NACE Paper No.

11036
Low temperature mechanical properties of passive fire protective coatings
 NACE Paper No. 11036
Low temperature mechanical properties of passive fire protective coatings

Paul P. Greigger Abstract

PPG Industries
151 Colfax Street Passive Fire Protective coatings (PFP) are applied at
Springdale, PA 15144 much higher thickness than most regular paints. Typical
thicknesses are in the range of 0.1 inch to 0.75 inch (2.5-
Jonathan M. Hills 19mm). In many ways, it is best to think of PFP materials
PPG Industries as composite plastics rather than as coatings. As such,
151 Colfax Street physical properties that are important with a material
Springdale, PA 15144 applied at five mils may not be relevant to a coating
applied at 100 times that thickness. Properties of thin
film coatings that are considered attributes may not allow
the PFP to cope with the rigors of in-service conditions.
Vibration, flexing of steel members and rapidly changing
temperatures can negatively impact thick film coatings.
This paper explores the room temperature and low
temperature properties of epoxy intumescent PFP
coatings. Tensile properties and adhesion values at room
temperature down to –40°C have been measured and
will be discussed. A comparison between flexible, tough
PFP coatings and hard, brittle PFP coatings based on
apparent glass transition temperatures, adhesion, tensile
strength, and elongation will be presented.

Key words: Passive fire protection, intumescent, low

temperature, tensile strength, adhesion.

Introduction

Passive fire protective (PFP) coatings are used to protect

structures in the case of fire. They differ from “active”
protection methods in that they require no additional
action to function, such as activation of a sprinkler
system. Several varieties of PFP are used for different
markets and applications. Epoxy based fire protective
coatings are used where light weight, exterior durability,
and corrosion resistance are needed, such as exterior
structural steel in the petrochemical industry. The
chemistry of epoxy PFPs, their application methods,
and their typical end uses lead to unusual requirements
for coatings properties. Among these is good adhesion
well below room temperature, and well below normal
service temperatures for other coatings. Petrochemical
installations, one of the major end-uses of hydrocarbon
PFPs, are often in regions like Alaska and Norway
where temperatures reach as low as -40C. As with
many aspects of the epoxy intumescent field, no prior
published research is available on the reactions of these
coatings to changes in temperature. In this paper, the low
temperature adhesion and tensile strength properties of
epoxy based intumescent coatings are explored.

2 NACE Paper No. 11036 Low temperature mechanical properties of passive fire protective coatings
Epoxy PFP coatings are usually mastic coatings, meaning
that they are applied at high film thickness. The thickness
required can be 100 to 200 times that of a typical coating
thickness (12mm v 0.12mm). Like most crosslinking
coating systems, there is a net reduction in the volume
of the coating on curing or drying that increases with
crosslink density. Epoxies, because there is a ring
opening in the cure mechanism, tend to have lower but
still significant volume reduction compared to other
chemistries. This shrinkage introduces residual stress
within the coating, which increases with coating thickness
and crosslink density. The net shrinkage in a system will
also fluctuate with temperature. At higher temperatures,
crosslinked coatings may continue to cure leading to
a moderate increase in the internal stress of a coating.
Organic materials have a larger temperature-related
fluctuation in length than do metals, which becomes
important when organic coatings are applied to metal
substrates which are then subject to heating and cooling.
Because coatings including epoxy PFP coatings will be
used to protect exterior structural steel it is important
to understand a coating’s response to temperature
variations. It is very typical to “accelerate” test results by
exposing samples to higher than normal temperatures
to take advantage of the increase in reaction rate
with increased temperature. For example, salt fog
testing, using ASTM B-1171 is run at 95°F (35°C), and
accelerated UV exposure testing using ASTM G 154
can subject the test specimen to temperatures as high
as 176°F (80°C)2. Because of this, high temperature
behavior of coatings is fairly well understood. However,
in real-world applications, most exterior structures
experience temperature well below 77°F (25°C). At the
expected service temperatures for epoxy PFPs, the
amount of shrinkage will be high which will increase the
amount of internal stress. If the coating internal stress
exceeds the adhesion force to the substrate, the coating
could relieve this internal stress by disbonding from the
substrate or cracking. Neither result is desirable and can
compromise the integrity, durability, corrosion and fire
protection of the PFP. The question remains: do flexible
PFP coatings maintain those flexible properties at low
temperatures, and what happens to hard, brittle coatings
as the temperature drops?
In the paper below, the experimental procedure is
outlined in further detail, followed by the results, and
a conclusion discussing the general meaning and
importance of this work. First, some background
information on the testing performed may be helpful.
In order to test the low temperature properties of these
coatings, two standard test methods were employed:
tensile testing and lap shear testing. Tensile testing
determines the strength of materials by measuring the
amount of force necessary to pull them until they break.
Test methods such as ASTM D6383 use a sample
shaped like a dog bone, with wide areas at the end for
grip and a narrow test area with a known cross-sectional
area. During the test, a sample of the coating is pulled at
a constant rate, measuring the percent elongation and
maximum stress required to break the sample. Elongation
is generally expected to decrease with decreasing
temperature, while maximum stress typically increases.
At some temperature, the polymer binder in the coating
will pass its glass transition temperature, below which it
will behave more like a glassy solid than an elastic solid.
This means that below the glass transition, a coating will
have more of a tendency to snap than to tear, and will
often take more stress to break. However, the individual
performance will vary based on the coating according
to factors such as the architecture of the resin and the
nature of the fillers used. It is therefore necessary to
consider more absolute measurements like elongation at
expected service temperature rather than simply noting
whether a coating will be used below its glass transition.
Typical reporting properties for tensile tests are strain,
maximum stress, and modulus. Strain, or percent
elongation, is simply a measure of how far a material can
be pulled before it breaks, and is typically reported as
a percent increase in length. Maximum stress or tensile
strength has units of pressure, and is the amount of force
used to break the sample divided by the cross sectional
area in which the break happens. Modulus is often
interpreted as a measure of the “stiffness” of a material.
As the slope of the stress/strain curve, it also has units of
pressure.
Lap shear testing, described in ASTM D10024, is typically
used for measuring the bond strength of adhesives. Two
pieces of a stiff substrate, steel in the present study, are
glued together using the subject material, and then pulled
apart using the same equipment as a tensile test. The
area of contact is either known or measured so that the
force used to pull the sample apart can be normalized,
similar to the known cross-sectional area used in tensile
testing. After testing, the failure is characterized as either
adhesive (that is, the material pulling from the substrate)
or cohesive (failure within the bulk of the subject material).
The percentage of cohesive failure is typically reported
along with the maximum stress, as in tensile testing. As
with tensile testing, polymeric coatings or adhesives are
expected to behave differently above and below their
glass transition temperature.
3
 Experimental procedure -
Low temperature mechanical properties of passive fire protective coatings

