Polyurea Spray Coatings: General Overview with

Practical Applications in Brazil

Daniel Rosenvasser, Huntsman Polyurethanes

Marcelo Alarcon Lui, Radial Revestimentos Tecnicos

Feiplar Composites & Feipur

November 6-8, 2012
Polyurea Spray Coatings: General
Overview

Polyurea is a remarkable
coatings, linings and joint sealant
technology.

A polyurea system has a very fast

application rate and when fully
Cured, it becomes a very tough and
flexible material with excellent
wear and chemical resistance
properties.

Polyurethanes
Spray Polyurea Coatings: An
Introduction

ƒ Polyurea Applications
ƒ Why Polyurea?
ƒ Brief History
ƒ Polyurea and Polyurethanes
ƒ Raw Materials
ƒ Formulation
ƒ Physical Properties
ƒ Chemical Resistance
ƒ Processing Variables

Polyurethanes
Bridge Coatings

A polyurea outlasts paint and fights

out corrosion, a major reason these
systems are specified for bridge
deck and structure coatings.
The most common applications are
over steel and concrete.

Polyurethanes
 Bridge Deck Coating

Asphalt Overlay
Deck Tack Coat
Polyurea Membrane
Primer
Substrate

With permission by owner.

Polyurethanes
Railways

Polyurethanes
Railway Bridge Deck Coating

Ballast
Polyurea
Primer
Substrate

With permission.

Polyurethanes
High Speed Railway

China plans to expand it’s high

speed railway network to
10,000 miles in 2020.

Polyurethanes
Design Concept for a Sealer/Primer

Primer Sealer
Good film-forming Good penetration

Epoxy Silane
Acrylic Siloxane
Polyurethane
Vinyl

Sealer/Primer: Both good film-forming and penetration

Polyurethanes
Combination of PU Sealer/Primer with
Polyurea

Polyurea or
other topcoat

PU Putty

PU
Sealer/Primer

Concrete

Polyurethanes
Case Study of PU Sealer/Primer for Spray
Polyurea

Polyurethanes
PU Sealer/Primer for Spray Polyurea

Blank Concrete Spray Polyurea

PU Sealer/Primer PU Putty Spray Polyurea

Polyurethanes
Fracking

ƒ Induced hydraulic fracturing or fracking, is a technique used to

release petroleum or natural gas for extraction. It creates fractures
from a wellbore drilled into reservoir rock formations.

ƒ The energy from the injection of a highly pressurized fracking fluid

creates channels in the rock, which can increase the extraction rates
and recovery amount of the hydrocarbons.

ƒ Fracking is probably the singly, most important event in the last 50

years for the U.S. chemical industry. Natural gas became a cheap
and abundant raw material and a source of ‘clean’ energy.

ƒ The potential for environmental impact could be very important and

needs to be understood.

Polyurethanes
Fracking

Polyurethanes
Chemical Resistance ASTM D 3912

ƒ Methanol D
ƒ Gasoline C
ƒ Diesel Fuel A
Exposure by immersion for one year at
ƒ Toluene E
25C unless otherwise noted.
ƒ MTBE B
ƒ Motor Oil C
ƒ Hydraulic Fluid A
A no visible damage
ƒ 2-Methylbutane A B slight color change
ƒ Water, 82°C/14 days A C slight surface discoloration
ƒ 10% NaCl, room temp A D swelling < 48 hours
ƒ 10% NaCl, 50C/14 days A E swelling < 24hours
ƒ Sulphuric acid, 10% A
ƒ Hydrochloric acid, 10% A
ƒ Ammonium Hydroxide, 20% A
ƒ Sodium Hydroxide, 20% A
ƒ Potassium Hydroxide, 20% C
ƒ Sodium Hydroxide, 50% C
ƒ Acetic Acid, 10% A
ƒ Sodium Hydroxide, 1%, 50C,
14 days C

Polyurethanes
Manhole & Sewer Linings

Polyurea is able to solve many issues with

groundwater infiltration and installation speed. With
proper surface preparation and substrate conditions,
primers and polyurea can be applied very fast to
return the cavity to service. Polyurea forms a
monolithic, durable liner that protects the cavity from
sediment and groundwater infiltration into municipal
wastewater systems.

