REPORT 2012 - ATIPAT Emerging technologies.pdf · Automotive Coating System Funke, W., J. Oil Colour Chem. Assoc., 59 (1976) 398-403 ATIR of functional polymers show different group

8/20/2012

1

Jamil Baghdachi, PhDCoatings Research InstituteEastern Michigan [email protected]

734‐487‐3192

Agosto 29, 2012Costa Salguero, Buenos Aires. Argentina

REPORT 2012

Tecnologías Emergentes en Recubrimientos

8/20/2012

2

Energy & Energy Storage

Smart Coatings

Green Coatings

Emerging Technologies

Energy & Energy Storage

Smart Coatings

Green Coatings

CONTENIDO

Tecnologías Emergentes en Recubrimientos

What is a smart coating ?`1ASD

Emerging Technologies: Products

Gaps in our knowledge

Coatings

Paints

Plastics

High Efficiency by Rational Design

8/20/2012

3


Self-Stratifying

Self-healing

Coating Technologies


Most recent contributions:

VOC reduction-super high solids Coatings from renewable resources Hazardous materials reduction/elimination Functional coatings

• Self-healing/self-stratifying• Self-cleaning• Antimicrobial• Color shifting• 2C1B-3C1B

8/20/2012

4

What is a smart coating ?`1ASD


Gaps in our knowledge

Science Technology Product

Total acid or hydroxyl number in mg/KOH


Technology changes at much faster rate then ever

With globalization, competition has gotten tougher

The life cycle of products have decreased drastically

Customers have gotten more informed and demanding

BusinessMovesat ever

increasing speed

8/20/2012

5


At first people refuse to believe that a strange new thing can be done

And then they begin to hope it can be done

Then they see it can be done

When, it is done, all the world wonders why it was not done centuries ago!

-Frances Hodgson Burnett, The Secret Garden

Scratch Resistant Self-healing Coating


TOKYO (Dec. 2, 2005)-- Nissan Motor Co., Ltd

New scratches One week later

8/20/2012

6


Engagement in Emerging Technologiesin Today’s World is a Must Both for

Established Leaders and Those Who Want to Become Leaders

Create the Future


Conventional approaches for developing raw materials and coatings follow the proven structural

property relationships derived from previous performances and successes

La Innovación Afianza el Futuro

Conventional Technologies vs Emerging Technologies

8/20/2012

7

Multi-Functionality

Nano-technology

Value Added

Products

Driving Forces for Emerging

Technologies

Driving Force

Emerging Technologies Science & Technology Research and Development Applications and markets

Innovation

Secures

the

Future

Driving forces behind


Multi-functionality

Protection

Decoration

Sensory

Properties

Pigments

Polymers

Additives

Emerging Technologies Science & Technology Research and Development Applications and markets

8/20/2012

8



Multi-functionality


AdditivesMultifunctional Additives

- Nano-dispersants- Hyper defoamer- Reactive anionic surfactant- Organic scratch resistant modifiers- Stimuli responsive catalysts

Polymers/coatings/pigments Emulsifier-free polymers Responsive materials Reactive pigments-Graphene BPA replacement

In today’s global competition, it is not the big that swallows small, it is the fast that swallows all

NanotechnologyEngineering and Technical contributions to-2012

Solid state physicsDevice miniaturization

Thin filmsPhotonicsSensors

BiomedicalDrug delivery

Coatings

Coatings Research Institute

8/20/2012

9

AntimicrobialAntireflective/anti-glare Barrier propertiesCorrosion resistanceElectro-magnetic propertiesFire retardantHydrophobicity/hydrophilicityScratch and wear resistanceUltraviolet shielding

Nanotechnology Contribution

Coating Technologies Based on Nanotechnology

Technology Material Application Time-to-market

Nano-particulateCoatings

PolymericNano-materials

ZnO, Al2O3

CeramicsSilverTeflon™

DendrimersPOSSATRP/SIPSupramolecules

Corrosion controlFuel cellsGlass coatingPlastic coating

TopcoatCorrosion control

Current-3 yrsCurrent-5 yrs2-5 yrsCurrent-3 yrsCurrent-3 yrs

2-3 yrscurrent2-3 yrs

Nanotechnology in Coatings

%Effort 95

%Effort 5

8/20/2012

10

Volume sales

Extraordinary Margins

Value Added Products



There are substantial gains for both Users and Suppliers


Not yet!



