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Nano Technology in Marine Coatings (Paints) October 30, 2008 Dr. S. K. Kim

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Nano Technology in

Marine Coatings (Paints)

October 30, 2008

Dr. S. K. Kim

STORY

Of

TODAY

Progress in Protective Coatings

Nano Technology in Marine Coatings

Conclusion

Paint vs. Composite

PAINT

Before Application

Resin

Filler & Pigment

Additives

Solvents

Fluid

After Application

Resin

Extender &

Reinforcements

Additives

Material

Drying

And/or

Curing

1. Paint vs. Composite

INGREDIENTS

PROPERTIES

NEEDED

FUNCTIONS

PAINT COMPOSITE

RESINS

FILLERS & PIGMENTS

ADDITIVES

SOLVENTS

RESINS

EXTENDERS

ADDITIVES

ADHESION

PERMEABILITY

HEAT & LIGHT STABILITY

APPLICATION

TOUGHNESS & STRENGTH

HEAT RESISTENCE

DIMENSION STABILITY

PROCESSING

PROTECTION / DECORATION

of MATERIALS or STRUCTURES

PARTS OF MACHINERY

STRUCTURE FRAME

HOUSING

1. Paint vs. Composite

2. Progress in Protective Coatings

Next Protective

Coating Series

Tar Free

Epoxy

Coal Tar

Epoxy

Series

Red Lead

Alkyd

Series

- Good materials for barrier protection, economic,

- Good Flexibility & Substrate tolerance

- Dark color only available, Tar bleeding, Carcinogenic etc.

-1940s ~ 1950s

- Use for long life protection of steel structures

- Need for greater protection performance &

- Zinc-Rich Primers were introduced

- Strongly resistance to chemicals & seawater

- Excellent anticorrosion, Light color available & easy inspection

- High solid & Low VOC, Good workability & fast cure

- Upgrade the coating performance

- Environmentally friendly (Low VOC & Solvent –Free)

- Meet the IMO PSPC Regulation

- Upgrade & Integration Universal Primer

2. Progress in Protective Coatings

Solvent Free

Epoxy

Modified

Epoxy

Pure Epoxy

Full Application in Water Ballast Tank

- Modified Epoxies are commonly specified by Chinese and Japanese Builders.

- Korean builders prefer usually Pure Epoxy system (Yard Standard).

- Recently, Solvent-Free Epoxy system is emerged as the Water Ballast Tank

coating in some European market.

- 90% ~ 95% of Water Ballast Tank are now coated with either Modified Epoxy

or Pure Epoxy systems.

2. Progress in Protective Coatings

Materials

Structure

Function

TECHNIQUE

Introduce New Technology

To Marine Coatings

anticorrosive Pigments selection

Resin Technoloyg & Synthesis

Filler Charging & selection

Accumulated Formulation skill

3. Nano Technology in Marine Coatings

Nano Technology- Contain very small number of particles : Size Effect

- Electronic states quite different from those of bulk : Size Effect

- Contain large portion of surface particles : High surface activity

Encapsulating Technology of PCMs- Upgrade the performance of Nano Characteristics

- Maintain the integrity of the enclosed materials

- Possible to manage the thermal equilibrium in situations

- Possible to control the performance of end-use applications

Surface Modification

3. Nano Technology in Marine Coatings

Definition of Nano Particles by SIZE

- Particles having size less than 0.1㎛(100㎚)

- 1st Generation Nanoparticles : < 100㎚

- 2nd Generation Nanoparticles : < 10㎚

3.1 Nano Technology

1. Small size effect

- Contain very small number of particles

- Electronic states quite different from those of bulky particles

2. Large surface effect

- Contain large portion of surface particles

- High surface activity

3. Change the dimensional properties

- Three-dimensional ⇒ Two-dimensional

Nanocomposite

Mechanical Properties

-Dissemination and interfacial

interactions with the polymer

matrix

-Possible to obtain different

reinforcing levels on mechanical

properties such as abrasion and

impact strength

Chemical Properties

-Reactivity is enhanced by high

surface area / volume ratio and

potential homogenous distribution

of nanoparticles

-Possible to obtain different

reinforcing levels on properties of

adhesion, barrier effect and crack

resistance

Other Properties

-Magnetic Properties

-Optical Properties

-Electrical Properties

-Thermal Properties

-Biological Properties

Characteristic of Nano Particles & Nanocomposite

<Inductive Effect>

-Epoxy resin / Nanoparticles composite can bring out an “ inductive effect”

-Inductive effect can produce large amount of “ Crazes”

-The amount of mechanical and abrasive energy could be absorbed

<Surface Effect>

-The well dispersed Epoxy resin / Nanoparticles composite have great

interaction with each other

-More shear and tensile energy could be absorbed when crack occurred

Mechanism of Mechanical Property Improvement

Test Results of Corrosion Protection Improvement

Nanocomposite enables more particles per unit area…and..Enhance the compactness of the coating film.