Two experiments were performed to determine behavior Other formulations are either unknown or cannot be
of epoxy mastics at low temperature: one for tensile disclosed.
strength, and one for adhesion. For both experiments,
four mastics were used. Subject 1 was a commercially Tensile samples were prepared by casting the mastic
available mastic advertised as being flexible and having in a silicone mold, and were allowed to cure at room
good low-temperature and thermal cycling performance. temperature overnight before demolding and a minimum
Subject 2 was also a commercially available mastic of a week before testing. The tensile samples were
whose manufacturer does not make any special claims approximately 0.125 inch (3.2 mm) thick, with a test
about low temperature performance. Subject 3 was area 0.5 inch (13mm) wide and 3.5 inches (89mm) long.
an experimental material formulated with a goal of Tensile properties were tested on an Instron 55675
maintaining some cold weather performance while equipped with a 30kN load cell using a crosshead speed
increasing room temperature adhesion. Subject 4 was a of 50mm/min. Elongation was measured as a percentage
low-flexibility mastic formulated specifically for this study, based on the distance traveled by the crosshead.
consisting of a liquid BPA epoxy (such as Epon 828) Temperatures below room temperature were maintained
cured with a polyamine (Versamid 150) and using a 1:1:1 using the instrument’s environmental chamber in 10°C
blend of pentaerythritol, ammonium polyphosphate, and increments starting at -40°C and increasing to room
melamine at 35% PVC. This combination was designed temperature. The samples for the low temperature tests
to give a brittle, highly crosslinked coating. were left in the chamber between testing to allow them to
equilibrate at the target temperature more quickly. Four
samples were run for each condition, and an average of
Table 1 the results presented.
Schedule of experimental materials
Adhesion was tested via lap shear. Samples were
Material Commercial or Expected prepared on cold-rolled steel 1/16th inch thick, with a
Experimental Stiffness contact area of approximately one quarter square inch
Subject 1 Commercial Flexible
(contact area one half inch by one half inch). Samples
were “glued” together using the appropriate mastic,
Subject 2 Commercial Stiff allowed to cure at room temperature for three days,
and then cured at 140°F for three days. Samples were
Subject 3 Experimental Between 1 and 2
normalized to the appropriate test temperature in the
Subject 4 Experimental Stiff same manner as for tensile properties, and lap shear
tested on the same equipment as tensile strength.
Temperature selection for the adhesion portion of testing
Table 2 was adjusted based on the results of tensile testing.
Formulation for subject 4 As discussed in more detail below, glass transition
temperature was estimated for the materials during
Material Mass (%) tensile testing. Temperatures were selected for adhesion
testing so that materials were tested both above and
BPA Expoxy 28.8
below their estimated glass transition.
Polyamide 24.1