• Architectured polymers• Functionalized pigments• Responsive pigments• Reactive pigments• Graphene/Graphite• Porous polymers• Reactive additives

• Projected low volume• Application• Long term evaluation• Regulatory/Safety• PMN

Unmet needs

Opportunities Challenges

8/20/2012

11


Multifunctional dendritic/hyperbranched additives Materials for Energy (Organic) Materials for Medical implants, tools and diagnostics Non-fugitive additives (unmet needs for all industries) Crosslinkable switchable liquid ionic materials Biodegradable surfactants Disintegrating ionic liquids Architectured polymers

Vision 2020: Raw Materials


Crosslinking tunable prime pigmentsSensitizing/conducting organic pigments for energy devicesSolid core soft brush polymers (SCSBP): SiO2 / Clay Chemically tint-able pigmentsStimuli responsive pigmentsOrganically functionalized Graphene/Silica particles and colloids

Vision 2020: Raw Materials- Pigments

8/20/2012

12


Coatings from renewable resourcesSelf-stratifying/self-cleaning/self-healing coatingsCoatings for medical implants and toolsCorrosion and degradation sensing coatings*UV/temp./humidity activated color variable coatingsEnvironmentally friendly anti-fouling coatingsElastomeric thermal shielding coatings (textile application)*Thin film corrosion protection*Drug delivery cosmetics* Surfactant-free soaps and cleansers*Antimicrobial/anti-inflammatory cosmetics

Vision 2020: Coatings


Moisture/gas permeability

Thermochromic Coating

Thermochromic Coating

8/20/2012

13

[email protected]


NoDefect SeenUnder Room Light

UV 365

Daylight

Photo-responsive Materials

Applications:

• Epoxy-based primers and topcoats• Polyurethane topcoats

Defect SeenUnder UV Light


US Patent Appl. No. 20100317787

8/20/2012

14

Applications:

• Seed coatings-controlled permeation• Packaging• Temperature activated adhesives• Catalyst encapsulation• Personal care products

Thermally Triggered Coatings

Thermally activated latent cobalt catalyst structure.

Packaging with breathable label.

Soybean and Winter Wheat

1

23

Tunable Polymeric Reactive Pigments

Self-pigmented resin

Joint project Fudan Univ., Shanghai and EMU

8/20/2012

15

Nanoparticle

O C

O

RInhibitorOH

-Nano

particle + HO C

O

RInhibitorNano

particle

Metal

Film former

At the Anode: Fe Fe+2 + 2eAt the Cathode O2 + 2H2O + 4e 4OH

_

Cook, R. TDA Research, www.tda.com

Self-healing Coatings

What is a smart coating ?

A smart coating ?

Tools for Emerging Technologies

Interdisciplinary approaches for formulation New polymer technologies (ATRP, etc…) Silicone, fluorine and organic/inorganic systems Particle chemistry and physics Nano-materials Polymer-biology interface

Emerging Technologies Tools

8/20/2012

16

Emerging Technologies Tools

Living Radical Polymerization Layer-by-Layer Assembly Click Chemistry Polymer brushes Sol-gel Technologies Hybrid Organic Inorganic systems Bioactive polymers Stimuli responsive materials Hyper branched and Dendritic Mtl’s


The nature of stimuli and the responsive functional material are the two main variables in all self-healing technologies

The most widely investigated trigger mechanisms:

Mechanical forces-microcracks, phase separation, etc.

Physical and chemical changes-pH, acids/base formation, electrical field, light, etc.


8/20/2012

17

Responsive “Self-healing” Technologies

Inorganic-organometallic-Chromate, Zn surface treatments-SiC, MoSi2, TiCl4, NiTi, Ti3AlC2,Cementitious materials-Clay (montmorillonite)-Corrosion inhibiting agents

Organic-Thermoplastic materials-fluoropolymers-Thermosetting healing agents



Ionomers and self-healing

Self-healing and Mendable Systems

CH3

OHO

Nucrel

Surlyn

CH3

O O-Na

+

http://www2.dupont.com/Surlyn/en_US/; http://www2.dupont.com/Products/en_RU/Nucrel_en.html.A. Huber and J. A. Hinkley, NASA Tech. Man., 2005, 213532.