Polyurethanes
Pipe and Pipeline Coatings and Linings

Polyurea coatings protect steel

pipes from corrosion.

It is a protective coating system

for polyurethane foam insulated
pipes and used to line the inside
of water and sewer pipes for
rehabilitation work.

Polyurethanes
Secondary Containment

Polyurea is resistant to many fuels and

chemicals and is commonly used in fuel
pits and secondary containment.
Polyurea is not resistant to all chemicals
and compatibility tests and surface
preparation are always required.

Polyurethanes
Chemical Resistance (ASTM D 1308)

ƒ Acetone A Spot test or watch glass method,

ƒ Brake Fluid B simulates coating exposure through
ƒ Bleach, 10% NR possible spillage (7 days).
ƒ Gasoline A
A no visible damage
ƒ Hexane A
B little visible damage
ƒ Hot tub water B NR not recommended
ƒ Hydraulic oil A
ƒ Methanol A
ƒ Motor oil B
ƒ Sodium Hydroxide
– 5% A
– 10% A
– 25% A
– 50% B
ƒ Sulfuric Acid
– 5% A
– 10% B
– 50% NR

Polyurethanes
Roof Coatings

Polyurea makes an excellent protective covering for

polyurethane foam roofs. It can be formulated to meet specific
performance requirements as well as make them reflective to
further reduce the energy consumption of the building.

Polyurethanes
Line Striping

Polyurea is ideal for use in line

striping and pavement marking. It
can be returned to service for traffic
and pedestrian use in only a few
minutes after application. Polyurea
is much more durable than paint
and will last longer between
maintenance cycles.

Polyurethanes
Marine

Above and below the water

line, polyurea can be very
effective in protecting steel,
aluminum and fiberglass in
a variety of water sport and
commercial marine
applications.

Polyurethanes
Water Parks, Playgrounds, Aquariums

Molded slides, protective coatings of seats for wet/dry amusement

rides, tank linings, water containment, aquariums, and concrete
stadium seats are a few polyurea applications in the amusement and
theme park industry. Polyureas replace paint and fiberglass because
of it’s fast cure and ability to reduce maintenance cycles.

Polyurethanes
Theme Park and Decorative Design

Theme Parks often use polyurea to protect foam, EPS and other structures
to create ornamental building, themed characters, artificial rocks, pools and
environments.

Polyurethanes
Architectural Coating

Polyurethanes
Waterproofing

Polyurethanes
Joint Fill/Caulk

Polyurea is being used as a multi-purpose joint fill, caulking and

sealant material. It can provide a flexible, durable, weather tight and
traffic resistant seal for expansion joints. It has excellent crack-bridging
properties with high elongation and tensile strength.

Polyurea caulk may be formulated to be applied in cold chambers at

freezing temperatures.

Polyurethanes
Truck Bed Liners

Polyureas (typically hybrid

PU-polyurea formulations)
are used to make a durable,
water and air-tight
permanent liner for the
exterior of pick up trucks,
dump trucks and steel
containers, to protect them
from their harsh duty
environments. The liners are
easy to clean and protect
against rust and corrosion.
They can be wrapped over
the top edge of the truck bed
to provide added protection
from impact and abrasion.

Polyurethanes
Truck Bed Liners

Polyurethanes
Truck Bed Liners

Polyurethanes
Why Polyurea?

Polyurethanes
Why Polyurea?

Fast cure. No drip or run formation.

Relative humidity, residual moisture or

temperature have little effect on adhesion
or coating performance.

Two component, one coat system, 100%

solids.

Excellent physical properties.