Nano-composite systemMicron-composite system

Water (H2O) Water (H2O)

Micron Particles

Nano Particles

Maximize Barrier effect !!

0% Nanoparticle

Composed

5% Nanoparticle

Composed

10% Nanoparticle

Composed

Cycle Corrosion Test (ISO20340)

3.2 Encapsulating Technology of PCMs

Characteristic of Phase Change Materials(PCMs)

Energy

Energy

Solid

State

Liquid

State

Energy

Energy

Phase Changing Point

General PCMs are changed from liquid to solid &

solid to liquid with the temperature range

Surface Modification &

Encapsulating

Unstable !!

Solid

State

A

Most stable !!

Solid

State

B

Surface Modification & Encapsulation PCMs are not changed

from liquid to solid & solid to liquid with the temperature range

Phase Changing Point

Encapsulated double Skin

1. Patent : 10-0481283

2. Patent App. : 10-2004-0056752

3. Patent App. : PCT/KR2005/002371

3. Nano Technology in Marine Coatings

Mechanism of Mechanical Property Improvement

2nd Encapsulated Skin

1st Encapsulated Skin

Hydrophobic Surface

Nano Particle Size

(100nm ~ 200nm)

Nano Particle Size1) Small size effect

2) Large Surface effect

3) Maximize Chemical bond & adsorption

4) Improve crack & abrasion resistance

Hydrophobic Surface- Improve anticorrosive Properties

Phase Change & Latent Heat 1) Not occur phase change & Crack Resistance

2) More stable wide range of temperature

3) Free Volume effect

- Extend recoating Interval

- Enhance interface adhesion

102nm

Test Results of Coating Performance Improvement

0% Nanoparticle

Composed

10% Nanoparticle

Composed

10% Encapsulated

Nanoparticle Composed

Thermal Shock Cycle Crack Test

0% Nanoparticle

Composed

10% Nanoparticle

Composed

10% Encapsulated

Nanoparticle Composed

Salt Fog Test(1,500 hours)

Composite Nanocomposite Encapsulated Nanocompostie

Mechanism of Re-Coating Interval Improvement

Easily Penentrate

Resins & Solvents

2nd

Coat

Substrate

1st Coat

General Pigments

Resin & Co-Polymer

PCMs

Free Volume

PCMs

Heat(30℃~60℃)

Absorb heat energy

Volume expansion

Free Volume

Maximize!!Surface Area

Chemical Bond

Physical Adsorption

Improve!!Recoating Interval

Interfacial Adhesion

4. Conclusion

1st Generation Epoxy AC SeriesStrong resistances to chemicals & seawater Excellent

anticorrosion, Light color available High solid & Low VOC,

Good workability & fast cure

Adopt Nano Technology & Nanocomposite- Modified Double Skin Encapsulated PCMs

- Increase the effect of Nano-particles

- Improve the film performance

- Improve Re-Coating interval

Adopt Aluminum pigment to Improve Performance- Improve barrier effect for anticorrosive properties

- Improve crack & abrasion resistance

Adopt Nanocomposite & Double Skin Encapsulated PCMs

- Maximize barrier effect

- Maximize crack & abrasion resistance

- Upgraded & Integrated Universal Primer of

KCC’s Anticorrosive Coating Series…………

2nd Generation Epoxy AC Series

Next Generation

► Linda S. Salem, Carboline Company “ Epoxies for Steel”

► Johnny Eliasson, Stolt-Nielsen Transportation Group, and Rodney Towers, Safinah

Limited “ The Future of Ballast Tank Coatings”

► Christopher D Rudd, University of Nottingham Robert W Shaw, US Army European Research

Office “ Nanostructures in Polymer Matrices”

► Dr. Lgor Chmutin, Head of Laboratory of nanocomposites “ Polymer Nanocomposites : Prospects

of application”

► Quan Shi, Li Wang, Haojie Yu, Song Jiang, Zhao, Xiaochen Dong “ A Novel Epoxy Resin / CaCO3

Nanocomposite and its Mechanism of Toughness Improvement”

► Brady, Dr. Robert, Jr., and Clive H. Hare. “The Development of a High-Solids Epoxy Polyamide

Coating Line” Journal of Protective Coatings & Linings of April 1989 : 21 - 36

► Munger, Charles G. “Corrosion Prevention by Protective Coatings”

► R. Zandi-Zand., A. Ershad-Langroudi., A. Rahimi. “Silica based organic-Inorganic hybrid

nanocomposite coatings for corrosion protection”

[Reference]