Marine Protect Coatings.ppt

NEO Chemical Seminar 2007
Toine Dinnissen / March 28th 2007 Page 1
Marine Coatings &
Protective Coatings.

Marine & Protective Coatings
Main function of epoxy coatings is to
protect steel structures against
corrosion and against chemicals
• Marine and Offshore
• Industrial Steel Structures
• Industrial Maintenance
• Tanks
• Transportation
– Railcars
– Large vehicles
– Sea containers [China]

Key Market Segments in Europe
Worldwide consumption of anticorrosion coatings estimated at
ca. 1.1 Millions MT, with a value of ca. $ 5 Billions in 2001.
M&PC coatings represent 4% of the global coatings volume,
but 8-9% of the total value.
Petrochemical plants
10%
Public Utilities
11%
Oil & gas production &
transmission
11%
Bridges & infrastructure
13%
Water and sew age
7%
Food & beverage plants
8%
Pulp and paper
3%
Others
7% Marine
30%
Source: SRI Consulting

Marine Coatings
Ballast tanks
The role of epoxy coatings is to protect against corrosion each part of ships,
which are continuously exposed to severe conditions, i.e. sea water
immersion, splashes of sea water, UV rays
– maintain the value of the assets
– ensure vessel safety
– protect cargoes, e.g. grain or liquids

Marine sub-segments
– Water ballast tanks
– Under water hulls and sides
– Cargo tank linings
– Cargo holds
– Boot-topping and splash
zones
– Topsides and external
superstructures
– Offshore oil drilling
platforms
Key Performances
requirements
Resistance to corrosion
Chemical resistance
Mechanical resistance, e.g.
abrasion
Weatherability

Oil & Gas Chemical
Processing
Power
Generation
Pulp & Paper
Mining & Metals Bridges & Infrastructure
Typical Protective Coatings Markets
Pictures downloaded from Akzo Nobel Coatings’ web-site

Non-generic Competition
Source: SRI report 2001
• Epoxy Resins are essential raw materials for Marine & Protective
Coatings.
• Epoxy systems offer an outstanding balance between performances
[durable corrosion protection] and costs.
Consumption of High-Performance Anticorrosion
Coatings by Resin Type in Europe
20%
7%
6%
2%
5%
2%
10% 3%
45%
Epoxy
Urethane
(aliphatic)
Urethane
(aromatic)
Inorganic Zinc
Vinyl
Acrylic
Chlorinated
Rubber
Alkyd
Other

Desired Properties of M&PC Coatings
Each end-use requires an optimum balance between:
– Ambient application window
– Ease of applying [ spray, brush, roll ]
– Solids content, VOC content
– Film thickness
– Drying time
– Sufficient hardness / flexibility
– Edge covering
– Impact resistance
– Overcoating time window,
– Long term corrosion protection
– Long term adhesion, adhesion in wet
environment
e.g. in water immersion conditions
– Resistance against chemicals { acids,
solvents, caustic,… }

• Chemical cure 2 pack systems
Limited pot life
• Excellent adhesion on many substrates
• Excellent corrosion protection
• Superior resistance to water, chemicals, solvents & oil
• Extremely resistant to mechanical stress
• Good surface preparation required
• Curing rate depends upon temperature.
• Chalking when exposed to sun light
• Over coat-ability limitations
Minimum & maximum intervals between layers to be respected
• Cathodic disbondment resistance required in some applications
Properties of ambient cured epoxy coatings

Main Dow resins employed in M&PC
• Bisphenol A epoxy resins & solutions
– D.E.R.™ 331™
– D.E.R. 337X80
– D.E.R. 660X80
– D.E.R. 671
– D.E.R. 671X75
– D.E.R. 671XB70
• Bisphenol F epoxy resin
– D.E.R. 354
• Epoxy novolac resins
– D.E.N.™ 425
– D.E.N. 431
– D.E.N. 438X80
™ Trademark of the Dow Chemical Company
}Best chemical
resistance
Trend towards Liquid Epoxy Resins
and Semi-Solid Epoxy Resins
expected in Europe due to more
stringent VOC regulations