CH3

OHO

Nucrel

Surlyn

CH3

O O-Na

+

8/20/2012

18


Self-healing Polymers and Coatings

Polymers have a finite life time. Mending at molecular level may restore original properties and extend the service life

Challenges:

Molecular-size damage Appearance/workability Media compatibility Shelf life

Molecular level damage Micro-cracks Cracks

H. Kautz, D. J. M. van Beek, R. P. Sijbesma and E. W. Meijer, Macromolecules, 2006, 39, 4265.H. Ohkawa, G. B. W. L. Ligthart, R. P. Sijbesma and E. W. Meijer, Macromolecules, 2007, 40, 1453.

Hydrogenbonded

Polymers

Phase changes in a rubbery material based on poly(ethylene-co-butylene), modified with UPy. www.suprapolix.com.

2-butylureido-6-methyl pyrimidone


ealing_coating_SupraPolix

[email protected]

8/20/2012

19

Inherently Conductive Polymers “Self-healing”

Proprietarydopant

Kendig, M., Prog., Org., Coat., 47, 183-189, 2003

Commercial

Plot of current density vs. inverse length for a Cu RDE in aerated 5% NaCl

Y. L. Liu and C. Y. Hsieh, J. Polym. Sci., Polym. Chem., 2006, 44,905.


(a) Crosslinked polymer(b) Knife-cut sample(c) Thermally mended

@ 50 oC/12h(d) Thermally mended

@ 50oC/24h

Removability of TMI-TF@ 90 oC with NMP

d

a

8/20/2012

20

Self-repair Coatings

(B) SEM image of colloidal (3.8 μm polystyrene) aggregates around microcracks produced under a 2-VoltDC electric field.

W.D. Ristenpart, I.A. Aksay, D.A. Saville, Phys. Rev. E 69 021405 (2004).

Confocal spectroscopy images of a scratch obtained by using a 10g load and its profiles at variable healing times(moist + 50 oC) (a) side and (b) front view of the scratch

Self-healing by volume expansion of montmorillonite clay

Si

Si

Si

Si

Si

Si

Si

SiR

R

R

R

R

R

O

O

O

O

O

O

O

O

O

O O

OO

OO

O

H H

OOOO

2,4' Isomer

4,4' Isomer

H H

O

O

OO Cycloaliphatic

Amine

35% 65% 100%

Ce+3Ce+3∆, H2O, OH-

∆Environ > Tm =40 oC

+

Corrosion resistant Hybrid Organic-Inorganic Coatings

ASTM B117 testing: A, control;B, with healing agent after 960 hrs

A B

J. Baghdachi, et al, Coatings Research Institute, patent pending


8/20/2012

21

R

HN

HN

O

SiHN

HN

O

R

HN

HN

O

HN

HN

O

O

O

O

Si

O

O

O

Si

O

O

OSi

OO

O

Si

O

O

S u b s t ra te

Hybrid Organic-Inorganic Sol-gel Coating

Bis-Ureasil

HN NH

O

HN NH

O

SiMeO

OMe

MeO SiOMe

OMe

OMeR C2H5O Si

OC2H5

OC2H5

OC2H5+

10 PAlodine™

1200S1000 hrs

0 PControl

24 hrs

7 PCRI

Sol-gel1000 hrs

Mannari, V., et al, Eastern Michigan UniversityEvaluation: as per SSPC – Vis 2 (Pinpoint rusting standard)

Self-healing is triggered by the elements of the weather

H2O hv, T

Self-healed Chemical reactions

H2O T


The factors that cause the most damage also initiate self-healing and in proportion to the magnitude of the damage

8/20/2012

22


Challenges:

Small non-aggregating capsules Selective responsiveness Stability to media


+ Shell polymer

H2O, Matrix ∆ /H2O

Crosslinked film

Isocyanate Microcapsule

physical


a b

Results: Accelerated Testing

Corrosion Testing, ASTM B117at 840 hrs.

