Nano Technology in

Marine Coatings (Paints)

October 30, 2008

Dr. S. K. Kim
 Paint vs. Composite

Progress in Protective Coatings

STORY
Of
TODAY Nano Technology in Marine Coatings

Conclusion
1. Paint vs. Composite

PAINT

Before Application After Application

Resin Drying Resin

Filler & Pigment Extender &
And/or
Additives Reinforcements
Curing
Solvents Additives

Fluid Material
1. Paint vs. Composite

PAINT COMPOSITE

RESINS RESINS
FILLERS & PIGMENTS EXTENDERS
INGREDIENTS
ADDITIVES ADDITIVES
SOLVENTS

ADHESION TOUGHNESS & STRENGTH

PROPERTIES PERMEABILITY HEAT RESISTENCE
NEEDED HEAT & LIGHT STABILITY DIMENSION STABILITY
APPLICATION PROCESSING

PARTS OF MACHINERY
PROTECTION / DECORATION
FUNCTIONS STRUCTURE FRAME
of MATERIALS or STRUCTURES
HOUSING
2. Progress in Protective Coatings
-1940s ~ 1950s
Red Lead - Use for long life protection of steel structures
Alkyd - Need for greater protection performance &
Series - Zinc-Rich Primers were introduced

- Good materials for barrier protection, economic,

- Good Flexibility & Substrate tolerance
Coal Tar - Dark color only available, Tar bleeding, Carcinogenic etc.
Epoxy
Series - Strongly resistance to chemicals & seawater
- Excellent anticorrosion, Light color available & easy inspection
- High solid & Low VOC, Good workability & fast cure

Tar Free
Epoxy
- Upgrade the coating performance
Next Protective - Environmentally friendly (Low VOC & Solvent –Free)
Coating Series - Meet the IMO PSPC Regulation
- Upgrade & Integration Universal Primer
2. Progress in Protective Coatings
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.

Solvent Free
Epoxy

Modified
Epoxy

Pure Epoxy
2. Progress in Protective Coatings

Materials anticorrosive Pigments selection

Structure Resin Technoloyg & Synthesis

Introduce New Technology

To Marine Coatings
Function Filler Charging & selection

TECHNIQUE 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

Surface Modification

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
3. Nano Technology in Marine Coatings
3.1 Nano Technology

Definition of Nano Particles by SIZE

- Particles having size less than 0.1㎛(100㎚)
- 1st Generation Nanoparticles : ＜ 100㎚
- 2nd Generation Nanoparticles : ＜ 10㎚
Characteristic of Nano Particles & Nanocomposite

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 Chemical Properties Other Properties

-Reactivity is enhanced by high
surface area / volume ratio and -Magnetic Properties
-Dissemination and interfacial potential homogenous distribution
-Optical Properties
interactions with the polymer of nanoparticles
matrix -Electrical Properties
-Possible to obtain different -Thermal Properties
-Possible to obtain different reinforcing levels on properties of
reinforcing levels on mechanical -Biological Properties
adhesion, barrier effect and crack
properties such as abrasion and
resistance
impact strength
 Mechanism of Mechanical Property Improvement

<Inductive Effect> <Surface Effect>

-Epoxy resin / Nanoparticles composite can bring out an “ inductive effect” -The well dispersed Epoxy resin / Nanoparticles composite have great
-Inductive effect can produce large amount of “ Crazes” interaction with each other
-The amount of mechanical and abrasive energy could be absorbed -More shear and tensile energy could be absorbed when crack occurred
 Test Results of Corrosion Protection Improvement

Nanocomposite enables more particles per unit area…and..

Enhance the compactness of the coating film.

Cycle Corrosion Test (ISO20340)

10% Nanoparticle 5% Nanoparticle 0% Nanoparticle Micron-composite system Nano-composite system
Composed Composed Composed
Water (H2O) Water (H2O)

Micron Particles
Nano Particles

Maximize Barrier effect !!

3. Nano Technology in Marine Coatings
3.2 Encapsulating Technology of PCMs

Characteristic of Phase Change Materials(PCMs)

Encapsulated double Skin

Solid
State Energy
Solid Energy
State A

Phase Changing Point

Surface Modification Phase Changing Point
&
Encapsulating
Energy Solid
Energy Liquid State
State B

Unstable !! Most stable !!

General PCMs are changed from liquid to solid & Surface Modification & Encapsulation PCMs are not changed
solid to liquid with the temperature range from liquid to solid & solid to liquid with the temperature range

1. Patent : 10-0481283
2. Patent App. : 10-2004-0056752
3. Patent App. : PCT/KR2005/002371
Mechanism of Mechanical Property Improvement

Nano Particle Size

1) Small size effect
2) Large Surface effect
3) Maximize Chemical bond & adsorption
4) Improve crack & abrasion resistance

102nm

Hydrophobic Surface
- Improve anticorrosive Properties

Hydrophobic Surface

Phase Change & Latent Heat

1) Not occur phase change & Crack Resistance
2) More stable wide range of temperature
3) Free Volume effect
Nano Particle Size - Extend recoating Interval
(100nm ~ 200nm) - Enhance interface adhesion

1st Encapsulated Skin

2nd Encapsulated Skin
Test Results of Coating Performance Improvement

Thermal Shock Cycle Crack Test Salt Fog Test(1,500 hours)

10% Encapsulated 10% Nanoparticle 0% Nanoparticle 10% Encapsulated 10% Nanoparticle 0% Nanoparticle
Nanoparticle Composed Composed Composed Nanoparticle Composed Composed Composed

Composite Nanocomposite Encapsulated Nanocompostie

Mechanism of Re-Coating Interval Improvement

General Pigments PCMs

Resin & Co-Polymer Heat(30℃~60℃)
Improve!!
PCMs Recoating Interval Absorb heat energy
Interfacial Adhesion
Free Volume

Easily Penentrate Volume expansion

Resins & Solvents

Maximize!!
Surface Area Free Volume
Chemical Bond
Physical Adsorption

2nd Coat

1st Coat

Substrate
4. Conclusion
Strong resistances to chemicals & seawater Excellent
anticorrosion, Light color available High solid & Low VOC, 1st Generation Epoxy AC Series
Good workability & fast cure

Adopt Aluminum pigment to Improve Performance

- Improve barrier effect for anticorrosive properties
- Improve crack & abrasion resistance

Adopt Nano Technology & Nanocomposite 2nd Generation Epoxy AC Series

- Modified Double Skin Encapsulated PCMs
- Increase the effect of Nano-particles
- Improve the film performance
- Improve Re-Coating interval

Adopt Nanocomposite & Double Skin Encapsulated PCMs

- Maximize barrier effect
- Maximize crack & abrasion resistance
- Upgraded & Integrated Universal Primer of
Next Generation
KCC’s Anticorrosive Coating Series…………
[Reference]

► 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”