Schematic epoxy coatings formulation
2- Pack Solvent Borne Systems
Component A Component B
Epoxy Resin(s) Curing Agent(s)
Pigments & Extenders Pigments & Extenders
Solvents Solvents
Additives Additives
Accurate Mix ratio.
Thorough mix prior to use.
Pot-life of 1 - 8 hours.
(Pot life depends on temperature, quantity, type of resin and
hardener)
Modifiers e.g. hydrocarbon resins or reactive diluents can be
used

Typical curing agents used in M&PC
Curing agents [mostly based on amine chemistry].
• Polyamidoamines [VersamideTM type]
• Amidoamines
• Epoxy - Amine adducts
• Mannich bases [Faster cure]
• Phenalkamines [Low temperature cure]
Typical accelerators
• Tertiary amines e.g. AncamineTM K54 type
• Alkyl phenols
Remarks:
• Induction time needed with some curing agents to overcome the
limited compatibility with epoxies and to minimize the “blushing effect”.
• Curing agents frequently used at under-stoichiometric levels to
minimize blushing [typical NH / epoxy stoichiometry = 80%]

Example of Anticorrosion Coating System
Metal Substrate
Epoxy
Topcoat; 150 µm
Epoxy
Epoxy, PU, Alkyd, Acrylate
ca 400 µm
Mid coat; 150 µm
Primer; 70 µm
• Top Coat: Appearance & Protection against UV-light
• Mid Coat: Barrier Protection effect. Intercoat
adhesion
• Primer: Corrosion protection & Adhesion

Examples of commercial coatings systems (1)
• Epoxy zinc primer 30 µ
• Epoxy primer 50 µ
• Epoxy tie coat 100 µ
• Epoxy top coat 50 µ
or weatherable PUR
• Epoxy zinc primer 30 µ
• Epoxy aluminium primer 300 µ
• Epoxy top coat 300 µ
}Steel protection
}
Superior
steel protection,
e.g. off shore

Typical Epoxy Polyamide Primer Formulation.
(Red oxide & Zinc Phosphate)
Epoxy resin component Parts by weight
• D.E.R.™ 671X75 Epoxy Resin Solution 18.7
• Pigment grinding additive 0.5
• Zinc Phosphate 10
• Silica Powder 5
• Iron Oxide Red 20
• China Clay 5
• Fumed silica thickener 1
• Xylene 17
• n-Butanol 7
Curing agent component:
• Versamide ® 115/70X 10.6
Or similar polyamido-polyamine hardener

Typical Properties of type 1 epoxy resin /
polyamide formulation.
• Pot-life: min 8 hours
• Coverage: 6 - 7 m2 per liter @ 100 µm
thickness
• Surface hardness: 300 s Persoz Pendulum
• Erichsen Flexibility: min 7 mm
• Salt Spray Test: min 1000 hours
• Low Temperature Cure: 10 °C
• Adhesion to all kinds of substrates
Note: Properties strongly depend on the surface
preparation

Interdependency between Pot life, Drying Times and VOC
Drying times
(full dry)
hours at low
temperature
Pot life @
20°C, hours
1 Hr
8 Hrs
8 Hrs
High VOC
[D.E.R. 671]
48 Hrs
24 Hrs
16 Hrs
Solvent
free
Low VOC,
<250 g / litre
Low VOC or VOC free epoxy systems exhibit a poorer balance
between drying time and pot life than high VOC systems.

Drying times and pot life - Additional comments
• The coatings are often stored in a heated warehouse to prevent
addition of solvent to adjust the viscosity to spray viscosity.
• The epoxy – amine reaction is exothermic
Increase of the pot temperature after mixing of the 2 components
• Coatings drying time dominated by the temperature of the substrate
and by the degree of ventilation.
 Faster reaction kinetics in the pot than in applied paint film,
especially in winter time.
• Generally lower viscosity epoxies have a lower EEW (a higher oxirane
content)
 Higher levels of hardener needed or hardeners with higher NH
content needed.
 High solids / solvent free coatings have a higher concentration of
reactive groups in the mixed paint, which goes against pot-life.