Permeability testing

-4.5

-4-3.5

-3-2.5

-2-1.5

-1-0.5

0

0 5 10 15 20

Elapsed time (day)

Wei

gh

t lo

ss (

gra

m)

UEC

EC

UESH

ESH

Water vapor permeability performance of control and self-healing coating films. U, unexposed; E, exposed; C, control; SH, self-healing

8/20/2012

23

Why stratifying polymers

Stratifying Polymers


Clear Coat

Base Coat

Primer

E-Coat

Metal treatment

EG Steel, SMC…)

Automotive Coating System Funke, W., J. Oil Colour Chem. Assoc., 59 (1976) 398-403

ATIR of functional polymers show different group conc. than in the bulk!

Applications Surface activity* Sensory functions* Economy of process Materials

Designing stratifying systems


Kuczynska, H, et al., J.Coat.Technol. Res., 6(3) (2009), 345-352

• Incompatible low surface energy resin

• Incompatible high surface energy resin

• kinetically competing reactions

Phase separation

T/t

∆Gm = ∆Hm - T∆Sm

8/20/2012

24

Stratifying Coatings


Applications

• Surface activity• Sensory functions• Multi-functionality• Economy of process

Opportunities

-Automotive/Aerospace-Industrial-Medical-Personal care-Military-Packaging-Electronics/Energy

Challenges

FormulationWorkability

Storage

• Media compatibility• Thermosetting• Pigmentation• Intercoat adhesion• Phase dimension• Material density• Durability

When and why polymer mixtures stratify?

Funke, W., J. Oil Colour Chem. Assoc., 59 (1976) 398-403 Verkholantsev, V. , European Coatings Journal 1-2 (2005) p.20-23Vink , P., Bots, T.L, Progress in Org. Coatings, 28 ( 1996) 173-181


• Incompatible polymers• Incompatible solvents• Differential kinetics• Surface tension gradient


8/20/2012

25

= Lower layer matrix= Upper layer matrix= Solvents= Crosslinking

Mechanisms and driving forces of stratification

• Mass transport- resin incompatibility- resin insolubility- viscosity & surface tension gradients- differential reactivity

Stratified film


Stages of Stratification


8/20/2012

26

US Patent: 7,863,375, 8,044,140 B2, US Pat. Appl. 20100317813; Baghdachi et al.


Components of Stratifying Coating:

Hydroxyl Urethane Dendimer

Fluorinated Hydroxyl Acrylic/Vinyl Ether

Aliphatic Diisocyanate

Epoxy/Hydroxy Silsesquioxane

DOH

FOH

NCO

POSS



LF-200+ HDI+ Dendrimer

Upper Layer Matrix Reaction

OH Reactivity toward NCO

1O Dendrimer OH >>> 2O Lumiflon OH

Reaction kinetics driving force

N

N

N

O

O O

HNNH

NH

CON

OH

OH

NOC

OH

NOC

OH

OH

XF

F

F X

F F F F

F X

O

R1

O

R2

F F F

F X O

R3

NH CO

NH CO

Kinetic and Mass Transfer Control



8/20/2012

27

Photographs of stratified composition

Formation of Stratifying Coating


Upper layer

Lower layer

Substrate

SEM image of stratified coating

Characterization and Instrumental Analysis


8/20/2012

28

SEM image of stratified coating

Self-stratifying coatings

Atomic concentration of selected elements in stratified coating.

0 24 hrs

RT


Characterization and Instrumental Analysis

SEM image and EDX of stratified coating


Adhesion 5B, MEK rubs > 200

F, 10.851Si, 0.741

F, 0.00Si, 15.760

8/20/2012

29

Pigmentation

Area1 Elt. Line Intensity

(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 8.52 0.825 86.573 180.7425 70.375 wt.% 0.2280 O Ka 0.11 0.094 0.479 1.0000 0.519 wt.% 0.0018 F Ka 0.72 0.241 0.956 1.9959 1.229 wt.% 0.0079 Si Ka 16.99 1.166 1.981 4.1359 3.766 wt.% 0.1013 Cl Ka 87.71 2.649 9.901 20.6715 23.758 wt.% 0.6522 Ti Ka 0.84 0.260 0.109 0.2279 0.354 wt.% 0.0088 100.000 100.000 wt.% Total


