Comparaison VER and Epoxy System &

Review of VER based applications in Oil &

Gas Industries

Guy Schneider

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Ashland: Leading Specialty Chemicals Business

Ashland
in sales − $3.4 B in Sales
− 5,000 Employees, 60+ global
facilities, sales in >100 countries

Performance
Materials Industrial
33% Specialties

Performance Materials: $1.1 B in Sales

34%

. World leader in VER.

Consumer
Specialties
. World leader in UPR.
33%

Ashland is dedicated to the Composite industry.

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 History of Vinylester Resins

− VER have been created more than 50 years ago, by

Dow Chemical under the name Derakane followed
shortly after by Shell.

− These two (ex) Epoxy giants have created VER to

solve corrosion problems in their plants.

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 Epoxy Vinyl Ester Resins are made from
Epoxy Resins and Methacrylic Acid

Dissolved in Styrene

Epoxy Vinyl Ester Resins

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 VER & Epoxy categories

− VER can be split in two major categories

(Bisphenol A based or Novolac based).

− Epoxies systems are made of either

Bisphenol A or Novolac Epoxy resins +
hardener. The nature of the hardener that
can represent a significant portion of the
system (20% - 40%) plays a crucial role on
the end properties. As a result comparing
VER and Epoxy Resin (EP) is not
straightforward.

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 VER properties
Properties

Mechanical Resistance
Similar to Epoxy Resins
Thermal Resistance

Viscosity Similar to unsaturated polyester

Handling resins (UP)

Cure
Chemical Resistance Better than Epoxy - or UP resins

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Comparison table
Typical Property Bis A based Novolac based (non MDA) Cycloaliphatic Test Method
VER VER aromatic amine amine + DGEBA
+ DGEBA Epoxy Epoxy
Tensile strength ISO 527 / ASTM
(MPa) 85 85 75 70 - 85 D-638
Tensile modulus ISO 527 / ASTM
(GPa) 3.4 3.6 3.5 2.2 D-638
Tensile
Elongation at ISO 527 / ASTM
yield (%) 5-6 3-4 3-4 4 D-638
Flexural strength ISO 178 / ASTM
(MPa) 150 130 155 120-160 D-790
Flexural modulus ISO 178 / ASTM
(GPa) 3.4 3.8 3.6 2.8-3.5 D-790
Heat Deflection
Temp (°C) at 1.8 ISO 75 / ASTM
MPA stress 105 150 147 110 - 150 D-648

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 Mechanical comparaison
− Pressure resistance: While most of the VER based case histories
refer to a pressure <35bars, they can be used to higher pressures
and as such are comparable to most Epoxy systems. CNG
(compressed natural gas) cylinders is a good illustration of that.
Pressure above 60 bars would however result in the use of EP.

− Regression curve (50 years): regression curve with extrapolated

values up to 50 years life time are comparable for EP and VER
under the condition that the same stress is applied. The creep
factor for both resin types varies from 1.1 to 1.3 as the stress
varies from 30% to 50% of the ultimate failure stress.

− Influence of reinforcement: Importance of the sizing of

reinforcement that plays key role in mechanical properties.

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 OTHER PROPERTIES:

− Permeation: As the cross link density of a pipe made of epoxy /

amine and epoxy vinyl ester resin is comparable the
permeation of pipes made with both resins are comparable.
When “no permeation” is allowed then a metal seal membrane
has to be used.

− Osmosis: Comparative tests of epoxy resins, cured with various

hardeners, and Deionized water (DI water) at 100 degC show a
weight gain (ca. 2.5 wt %) i.e. comparable to vinyl ester resins.
But the importance of the laminate structure should be
emphasized…

− Fire resistance: Whenever fire resistance is an issue, the epoxy

backbone of EP is modified with halogen (mostly Bromine).
These modified EP would then become the raw material for
making Brominated based VER. Styrene monomer as well as
hardeners do not contribute to the fire resistance therefore
brominated EP and VER have similar fire resistance properties .

− Coefficient of thermal expansion (COE): (CEO) of an EP or VER is

comparable and is ca. 60 m/m degC.
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 Corrosion resistance aspect:

− EP based FRP equipment are almost non existent in all the main
industrial segment that uses non metallic material to fight corrosion
(Chemical processing, Mining, Pulp & Paper, Air pollution control). Dow
Chemical is a good illustration of that.

− VER have intrinsic better corrosion properties that’s why they have
been created by Epoxy suppliers.

− The corrosion resistance is provided by a corrosion liner that is not

possible to make in many EP equipment, while this is not an issue with
VER based equipment.

− The requirement for postcure at high temperature associated with EP

would eliminate any equipment of significant size.