Tertiary Amine Accelertae 2.7

Diluent 3.6

Melamine 13.6

Ammonium Polyphosphate 13.6

Pentaerythritol 13.6

4 NACE Paper No. 11036 Low temperature mechanical properties of passive fire protective coatings
 Results - Tensile strength

Subject 1: tensile testing

Subject 1 was a commercial PFP, which was expected to
be flexible based on claims made by the manufacturer.
As is typical of elastic polymers, percent elongation
increased with temperature. The glass transition
temperature can be seen clearly in a change in slope
at about -10°C. Below that point, elongation was
roughly constant at 5%, while above that temperature,
elongation increased with temperature to about 25%
at room temperature. Also typical, maximum stress
(tensile strength) decreased with increasing temperature
to about 4.5 MPa at room temperature. Break strain (%
elongation) and maximum stress (tensile strength) are
plotted below against temperature.
Qualitatively, materials tested at low temperature had
cleaner breaks than those tested near room temperature.
This is consistent with a glassy fracture at low
temperature, and higher elasticity leading to more tearing
at room temperature.
Modulus was relatively low for this material, increasing
steadily with decreasing temperature. This is consistent
with a soft, flexible material becoming more brittle with
lowering temperature.
Strain, stress and modulus results are tabulated in Table
3 below.

Figure 1 Table 3
Elongation and tensile strength v. temperature - Tensile properties at various temperatures - Subject 1
Subject 1
Temp Elongation Max stress Modulus
30 (ºC) (%) (MPa) (MPa)

25 25 24.3 4.45 30

20 10 17.7 10.8 96

15 0 10 15.3 292

-10 6.1 18.0 465

10

-20 5.2 20.5 535

5
-30 4.5 21.5 600
0
-60 -40 -20 0 20 40 -40 4.9 18.2 538

Temperature oC

Break Strain (% elongation)

Max Stress (tensile strength, MPa)

5
 Subject 2: tensile testing

Subject 2 was a commercial mastic, but its manufacture Table 4

makes no special claims about flexibility or low Tensile properties at various temperatures - Subject 2
temperature performance. It exhibited results consistent
with its expected brittle behavior compared to Subject 1. Temp Elongation Tensile Strength Modulus
Elongation stayed around 1-2% for the whole temperature (ºC) (%) (MPa) (MPa)
range tested, and no clear glass transition was present. 25 2 14.55 1529
It is possible that a glass transition occurred somewhere
between 10°C and 25°C, based on a slight increase in 10 1.5 14.28 1692
the slope of the strain v. temperature curve in that region.
0 1.2 15.97 1930
However, to determine whether this is in fact the case
would require more high temperature data points. -10 1.1 15.76 2006

-20 1.2 16.89 2415

Modulus of this material was the highest of the four
tested. Taken with the relatively low break strains and -30 1 16.5 2622
maximum stresses, this indicates a stiff, brittle material,
-40 0.6 11.08 2713
consistent with glass transition occurring somewhere
around room temperature.

Figure 2
Elongation and tensile strength v. temperature -
Subject 2

18

16

14

12

10

0
-60 -40 -20 0 20 40

Temperature oC

Break Strain (% elongation)

Max Stress (tensile strength, MPa)

6 NACE Paper No. 11036 Low temperature mechanical properties of passive fire protective coatings
 Subject 3: tensile testing

As discussed above, subject three was designed to be Table 5

less flexible and with improved low temperature adhesion. Tensile properties at various temperatures - Subject 3
It was expected to have lower low-temperature elongation
than Subject 1, and that turned out to be the case. Temp Elongation Tensile Strength Modulus
(ºC) (%) (MPa) (MPa)
The general shape of the curves is similar to that for 25 4.2 13.9 687
Subject 1. The glass transition occurs at a higher
temperature of about +6°C, and the slope of the 10 3.4 20.9 1159
line above this point is less steep, both of which are
0 2.4 22.4 1512
consistent with a less flexible resin system. Modulus is
higher for this material than for subject 1, consistent with -10 2 23.4 1677
a less flexible coating. Elongation and tensile strength
-20 2.2 25.2 1771
are plotted v. temperature below, with the numerical data
tabulated below. -30 1.8 22.8 2139

