neo chemical seminar 2007 toine dinnissen / march 28th 2007page 1 marine coatings & protective...

NEO Chemical Seminar 2007

Toine Dinnissen / March 28th 2007

Marine Coatings &

Protective Coatings.



Marine & Protective Coatings

Main function of epoxy coatings is toprotect 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 atca. 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 plants10%Public Utilities

11%

Oil & gas production & transmission

11%

Bridges & infrastructure13%

Water and sew age7%

Food & beverage plants8%

Pulp and paper3%

Others7% 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

ChlorinatedRubberAlkyd

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 environmente.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 chemicalresistance

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 & ExtendersSolvents SolventsAdditives 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, AcrylateEpoxy, 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

} Superiorsteel 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 rustsaltmill scaleweld spattergrease & oildirtold 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

EnvironmentWater-Based Acrylic Primer/Topcoat na 16.5 12 9Epoxy Primer/High-Build Epoxy Topcoat 6 18 12 9High-Build Epoxy Primer/High-Build Epoxy Topcoat

7.5 19.5 13.5 10.5

Epoxy Waterborne na 18 12 9High-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 cureto extend application window

• Surface tolerant coatingsto 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 BrochureDow Epoxy Novolac Brochure

Dow Epoxy Resin Product Stewardship ManualDow Epoxy Curing Agents Product Stewardship Manual



Solvents

Role of solvents: Reduce the viscosity and aid the film formationTypes 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 resinsKey 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

Curingagent



Typical Wt Composition of low VOC epoxy coatings

Typical VOC content: 200 – 250g / literLow 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

Curingagent



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 5Curing 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 temperatureDrying 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

Dry

ing

tim

e H

ou

rs

82% Solids

neo chemical seminar 2007 toine dinnissen / march 28th 2007page 1 marine coatings & protective...

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