(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 4.79 0.619 65.459 255.5590 39.990 wt.% 0.0939 O Ka 0.04 0.055 0.256 1.0000 0.208 wt.% 0.0005 F Ka 0.17 0.116 0.393 1.5331 0.379 wt.% 0.0014 Si Ka 101.46 2.849 20.860 81.4381 29.799 wt.% 0.4571 Cl Ka 15.28 1.106 3.337 13.0278 6.017 wt.% 0.0864 Ti Ka 44.79 1.893 9.695 37.8511 23.605 wt.% 0.3606 100.000 100.000 wt.% Total


SEM of TiO2 pigmentedsystem

TiO2 = 0.354

TiO2 = 23.60

EDX elemental analysis of area 1 and 2


(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 20.29 1.274 87.549 378.1348 72.723 wt.% 0.2532 O Ka 0.11 0.096 0.232 1.0000 0.256 wt.% 0.0008 F Ka 2.93 0.484 1.722 7.4387 2.263 wt.% 0.0138 Al Ka 0.16 0.113 0.008 0.0352 0.015 wt.% 0.0004 Si Ka 43.73 1.870 1.933 8.3507 3.755 wt.% 0.1073 Cl Ka 208.36 4.083 8.510 36.7555 20.865 wt.% 0.6212 K Ka 0.99 0.282 0.045 0.1950 0.122 wt.% 0.0033 100.000 100.000 wt.% TotalArea2 Elt. Line Intensity

(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 17.10 1.170 81.390 120.5672 64.550 wt.% 0.1962 O Ka 0.35 0.168 0.675 1.0000 0.713 wt.% 0.0023 F Ka 1.85 0.385 1.059 1.5690 1.329 wt.% 0.0079 Al Ka 55.43 2.106 2.880 4.2657 5.130 wt.% 0.1205 Si Ka 184.30 3.840 9.240 13.6869 17.135 wt.% 0.4091 Cl Ka 97.43 2.792 4.721 6.9938 11.052 wt.% 0.2618 K Ka 0.73 0.242 0.035 0.0519 0.091 wt.% 0.0022 100.000 100.000 wt.% TotalArea3 Elt. Line Intensity

(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 18.91 1.230 80.173 74.0265 63.802 wt.% 0.1940 O Ka 0.58 0.216 1.083 1.0000 1.148 wt.% 0.0034 F Ka 0.00 0.000 0.000 0.0000 0.000 wt.% 0.0000 Al Ka 1.98 0.398 0.100 0.0923 0.179 wt.% 0.0038 Si Ka 396.56 5.632 18.303 16.8999 34.060 wt.% 0.7831 Cl Ka 5.68 0.674 0.304 0.2811 0.715 wt.% 0.0136 K Ka 0.78 0.249 0.037 0.0343 0.096 wt.% 0.0021 100.000 100.000 wt.% Total

Aluminum flake-pigmented stratified coating


Aluminum flakes


Al = 5.130

Al = 0.015

Al = 0.179

8/20/2012

30

Alternative Chemistries


F = 15.516Si = 2.063

F = 0.196Si = 16.946

Amine cured epoxy/PE-PU Free radical UV cured BC/CC Bis-Ureasil primer/PE-PU

US Pat. Appl. No. 2010031555

• Silver-based antimicrobial agentsReview article: Efficacy of antiadhesive, antibiotic and antiseptic coatings in preventing catheter-related infections, Donelli G.; Francolini, I; J. Chemotherapy, 3 (6): 595-606, 2001.

• Alkylammonium saltsPolymer surfaces derivatized with poly(vinyl-N-hexylprydinium) kill airborne and waterborne bacteria, Tiller, J.; Lee, S.; Lewis, K; Kilbanov, A., Biotechnology and Bioengineering79, (4) 465-471, 2002.

• N-Halamine (Hydantoin-based)Biocidal polyester, Lin, J.; Winkelmann, C.; Worley, D.; et.al., J. Appl. Polym. Sci.85, 177-182, 2002.

• Titanium Dioxide Nanocomposites Sunada K., Watanabe T., and Hashimoto K., Environ. Sci. Technol. 2003, 37, 4785-4789.

Biocidal Polymers and Surfaces

8/20/2012

31

“Sustainable development is development that meets the needs of the present without compromising the ability of future generations to meet their own needs”

World Commission on Environment and Development (WCED). Our common future. Oxford: Oxford University Press, 1987 p. 43.