Stable up to 175 °C.

Formulation flexibility.
Pigments and colorants may be added.
Reinforcement fibers and fillers can be
incorporated during application.

Polyurethanes
Historical Review

1980s

Polyurea elastomers were first introduced by the Texaco Chemical

Company, focusing on RIM applications for automotive parts:
fascia and body panels.

ICI Polyurethanes started development of special polyurea

prepolymers.

Texaco introduced the concept of polyurea spray coatings.

1990s

Huntsman acquires Texaco Chemical Co. (1994) and later ICI

Polyurethanes (1999)

The creation of PDA, Polyurea Development Association further

promotes the growth of polyurea based spray coatings

Polyurethanes
Isocyanate Most Common Reactions

POLYURETHANE
O O
Catalyst R R'
OCN NCO + HO OH N O O N
R R'
n
Isocyanate Polyol H H
Prepolymer

Urethane
POLYUREA link
O O

OCN NCO + R R'

H2N NH2 N N N N
R R' n
Isocyanate H H H H
Polyamine
Prepolymer

Urea
link
Polyurethanes
Interfacial Area Detail
O
Hard segment
R C R
N N

H H

R C R
N N

H H
Hard segment cohesiveness
aromatic ring interactions
tridimensional H-bonding network
Interfacial area
Aromatic polyisocyanate Connectivity soft-hard segment critical
Diamine extender
Soft segment polyamine Typically the isocyanate is provided as
a prepolymer containing part of the
flexible segments

Polyurethanes
Elastomer Families

Resin
POLYUREA HYBRID HYBRID POLYURETHANE
components

Primary Polyether amine Polyether amine Polyether polyol Polyether polyol

Aromatic or Aromatic or
Extender Glycol Glycol
aliphatic diamine aliphatic diamine

Catalysts None yes yes yes

Other additives: UV stabilizers, pigments, adhesion promoters,

compatibilizers, viscosity reducers, fillers, moisture scavengers

Polyurethanes
Polyureas vs. Polyurethanes

POLYUREAS POLYURETHANES
- Fast cure – no catalyst - Slower cure. Requires catalysts.
- Lower reaction activation energy - Higher activation energies: more
- Broader temperature application dependence on component
range – mainly lower temperatures temperature
- Independent from ambient humidity. - Broader formulation range:
- Good physical properties - Harder and softer coatings
- Generally good chemical resistance - Lower stability at high temperatures
- Better temperature stability - Physical properties have a wide
- Typically 100% solids range
- Higher cost - Typically will require moisture
scavengers.
- Lower cost

Polyurethanes
 Reaction Conversion

POLYUREAS POLYURETHANES
- Fast cure without catalyst - Catalysts used to adjust cure kinetics
- Lower reaction activation energy - Higher activation energies: more
- Broader temperature application dependence on component
range, mainly lower temperatures temperature
- Maximum rate of reaction not at start

1.00 1.00
0.90 0.90
0.80 0.80
0.70 0.70

Conversion
Conversion

0.60 0.60
0.50 0.50
0.40 0.40
0.30 0.30
0.20 0.20
0.10 0.10
0.00 0.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time Time

T = 10C T = 25C T = 40C To = 10C T = 25C T = 40C

Polyurethanes
Raw Materials for Polyureas and Polyurethanes

Polyurethanes
MDI-base prepolymers

Polyurethanes
Comparison Between Main Isocyanates

AROMATIC ALIPHATIC
Very fast cure Slower cure
More cost competitive Higher cost
Wide variety UV stable: suitable for
Not UV stable: finishing coatings
will yellow

HUNTSMAN
POLYURETHANES
SUPPLIES ONLY THESE
PRODUCTS

Polyurethanes
Common MDI Prepolymers

MDI polyisocyanates Main variables in prepolymer

design:
NCO

CH2 CH2 Isomer ratio

Polyether type:
OCN NCO OCN
Functionality
EO content
4,4'-MDI 2,4'-MDI Functionality via
Isocyanate
Polyol
Polyether polyols Viscosity modifiers

What is the influence on

performance?
O O
HO m O p nH

Polyurethanes
MDI-based Polyurea Prepolymers From
Huntsman

Viscosity @
Prepolymers NCO% Functionality Comments
25°C

RUBINATE® Fast gel times. Hard polyurea.

