Wikipedia

Figure 6.1 If the gull lands on the aircraft carrier he will delve deeper by 1 nm (assuming a theoretically smooth sea).

2 Nature and Principles of the Effects Optical Principles of Pigments 7 Source: Pfaff

Transparent Effect-Pigments: Reflection, Refraction + Interference, partially Absorption

Metallic Effect-Pigments: Reflection

Absorption Pigments: Absorption, Scattering (Diffuse Reflection)

Roofing Effect: f (Density, Viscosity)

Effect 1: Viewing angle-dependent color impression through nano-coating of micro-interference pigments 8 Source: Pfaff

Figure 8.1: Dependence of the interference color based on the layer thickness. This per se known effect is improved, expanded and polymer-chemically integrated, so that a functional coating results, which also has the required environmental resistance.

Viewing angle-dependent color impression through nano-coating of micro-interference pigments 9 Source: Pfaff

Figure 8.1: Schematic representation of the effect of material and layer combinations in order to exploit the color space.

Pigment-Analysis 10

Figure 10.1 SEM-Record of Interference-Pigments NPI00401-00.

Pigment-Analysis 11

Figure 11.1 SEM-Record of Interference-Pigments NPI00401-21. Dimension of Nano-Coating: 30-50 nm.

Pigment-Analysis 12

Figure 12.1 Polarization-Micrograph of Interference-Pigments NPI00401-(Übersicht2Polarisation).

Theoretical Aspects of Nano-Stabilization 13 Source: Penth

Thermodynamic Effect

Desired Free Energy

Necessity for Stabilization ->

Surface Treatment

Kinetic Aspect

r (Nano-Formation) >> r (Growth, Agglomeration)

Theorectical Aspects – Potential and Field-Theory 14

Equation 1 Calculation of Surface Potential U according to Poisson-Boltzmann-Equation (1) in order to make a suitable selection of chemical additives enabling stabilization and preventing from reagglomeration. B correlates with kH (Hamaker Constant) of Van der Waals Interaction. This type of interaction has to be reduced.

2 2 2 22

2 2 2 2 2

2

2

(cosh cos ) (cosh cos ) sinh *(cos cos )( , ) * * *

(cosh cos ) 1(cosh cos )*sin * * sinh( ( , )) (1)

tan

U: Reduced Ele

U U UU

B B B

UU

B

ctrostatic Potential, B: Constant in Bispheric System of Coordinates

Theorectical Aspects – Potential and Field-Theory 15 Source: TU-Darmstadt

Figure 15.1: Theory of Nano-Particle-Stabilization: FE-Calculation of Electrostatic-potential-gradient between two Al2O3-Particles (5 nm) as a Function of pH and Electrolyte-concentration (left pH2, 0.1 M NaCl, right pH4, 0.001 M NaCl)

Effect 2: Plasmon-Luminescence-Lightingeffect 16 Source: Aldrich

Figure 10.1: The plasmon effect is expected from nanotechnology. In metallic nanoparticles (shown above by the example of nanosilver) light excitation (in the sense of electromagnetic radiation) of the free metallic conduction electrons causes collective resonant oscillations of these "charge clouds". These surface plasmons leads to a lighting effect, if the resonant frequency is in the visible range of the electromagnetic spectrum. The resonance frequency is adjustable via the size of the nanoparticles.

Effekt 2: Plasmon-Luminescence-Lightingeffect 17 Source: Mineralienatlas

Figure 11.1: Additional use of the luminescence effect. Light activation in the UV / VIS range can lead to three types of excitations: Electronic excitation of valence electrons, rotational and vibrational excitation of molecules. If we restrict to the electronic excitation of valence electrons, the electrons are first lifted from the ground state S0 to the higher energy levels of S1 and S2 (HOMO - LUMO transitions). The relaxation occurs by complex laws with additional consideration of the electron spins. The P-transition (shown above in red) finally leads to radiation emission.

Effect 3: Switchable Thermochromic Effect / Change of IR Reflection 18

The Thermochromic Effect is represented by a reversible chemical reaction that leads to a change of the electronic conjugation of double bonds. This effect is performed in a switchable way - as a function of temperature -, where reaction temperature was set to 30 0C for this specific application. For this function nanoparticles additionally play an important role. When heated, the color of the system changes from black to transparent. This is not only an example, usable as an advertising gag -, since it changes the IR reflection coefficient dramatically, heat balancing layers can be produced in this way.

Main Steps from Nano-Particle-Production to Applications 19

Stabilization

System-Integration Polymer-Technology Processing-Technology

Nano-Particle Synthesis

Technical Applications

Transformation in Liquid Phase

Analysis / Characterization

Medical Applications

Nano-Analysis, Characterization 20

STM Scanning Tunnel M.