-40 1.6 24.8 2269

Figure 3
Elongation and tensile strength v. temperature -
Subject 3

30

25

20

15

10

0
-60 -40 -20 0 20 40

Temperature oC

Break Strain (% elongation)

Max Stress (tensile strength, MPa)

7
 Subject 4: tensile testing

The fourth system was designed to create a known Table 6

composition to give a brittle, highly crosslinked system. Tensile properties at various temperatures - Subject 4
As would be expected, the elongation is lower through
the whole range of testing, holding steady at about Temp Elongation Max stress Modulus
1.5%. There is no clear glass transition, although from (ºC) (%) (MPa) (MPa)
the distribution of the data points it is possible that such
25 2.5 13.5 1092.7
a transition occurs somewhere above +10°C. However,
the practical point is that the glass transition temperature 10 2 17.7 1574
continues to increase, and that a material without a
0 1.9 18.5 1520
flexible component will be expected to be brittle at
temperatures near room temperature or just below. -10 1.8 18.8 1751
Although the break strain is comparable to subject 2,
-20 1.4 18.9 2070
the modulus is not as high.
-30 1.6 20.4 2082

-40 1.5 18.2 1738

Figure 4
Elongation and tensile strength v. temperature -
Subject 4

25

20

15

10

0
-60 -40 -20 0 20 40

Temperature oC

Break Strain (% elongation)

Max Stress (tensile strength, MPa)

8 NACE Paper No. 11036 Low temperature mechanical properties of passive fire protective coatings
 Results - Lap shear adhesion testing

Subject 1: Lap shear testing Subject 2: Lap shear testing

Lap shear results were more complex than those for
tensile strength for all samples, but Subject 1 was a
typical case. The glass transition temperature was
determined to be approximately -10°C in tensile testing,
so lap shear was tested at -40°C, -20°C, +20°C, and
+24°C. Adhesive strength was initially very high, at 14
MPa at -40°C and increased slightly as temperature
approached the glass transition, but then decreased
rapidly beyond that point. The percentage cohesive failure
followed a similar pattern, increasing from 14% cohesive
failure at -40°C to 74% at -20°C, but dropping to 42% at
24°C. Adhesive strength versus temperature is shown in
figure five below, with results tabulated in table five.
Figure 5
Adhesive strength v. temperature - Subject 1
20
Adhesive Strength, MPa
Subject two had a different lap shear behavior than
subject one. Based on its tensile performance, which
resulted in a suspected glass transition around +10°C,
testing was performed at slightly higher temperatures
than for Subject 1. The initial rise in adhesive strength
from -30°C to -10°C was much steeper, with adhesive
strength leveling out around 6-7MPa above that point. At
40°C, the adhesive strength increased slightly compared
to the result at 24°C. This may be due to variance in the
measurement, meaning that this region is roughly linear.
Failure for this material was 100% adhesive in all tests.
This may be related to the relatively high modulus and
low break strain for this material, indicating overall that
it has a high affinity for itself. It should be noted again
that testing was performed for all samples with untreated
cold-rolled steel, while in practical application, all of
these materials would most likely be applied to sand
blasted steel which would most likely improve adhesion,
perhaps enough to force this material to some cohesive
failure. Adhesive strength results are shown in Figure 6

18
16 below, with the data tabulated in Table 8.
14
12
10
8 Figure 6
6
4 Adhesive strength v. temperature - Subject 2
2
0
8
Adhesive Strength, MPa

-80 -60 -40 -20 0 20 40

7
Temperature oC 6
5
4
3
2
Table 7 1
Adhesive strength v. temperature - Subject 1 0
-40 -30 -20 -10 0 10 20 30 40 50

Temp Adhesive strength Cohesive

Temperature oC
(ºC) (MPa) failure (%)

-40 14.1 14

-20 17.7 74 Table 8

Adhesive strength v. temperature - Subject 2
20 15.3 84

24 6.2 42 Temp Adhesive strength Cohesive

(ºC) (MPa) failure (%)

-20 1.1 0

-10 6.53 0

20 6.97 0

24 5.96 0

40 6.54 0

9
 Subject 3: Lap shear testing Subject 4: Lap shear testing

Subject 3 followed a pattern similar to subject one, but
with higher values for adhesive strength. This is consistent
with the higher tensile strength values found in that testing.
Percent cohesive failure was also higher, with increasing
difference between the two as temperature increased.
Of the four samples, this subject had the highest percent
cohesive failure in general, possibly indicating a balance
between inherent strength of the coating with low-
temperature flexibility relatively high break strain.
Figure 7
Adhesive strength v. temperature - Subject 3
30
Subject 4 performed roughly the same as Subject 2,
but with less variability overall. The variation among the
samples is roughly two MPa, while for Subject 2 there
is a difference of about six MPa between the lowest
and highest figures, meaning that the adhesive strength
for Subject 4 is fairly constant over the range tested.
However, some of the same features seen with the curve
for Subject 2 remain, such as the increase in adhesive
strength between 24°C and 40°C. This may indicate a
higher temperature effect that was not anticipated which
may warrant further study of high temperature properties
of these materials. Figure 8 is a graph of adhesive
strength versus temperature, and the remaining data
follow in Table 10 below that.