16.0 2.13 1,250
9009 High physical properties.

SUPRASEC® Low viscosity. Good water

16.0 2.0 250
9603 resistance.

Longer gel time, low viscosity,

RUBINATE®
15.2 2.0 370 good mix quality. Good low
9480
temperature stability.

RUBINATE®
15.1 2.06 400 Low viscosity, fast cure
9495

RUBINATE® Higher viscosity, soft

12.1 2.03 1150
9447 elastomers
RUBINATE® High viscosity, very soft
8.4 2.0 2400
9272 elastomers

Contain Jeffsol PC as viscosity modifier

Polyurethanes
Hard Polyurea Issues

DEPENDENCE OF HARDNESS ON NCO% Implications of hard polyureas:

100 ƒ Higher NCO prepolymers
Hardness, Shore A

95 ƒ Simple formulations contain

90 too much extender
85 ƒ Reaction is very fast and
80
product may be extremely
75
brittle
70
12 14 16 18 20 ƒ Mixed chain extenders and
secondary amines are
NCO% of Prepolymer
commonly used

Polyurethanes
Water Absorption vs. Prepolymer NCO
HARDER POLYUREAS HAVE LESS
TENDENCY TO ABSORB WATER

2.00
Water absorption, %

1.50

1.00

0.50

0.00
8 10 12 14 16 18 20
Prepolymer NCO%

Polyurethanes
Amine Terminated Polyols

Polyurethanes
Polyether Amines From Huntsman

H2N CH2 CH2 NH2

CH O CH
x
CH3 CH3

Reference x
®
JEFFAMINE D-400 5-6 CH2[OCH2CH(CH3)]NH2
JEFFAMINE® D-2000 32-34 x
HC [OCH2CH(CH3)]NH2
y
CH2[OCH2CH(CH3)]NH2
z
x + y + z = ~81
JEFFAMINE® T-5000

Polyurethanes
Common Aromatic Chain Extenders
Most common
aromatic diamine
chain extender
H3C
CH2

NH2

CH3
H3C CH2

NH2

ETHACURE® 100 HN NH

H3C CH3
NH2 CH2 CH3 H3C CH2
H3C S
CH3
UNILINK ® 4200
NH2

S
H3C

ETHACURE® 300

Polyurethanes
Physical Properties

Polyurethanes
Tensile Strength Development
FULL PROPERTY
DEVELOPMENT MAY
TAKE UP TO TWO
25 WEEKS
Tensile strength, MPa
20

15

10

0
0 200 400 600 800
Time since application, hrs

RUBINATE 9009 MDI RUBINATE 9480 MDI

Polyurethanes
Elongation Development

Ultimate elongation, % 600

500
400

300

200
100

0
0 200 400 600 800
Time from application, hrs

RUBINATE 9009 MDI RUBINATE 9480 MDI

Polyurethanes
Tear Strength Development

100
90
Tear Strength, N/mm

80
70
60
50
40
30
20
10
0
0 200 400 600 800
Time since application, hrs

RUBINATE 9009 MDI RUBINATE 9480 MDI

Polyurethanes
Water Immersion at 50°C

30
T e n s ile S tre n g th , M P a

25 25 26
25 24
22 23
18 18 19
20 17
15

10

0
0 1 2 4 8
Exposure weeks
RUBINATE 9480 MDI RUBINATE 9009 MDI

Polyurethanes
ASTM Oil Exposure
HIGHER PREPOLYMER FUNCTIONALITY
IMPROVES RESISTANCE TO SWELLING
AND LIQUID ABSORPTION