AFM Atomic Force M.

Morphology: SEM

Particle Size Distribution:

PCS Low Surface Energy of Dispersion-Media improves Wettability.

Chem. / Structure: X-Ray Diffraction

Analytical Methods

TEM (IKP)

Transmission e- M.

X-Ray Fluorescence

AES - ICP

Theoretical Aspects – Safety Concept 21

Chemisorption Physisorption

Van-der-Waals

Kovalent

Ionic

Metallic

Intra- and intermolecular Bounding

Particle-Size

Dependency

Crystal-Field-Theory

Molecule-Orbital-Theory

Surface-Thermodynamics

Potential-Theory

Mech. Anchoring

Weak Elektrostatic

Interakt.

Transition-State-Theory

Partial-Charge, Dipole-I.,

(H-)Bridges: 20 x VdW

3 Cooperation within the Consortium 22

Pigments, Effect Substances

Organic Binders; 1 C, 2 C

Project Partners 2+3: Coating, Application

Project Partner 1: Additiv-Integration

Waterborne System

ICT: Concept, Samples, Analysis

Technology Platforms

4 Sample Examples / Final Applications 23

Figure 14.1: Coating of a wire tape to achieve a viewing angle-dependent color impression using the nano-coated particles NPI00401.

Sample Examples 24

Figure 15.1: Coating of a wire ribbon to achieve a plasmon / luminescence effect using the particle NPI00501. The radiation can be seen in the lower part of the picture.

Sample Examples 25

Figure 16.1: Coating of a wire tape to obtain a - as a function of temperature – reversible switchable thermochromic effect using the additive NPI00601. The left sample part was heated to 31 0C and changed the color from black to transparent.

Environmental Testing, UV-Tests 26

Figures 26.1-4 Results of microscopic evaluation for the nano-

gold lacquer NFO00101 (4), area B1, 241 h (top), area B2, 193 h

(bottom). There are no visible defects.

Environmental-Testing: Condensation Water / Climate Change Cycling Tests 27 Sources: Mendl

Test Conditions Cycle: -8 h including warm up at (40 ± 3) °C; rel. H ~ 100 % with condensation at samples -16 h including cool down (closed climate chamber) at (18 – 28) °C; rel. H. ~ 100 % (~ saturated) Number of Cycles: 3 Total Test Duration: 72 h Visual Inspection

Test Device: Corrosion Chamber Liebisch SKBWF 1000 A-TR

Condensation Water / Climate Change Cycling Tests, Air Temperature Changes according DIN EN 6270 AT

Sample Examples / Final Applications 28

Figure 17.1: Coated sample “Nano-Gold” at Freeport, Singapore.

Final Applications 29

Figure 17.1: Indoor application (left picture) and outdoor use as cladding of a parking garage in Barcelona (right picture) of woven nano-coated metal wires / tapes.

Final Applications 30

Figure 17.1: Final applications shown by example of “Ticon”, Tripoli (Source: GKD). Architectural applications typically comprise large surface areas in the context of major orders. But applications of such coatings must not remain limited to architecture.

Nanotechnology plays a key role in multifunctional coatings.

As a matter of fact the topic "nanotechnology" has caused high

expectations in public perception that were not always met.

Therefore, it is interesting to clarify the question what can be

realized by relatively simple means of chemical nanotechnology.

Of particular interest are the following effects with product

relevance, which are explained in the presentation:

-Viewing angle-dependent color impression through nano-coating

of micro-interference pigments

-Plasmon-Luminescence-Lighting Effect

-Switchable Thermochromic Effect / Change of IR Reflection

For product development usually a combination with other

technologies, e.g. polymer technology is necessary.

To achieve a convincing technical solution all aspects of nano

particle production, stabilization, analysis and system integration

must be covered.

5 Summary / Conclusion 31

From the very beginning, the following aspects need to be

considered:

-Non-toxicity, environmental compatibility, safety concept and it´s

analytical review

-Economy aspects, production possibility and scale-up

-Homologation aspects and legislative injunctions

To enable a perspective market introduction the integration of a

partner with market access and experience is recommended.

5 Summary / Conclusion 32

• Further Nano-Products with additional functionality, will be put to market soon

• Numerous promising systems are still under development

• Multi-Functional Nano-Coatings are identified as a promising field of activity

• Recognizing the overall benefit, investments in this

technology makes sense. Fraunhofer-ICT is looking for further cooperations and product applications especially in your country

6 Outlook 33

Nano-Technologies

34

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