Surface preparation
• The removal of
rust
salt
mill scale
weld spatter
grease & oil
dirt
old paint depending upon quality
and rounding of sharp edges
are critical to achieve optimum performances of epoxy
coatings
• Surface preparation is labour intensive and represents a
significant part of total costs of the coating process.

• Blast cleaning Ideal
• Hydro jetting
• Mechanical wire brushing
• Manual brushing Poor
• Note:
Hydro jetting is increasingly popular.
But it poses some specific problems
Surface preparation techniques

Surface preparation rating
• SA 1 Light blast cleaning
• SA 2 Thorough blast cleaning
• SA 2 1/2 Very thorough blast cleaning
• SA 3 Blast cleaning to visually clean
• St 2 Thorough manual cleaning
• St 3 Very thorough manual cleaning
Optimum coatings performances achieved with SA 2 1/2
cleaning.

Cost of coating is less than 20 % of total cost of painting job
Typical cost structure of a Paint Job
[ Euros / m2 / 150 µm ]
( Brevoort Consultancy )
• Surface Cleaning
– Hand cleaning 4.6
– SA 2.5 blasting 8.0
– SA 3 Near White blasting 9.2
• Application
– Brush / Roller 2.1
– Spray 2.6
• Coating
– Alkyd 1.6
– Epoxy 1.9

Estimated Service Lives of High-Performance
Anticorrosion Coatings (years)
Coating System Salt Water
Immersion
Mildly
Corrosive
Environment
Moderately
Corrosive
Environment
Severely
Corrosive
Environment
Water-Based Acrylic Primer/Topcoat na 16.5 12 9
Epoxy Primer/High-Build Epoxy Topcoat 6 18 12 9
High-Build Epoxy Primer/High-Build Epoxy
Topcoat
7.5 19.5 13.5 10.5
Epoxy Waterborne na 18 12 9
High-Build Epoxy Primer/Acrylic Urethane
Topcoat
na 16.5 10.5 7.5
Inorganic Zinc/Epoxy Mastic/Polyester
Urethane Topcoat
na 31.5 22.5 16.5
Inorganic Zinc/Epoxy Mastic/Acrylic
Urethane Topcoat
na 30 21 15
Inorganic Zinc Primer/Waterborne Acrylic
Topcoat
na 24 16.5 12
Source: GH Brevoort et al
Epoxy based anticorrosive coatings provide long lasting service
life and corrosion protection

Single feed Airless pump & spray gun
Twin feed airless technology exists but is not widely
accepted, because of cost, less user-friendliness
and lower robustness
Typical pressure:
ca 250 Bars.
No pressurized airflow.
High fluid pressures force
the coating through a
small orifice
 Atomization
Minimum pot-life: 45 min
(time to spray 25 liters of
mixed paint)
Otherwise risk of gelation
in the pumps, hoses and
spray guns

Technology Trends & Some unmet needs
• Higher solids coatings
• Solvent-free coatings
• Water borne coatings
• Faster cure
• Low temperature cure
to extend application window
• Surface tolerant coatings
to reduce surface preparation costs
• Improved overcoatability window
• Flexible Epoxy Resins
• Improved balance between drying time and
pot-life
} VOC
reduction
Productivity
gains

Epoxy Resins in Marine & Protective Coatings
Epoxy Resins are essential raw materials for these high
demanding coatings segments, thanks to the
outstanding benefits they provide :
– Corrosion protection
– Chemical resistance
– Mechanical properties, e.g. adhesion
– Low VOC levels achievable
Marine & Protective Coatings, a large and growing
market for epoxy resins