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 Corrosion resistance aspect:

− EP based FRP equipment are almost non existent in all the main
industrial segment that uses non metallic material to fight corrosion
(Chemical processing, Mining, Pulp & Paper, Air pollution control). Dow
Chemical is a good illustration of that.

− VER have intrinsic better corrosion properties that’s why they have
been created by Epoxy suppliers.

− The corrosion resistance is provided by a corrosion liner that is not

possible to make in many EP equipment, while this is not an issue with
VER based equipment.

− The requirement for postcure at high temperature associated with EP

would eliminate any equipment of significant size.

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 Chemical resistance table

Chemical environment Concentration % Bis A based VER (°C) Novolac based VER (°C)
Crude oil, sweet and
sour 100 100 120
Diesel fuel 100 80 100
Fuel C (50/50
Isooctane / Toluene) 100 50
Fuel Oil 100 80 100
Jet fuel, general 100 60 60
Kerosene 100 80 80
Methanol 5 50 50
Methanol 20 NR 40
Phenol <2> 0-2 25 50
Water 100 80 80
Seawater 100 100 100
Gasoline, no alcohol 100 50
Gasohol (1-100%
Alcohol) 100 40
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 Cost comparaison:

− Raw material costs: VER cost will always be linked to the cost of EP, but
the cost of the Epoxy system will be very dependent on the cost of the
hardener, and apart from few cases, VER will always be cheaper.

− Processing cost: The processing of VER is easy, can be quick as cure

time can be adjusted by additives and/or temperature unlike EP. In
addition to that postcure at high temperature is needed for EP which
requires time energy and equipment.

− Fabricator landscape: The ease of processing VER (like UPR) results in

having several fabricators per country as opposed to a few
companies per continent able to make EP based FRP…

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 Piping

CourtesyLicensed
of Future
for thePipe Company
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 Fire Water Distribution Network

− Location/Year: France/1976
− Service:
water of pH 6 containing 6% of an
emulsifier.
− Service pressure:12 bar
− Design pressure is 18 bar.
− Fabrication: filament winding
− with Derakane 510A due to
significant fire hazard.

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 Piping: VER liner + UPR

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Pipeline for carbon dioxide recovery

− Location/Year: Offshore oil platform/1993

− Service: designed to withstand crude oil and water at 40°C
− Temperature: 40°C, short-time 70°C
− Low pressure and up to PN25 for seawater service
− Fabrication: filament wound with bell and spigot connection
for fast installation with Derakane 411 resin
− Dimension: DN500 to DN1000
− Design life: 30 years

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Lining on Tank Floor and Lower Wall

− Location/Year: USA/1985
− Service: Crude oil carbon steel storage tank in service for 12 years
− Fabrication: hand lay-up with CSM and Derakane 470 resin
− Dimension:
Diameter 33.5 m
Height 14.6 m
− Installation:
21 days including works as
Sandblast surface,
Apply Primer,
Seal seams with putty,
Finishing layer with gelcoat

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Floating Roof on EDC Tank

− Location/Year: 1996 and 2001/The Netherlands

− Service: Ethylene dichloride (EDC, 1.2-
dichloroethane, ethylene chloride).
− Operating temperature: 4 to 35ºC
− Fabrication:
in situ hand lay-up in sandwich
design (PP honeycomb embedded
in skin laminate) or assembling
of pre-manufactured panels
(RTM or Va-RTM) both with
Derakane 470 resin
− Dimension: Diameter 18 m
− Engineering: DM Tank Systems
Berheer

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 Composite floor with leak detection for big storage tank of
petroleum

− Location/Year: The
Netherlands
− Service: floor with leak
detection for petroleum
storage tank, hydrocarbons
at ambient temperature
− Fabrication: hand lay-up
using 3D-fabric and structural
laminate Derakane 470 resin
(Primer Derakane 8084 resin)
− Dimension: Diameter 12 m,
Double walled
− Design: vacuum and liquid
pressure of 2 bars

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 Storage tanks of unleaded gasoline

− Location/Year: Finland/1983
− Service:
Storage of petroleum products including unleaded gasoline
formulations containing methanol, ethanol, tertiary butyl
alcohol (TBA) and methyl tertiary butyl ether (MTBE).
− Fabrication: chopped roving
/filament winding with
Derakane 470 resin
− Storage capacity: up to
50 m³

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 LPG Cylinders

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 Conclusion

− VER have similar properties than most of the Epoxy

Systems apart for cases that combine high
pressure and high temperature.

− VER provides better corrosion resistance and

much easier processability along with cost
advantage.

− VER have proven performance in the Oil & Gas

industry for more than 30 years for many
applications.

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 Thank you !

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