Sustainability is about living and working in a way that meets and integrates existing environmental

economic and social needs without compromising the well-being of current and future generations.

Environment, Energy and Sustainability

Minimal Environmental

Impact

Management of Energy

and Economy

Sustainability

Manufacturing with lowest Energy/Waste and Longer Service Life Materials and Energy from Renewable Resources


8/20/2012

32

What are the choices?


What are the choices?


8/20/2012

33

Some Figures

Each windmill uses as much paint coatings as:

60 average rooms30 average size cars10 houses5 highway bridges

Estimated $ worth of materials using polymers and coatings is 3.5‐4.0 Trillion

Estimated $ worth of coatings and paints87 Billion

2011

The Impact of Polymers and Coatings

8/20/2012

34

OpportunitiesChallenges

Environmentally friendly materials

Reduce carbon foot print

Minimal negative economical impact

Maintain current and future quality of life

New approaches

‐Chemistries & Materials

‐Applications & Processes

‐Multi‐functionality

‐Durability

Non‐fossil fuel energy

Potential Sustainable Chemical Technologies

Opportunities

New approaches

-Chemistries & Materials

-Applications & Processes

-Multi-functionality

-Durability

Non-fossil fuel energy

Challenges

Land use

Lack of established health effects

Effect on food supplies

Effect on environment

Costs


8/20/2012

35


Removal/replacement of solvents

Long life cycle

Low energy reaction chemistries

Materials from renewable resources

Removal of hazardous chemicals

Plant oils, glucose, fiber, biomass/waste…

Chrome VI, Hg, Pb, Sr. …

Radiation cure, latent catalysts, …

Self‐repair, materials …

Water‐based, powder, UV, high solids….

Soybean oil triglyceride and derivatives

Challenges

Seasonal and geographical variability

Unsaturation Characteristic smell Low modulus

O

O

O

O

O

O

O

HO

Renewable feedstock (Soybean oil)

8/20/2012

36

Renewable feedstock (Soybean oil)

Low viscosity, lightly colored, high boiling point, low evaporation rate

Renewable feed stock (Soybean oil)

Baghdachi, J., Li, D. LaForest, J., JCT, 74, 932, 81-87, 2002.

Baghdachi, J., Massingill, J. JCT., vol 73, No. 914, 2001.

Brian, CM, et al. J. Am. Chem. Soc. 126 (37) 11404, 2004.

8/20/2012

37

73

Current Commercial Timeline: Bio-based Resins

Alkyds

100 %

2010 2015 2020

Acr

ylic

s

%Rene-wable

Polyurethanes

0 %

Acrylics

Alkyds

100 %

2010 2015 2020

Acr

ylic

s

%Rene-wable

Polyurethanes

0 %

Acrylics

World production of plant materials =100 trillion kg new plant dry matter/yr.

= approx. 10 times the total worldwide use of all forms of energy (B. Dale, 2003)

Major crop residues = 100 trillion kg /yr.

Total US consumption of organic chemicals = 100 billion kg /yr.

Some Figures

１000 Trillion kg

IsThere

EnoughBiomass

Christian V Stevens, Ghent University, Belgium

8/20/2012

38

A smart coating is one which detects and responds dynamically to changes in its environment in a functional, and predictable manner.

What is a smart coating

Science and Technology already exists!


Smart ProcessesSmart Materials

Women’s slippers and men’s slippers by Smartdogs are constructed by the

finest materials

Smartdogs' Weblog

men smart shirts cotton -Alibaba.com

SmartBearSoftware

8/20/2012

39

Coatings and Polymers are Only Getting Smarter

Introduction of functionality into “mobile” locations in polymeric structure will ensure reactivity and interactivity that is required for

many emerging smart applications

Smart Coatings

To make microelectronics with no moving parts To extend the lifetime of coatings To replace mechanical sensors To deal with unpredictable contingencies To control function on demand To play a role in medical fields

And, more…

Why we need smart coatings

Science & Technology Research and Development Applications and MarketsSmart Coatings: Definition..