25
Adhesive Strength, MPa

Figure 8
20
Adhesive strength v. temperature - Subject 4
15

10
20
5 18
16
Adhesive Strength, MPa

0 14
-80 -60 -40 -20 0 20 40 12
10
Temperature oC 8
6
4
2
0
Table 9 -40 -30 -20 -10 0 10 20 30 40 50
Adhesive strength v. temperature - Subject 3
Temperature oC

Temp Adhesive strength Cohesive

(ºC) (MPa) failure (%)

-40 19 16
Table 10
Adhesive strength v. temperature - Subject 4
-20 26 94
Temp Adhesive strength Cohesive
20 24 99
(ºC) (MPa) failure (%)
24 16 90
-20 17.5 16

-10 18.5 23

20 16.25 23

24 16.5 86

40 18.97 83

10 NACE Paper No. 11036 Low temperature mechanical properties of passive fire protective coatings
Conclusions
The low temperature mechanical properties of some
PFP coatings were studied. The coatings selected for
this study were chosen deliberately to reflect extremes
of possible real-world performance, and reflected
the expected behaviors. At lower temperatures, the
elongation of hard brittle coatings approached zero
whereas the flexible coatings retained significant
elongation. The flexible system increased substantially in
tensile strength as the temperature decreased, surpassing
the maximum strength of more brittle material at any
temperature. The more flexible coatings tended to show
less adhesive failure to the substrate in lap shear testing,
but in all cases, adhesive failure (as opposed cohesive
splitting within the coating) was most pronounced at
the lowest temperature. These results match general
expectations of coatings at low temperature.
Low temperature lap shear and tensile testing has shown
differences in select PFP coatings and may prove to be
useful tools to predict long term durability, adhesion,
and resistance to stress induced cracking in thick film
intumescent coatings.
Future work
Epoxy PFP coatings continue to play an important role
in fire safety for the petrochemical industry. Due to
their chemical nature, epoxy coatings continue to cure
throughout their service life. Coatings are typically tested
for properties once they have achieved an initial set
after several days. This degree of cure is seldom fully
measured or understood. A possible avenue of research
would be to determine cure by end group analysis and
compare mechanical properties to measured degree
of cure as the epoxy PFP is exposed to NORSOK
M-5016 exposure conditions (a standard test method for
durability) and measure low temperature properties as
this paper has done on accelerated weathered samples.
In addition, it would be of interest to extend the low
temperature lap shear study to blasted and primed
substrates, in order to understand whether a surface
profile might improve the stress results. Use of primers,
especially low shear strength zinc rich primers, may show
more telling differences at low temperatures. The results
also indicate that PFP properties for temperatures above
room temperature should also be explored since, for
example, glass transition temperatures for some of the
commercial coatings tested seem to occur around room
temperature or perhaps slightly above room temperature.
11
References
1. ASTM(1) B-117 -09 “Standard Practice for Operating SaltSpray (Fog) Apparatus.” (West Conshohocken, PA: ASTM).
2. ASTM(1) G 154-06 “Standard Practice for Operating Fluorescent Light Apparatus for UV Exposure of Nonmetallic Materials.” (West Conshohocken, PA: ASTM).
3. ASTM(1) D 638-10 “Standard Test Method for Tensile Properties of Plastics.” (West Conshohocken, PA: ASTM).
4. ASTM(1) D 1002 -05 “Standard Test method for Apparent Shear Strength of Single-Lap-Joint Adhesively Bonded Metal Specimens by Tension Loading
(Metal-to-Metal),” (West Conshohocken, PA: ASTM).
5. Instron, 825 University Avenue, Norwood, MA, 02062-2643
6. NORSOK Standard,(2) M-501(Rev 5, June 2004), “Surface Preparation and Protective Coating,” (Lysaker, Norway, Standards Norway).

Acknowledgements
The authors wish to thank Dave Batorick, Jay Chao, and Beth Furar for their help with tensile testing.

ppgpmc.com
pmc@ppg.com
© 2013 PPG Industries, all rights reserved.
1405-986358-GLOB
Created December 2013

©2011 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.