Any questions I could possibly
answer on M&PC applications
?
End of the Marine & Protective Coatings Part
Further Technical as well as Product Stewardship related information can be found
on www.Dowepoxy.com.
e.g.
Dow Epoxy Products Portfolio incl. Corresponding technical datasheets,
Dow Liquid Epoxy Resin Brochure
Dow Epoxy Novolac Brochure
Dow Epoxy Resin Product Stewardship Manual
Dow Epoxy Curing Agents Product Stewardship Manual

Solvents
Role of solvents: Reduce the viscosity and aid the film formation
Types of solvents
• Aromatics, ketones, glycol-ethers, acetates … are suitable.
• Limitations with aliphatic alcohol's which must be used in
combination with better solvents.
• Aliphatic solvents are unsuitable with standard epoxy resins
Key parameters
• Solvency Power
• Hansen Solubility Parameters / Compatibility
• Evaporation profile
• Flash-point
• Solvent retention effect
• Influence on reactivity and pot-life
• Smell
• EH&S properties

Pigments & Fillers
• Opacity and colour
– Titanium dioxide
– Iron oxides
– Organic pigments
• Anticorrosion
– Zinc dust
– Zinc phosphates
– Borates
– Whole range of new
environment friendly
anticorrosive pigments
• Extenders
– Barium sulphates
– Talc
– Silica
– Calcium carbonates
• Barrier
– Aluminium flakes
– Miox
– Mica
– Micaceous iron oxide
• Abrasion resistance
– Glass flakes

Additives
• Accelerators
• Sagging control / Rheology modifiers
• Wetting agents
• Pigment and extender anti-settling additives
• Film Flow additives
• Craters, Orange Peel, Benard Cells
• Foaming / Air release
• Surface Tension
0.1 % of additive can significantly change the
performances

Typical Wt Composition of D.E.R. 671X75 based coatings
Typical VOC content: 300 – 350 g / liter
16%
21%
1%
7%
47%
8%
Epoxy
Solvents
Additives
Pigments
Extenders
Curing
agent

Typical Wt Composition of low VOC epoxy coatings
Typical VOC content: 200 – 250g / liter
Low VOC coatings are based on liquid epoxy resins or on
low viscous semi-solid epoxy resins
17%
15%
1%
8%
50%
9%
Epoxy
Solvents
Additives
Pigments
Extenders
Curing
agent

Types of epoxy coatings
• Shop primers
– Zinc rich primers
• Epoxy primers
– Zinc phosphate primer
• Glass flakes reinforced
coatings.
• Tie coats
• Putty / Caulking
• Transparent varnishes
• Winter grades
• Etc…..
• Solvent borne
• High solids
• Solvent free
• Water Borne

Examples of commercial coatings systems (2)
• Zinc silicate 70 µ
• Epoxy tie coat 50 µ
• High built epoxy coat 200 µ
• Weatherable PUR 50 µ
• Epoxy primer 30 µ
• Epoxy mineral flakes coat 300 µ
}
}Interior tank
lining
Steel protection,
e.g. off shore,
above splash zone

Typical Composition of High Solids Epoxy Primer
Epoxy Resin Component Parts by weight
• D.E.R.™331™ Epoxy Resin 21
• Pigment grinding additive 0.5
• Iron Oxide Red 10
• Barium sulphate filler 20
• Mica filler 20
• Fumed silica thickener 2
• Xylene 10
• Butanol 5
Curing Agent Component
• Ancamine® 2253 [Polyamide type] 12
Note: Hydrocarbon resins [e.g. Necires grades] often employed as
co-binders to reduce the brittleness of “pure” high solids
epoxy coatings.

Drying time versus temperature of commercial coatings
Drying time of epoxy coatings severely affected by temperature
Drying time strongly influenced by solids content
Note: More reactive curing agents generally employed in winter systems
0
5
10
15
20
25
30
35
40
-10 -5 0 5 10 15 20 25 30 35 40
Temperature, °C
68 % Solids
60 % Solids
100% solids
Drying
time
Hours
82% Solids

Marine Protect Coatings.ppt

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