8/20/2012

40

Conventional vs. Responsive Materials

To Guarantee

Survival

Dynamic,Reshape,Rebuild,

Reorganize

BonesCell Membranes

Most synthetic materials follow a permanently defined path and behave statically.

Biological materials:

Stimuli

Chemical Signals

Acid-base reactions Complexation Bond formation/breaking Electrochemical reactions Photochemical reactions

Physical Signals

pH Ionic strength Temperature Pressure/mechanical Surface tension Light and acoustic Electrical/magnetic fields

Smart Coatings: Definition.. Research and Development Applications and MarketsScience & Technology

8/20/2012

41

Types of smart coatings

• One-way systems-Stimuli responsive with permanent change

• Two-way systems-Reversibly stimuli responsive

Smart Coatings: Definition.. Research and Development Applications and MarketsScience & Technology

Anti-inflammatorySelf-healing

ThermochromicColor-shifting

Smart Coatings and Materials

Conductive polymers and coatings Thermochromic and photochromic coatings Piezoelectric and pressure sensing coatings Anti-inflammatory/antimicrobial coatings Self-cleaning coatings, Self-healing Self-erasing, stealth and RFI coatings

Commercially available!

8/20/2012

42

What is a smart coating ?


A smart coating ?

CostHow difficult is it to make

How difficult is it to Make?

How expensive is it to Make?

How difficult is it

sell/buy? $1.2 Billion in sales and 45% market share in 2010

• Responsive Additives/Pigments• Responsive Polymers• Coating System Design

Designing a Smart Coating

8/20/2012

43

Acid-base reactions

Hydrophobic Hydrophilic Protonation

Deprotonation

pH responsive

COOH HOOC COOH

COOH

C O

O CH2CH2 N

CH3

CH3 N

NH2 Ref. 1

Acid-base reactions

Hydrophobic Hydrophilic Protonation

Deprotonation

Responsive Materials

Ring opening

Thermal phaseTransition

BLUE WHITE

8/20/2012

44

Thermo-responsive Materials

Thermochromic response in hot water.Absorption spectra of a polyethylene film with 5% thermochromic composite.

Antimicrobial Antifouling Bio-catalytic Camouflage Color shifting Conductive Controlled drug release Corrosion sensing Defect/degradation sensing Light sensing Molecular electronics Molecular brushes

Nanotechnology-based Optically active Photo-catalytic Photochromic Pressure sensing Shape-memory polymers Self-cleaning Self-repair and healing Super hydrophobicThermally triggeredThermochromic

Examples of Smart Coatings

8/20/2012

45

System Stimuli Response Sensing

mechanism

Application

1 Mechanical force

Capsule rupture

Release of film former

Self-healing

Corrosion control

2 Temperature Hyrophilicity/

hydrophobicity

Config and morphol. change

Coatings for biomaterials

3 Aging H2O resistance Dielectric sensing

Durability monitoring

Stimuli responsive coatings

Xanthos, M, et al. Adv Poly Technol, 26, 1, 1-13, 2007

Smart Coatings: Definition.. Applications and MarketsResearch and DevelopmentScience & Technology

Stimulus Response Sensing Mechanism

Application

pH Color Diff. color

In ionic form

Corrosion

Sensing

Mechanical

Forces

Capsule rupture Dye release Ink transfer

TNT, nerve gas

Presence

Quenching

fluorescence

TNT bind to receptors

TNT & nerve

Gas sensor

Stimuli responsive coatings with functional colorants

Xanthos, M, et al. Adv Poly Technol, 26, 1, 1-13, 2007

Smart Coatings: Definition.. Applications and MarketsResearch and DevelopmentScience & Technology

8/20/2012

46

Emerging technology products are based oninterdisciplinary approach for material design andapplication

The products are the result of balanced approach inblending old technology and new science

There are many situations in which coatings basedon Emerging Technologies not only provide thebasic function of coatings but also achieveresults that cannot be attained any other way.

Summary

Thank You!Jamil Baghdachi

Coatings Research Institute Eastern Michigan University

Ypsilanti, MI, 48197 (USA)[email protected]

[email protected]

Documents

REPORT 2012 - ATIPAT Emerging technologies.pdf · Automotive Coating System Funke, W., J. Oil Colour Chem. Assoc., 59 (1976) 398-403 ATIR of functional polymers show different group