18

16

14
Weight gain, %

12

10

0
0 1000 2000 3000
Exposure hours

RUBINATE 9009 MDI RUBINATE 9480 MDI

Polyurethanes
Sulphuric Acid Exposure
POLYUREAS HAVE GOOD
RESISTANCE TO SOME
WEAK ACIDS
25% Sulphuric acid

25
Tensile strength, MPa

20
15
10
5
0
0 5 10 15 20 25
Exposure days

RUBINATE 9480 RUBINATE 9009

Polyurethanes
Nitric Acid Exposure
… BUT ARE GREATLY
AFFECTED BY STRONG
OXIDIZERS SUCH AS NITRIC 25% Nitric acid
ACID

25
Tensile strength, MPa

20
15
10
5
0
0 5 10 15 20 25
Exposure days

RUBINATE 9480 RUBINATE 9009

Polyurethanes
High Temperature Exposure
MOST AROMATIC POLYUREAS
RESIST CONTINUOUS USE
TEMPERATURES CLOSE TO 125°C

20
18
Tensile strength, MPa

16
14
12
10
8
6
4
2
0
0 2 4 6 8 10
Exposure weeks

125°C 150°C

RUBINATE® 9009

Polyurethanes
Immersion in Different Substances

Base: RUBINATE 9480

30
Tensile Strength, MPa

25
20
15
10
5
0
0 5 10 15 20 25
Days of exposure

Oil Caustic soda Ethylene glycol Acetone

Polyurethanes
Temperature Effect on Impact Resistance

25
Im pact resistance, N-m

20 20.3

15
13.8
10
8.8
5 4.2

0 0.3 0.3
-60 -40 -20 0 20 40 60 80

Temperature, °C

Approaching soft
segment Tg leads to
brittle behavior

RUBINATE® 9480-based Method: ASTM D 3763-93

Polyurethanes
Summary

9Polyurea properties can be adjusted with suitable formulation

approaches.

9Prepolymer choice influences key properties and processing

characteristics:
9Key variables for properties are functionality and NCO%
9Key variables for processing are viscosity, isomer content,
functionality and NCO%

9Polyurea coatings can withstand high temperature exposures

(ca. 125°C or 250°F) for extended periods.

9Polyurea coatings are resistant to chemicals but each situation

should be tested appropriately.

9Processing variables may have significant impact

Polyurethanes
Thank you

Daniel Rosenvasser
Huntsman Polyurethanes
2190 Executive Hills Boulevard,
Auburn Hills, MI 48326
Tel +1 248 322 7340 / +1 248 563 6700

Polyurethanes
Disclaimer

ƒ While the information and recommendations in this publication are, to the best of our knowledge,
information and belief, accurate at the date of publication, Nothing herein is to be construed as a
warranty, express or otherwise.

ƒ In all cases, it is the responsibility of the user to determine the applicability of such information and
recommendations and the suitability of any product for its own particular purpose.

ƒ Nothing in this publication is to be construed as recommending the infringement of any patent or

other intellectual property right, and no liability arising from any such infringement is assumed.
Nothing in this publication is to be viewed as a licence under any intellectual property right.

ƒ Except where explicitly agreed otherwise, the sale of products referred to in this publication is
subject to the general terms and conditions of Huntsman International LLC or of its affiliated
companies.

ƒ Huntsman Polyurethanes is an international business unit of Huntsman International LLC.

Huntsman Polyurethanes trades through Huntsman affiliated companies in different countries such
as Huntsman International LLC in the USA and Huntsman Holland BV in Western Europe.

ƒ SUPRASEC®, and DALTOREZ®, are registered trademarks of Huntsman Corporation or any

affiliate thereof, in one or more countries, but not all countries.

ƒ Copyright © 2012 Huntsman LLC or an affiliate thereof. All rights reserved.

Polyurethanes