Fire Resistive Materials:

Adhesion
Performance Assessment and Optimization
of Fire Resistive Materials
NIST
July 14, 2005
Microstructure
Experimental
3-D Tomography
2-D optical, SEM
Confocal microscopy

Modeling
3-D Reconstruction

Parameters
Porosity
Pore Sizes
Contact Areas

Properties
(all as a function of T)
Thermal
Heat Capacity
Conductivity
Density
Heats of Reaction

Adhesion
Pull-off strength
Peel strength
Adhesion energy
Fracture toughness

Equipment
TGA/DSC/STA
Slug calorimeter
Dilatometer
Blister apparatus
Materials Science-Based Studies
of Fire Resistive Materials
Environmental
Interior
Temperature, RH, load

Exterior
Temperature, RH, UV, load

Performance Prediction
Lab scale testing
ASTM E119 Test
Real structures (WTC)
Adhesive Performance of FRMs
Why should we care?
Opportunity: Recent events have
demonstrated the importance of in-service
adhesive performance in the ability of
FRM to protect steel.

What can we learn about existing adhesive
properties of FRM?
How do we measure adhesion?
Want a geometry independent property.
Adhesive Fracture energy, Gc



How do we measure Gc?
energy to create
a unit of surface area
units: J/m
2
What is Gc
Experimental: Schematic and Theory
4
16
|
.
|

\
|
=
a
w Eh
G
2
2
1
|
.
|

\
|
=
w
P
Eh t
G
3 / 4 3 / 1
4
16
1
|
.
|

\
|
|
.
|

\
|
=
a
P
Eh t
G
P
w
2a
2
4
1
a
Pw
t
= G
Assumptions: Thin, stretching membrane,
loaded elastically and at a point
Eh: Film Tensile Rigidity (modulus, E, thickness, h)
a
U
b width c
c
=
,
1
G
Experimental: Schematic and Theory
4
16
|
.
|

\
|
=
a
w Eh
G
3 / 4 3 / 1
4
16
1
|
.
|

\
|
|
.
|

\
|
=
a
P
Eh t
G
P
w
2a
Load-based equation (P)
displacement-based equation (w)
Experimental Set-Up:

N kg
Load suspended
from center of
specimen
3 / 4 3 / 1
4
16
1
|
.
|

\
|
|
.
|

\
|
=
a
P
Eh t
G
2
4
1
a
Pw
t
= G
WTC Material
Experimental: Shaft-Loaded Blister Test
for WTC Material
2
2
1
|
.
|

\
|
=
w
P
Eh
G
t
P
h
Kai Tak Wan and Yiu-Wing Mai,
International Journal of Fracture, 74, 181-197 (1995)
E: Youngs Modulus
coating
Rigid substrate
Mechanically driven
shaft attached
to Instron
Shaft attached
To instron
Stand to hold sample
Film is on the
underside
Of stand
Mirror to view
film
w
WTC Sample
P
Fire Retardant Material (3/4)
Primer
2 mil steel
For a bending plate:
2
2
2
|
.
|

\
|
=
w
P
Eh
G
t
The mechanical properties of the film
are estimated from:

Steel E (Pa) = 2 * 10^11
h (m) = 0.05 *10^-3
Adhesion Promotor
E (Pa) = 3 * 10^9
h (m) = 0.20 *10^-3

and:
E
composite
= v
2
E
1
+v
2
E
2
y = 8.7337x - 1.2149
R
2
= 0.9965
-0.5
0
0.5
1
1.5
2
2.5
3
3.5
4
0 0.2 0.4 0.6
w (mm)
P

(
N
)
0
1
2
3
4
5
0 0.2 0.4 0.6 0.8 1
w (mm)
P

(
N
)
54 % of the
samples were
entirely
debonded
when received
Experimental: Shaft-Loaded Blister Test
G = 17.3 +/- 12.8 J/m
2
Fire Retardant Coatings
Testing of Adhesive Joints:
Introduction to Sub-Critical Adhesive Fracture Testing
and the Wedge Test
Wedge Test:
a (t > 0)
a (t = 0)
4
3 2
16
3
ba
Eh BA
= G
v-G curves will tell you:
-rank order of adhesive
-failure mechanisms
-engineering design parameters
L
o
g

C
r
a
c
k

V
e
l
o
c
i
t
y
,


v

(
m
/
s
)

Crack Driving Energy, (J/m )
v

(
m
/
s
)

(J/m
v

(
m
/
s
)

G
(J/m
2
10
-10
v-G Curve Reveals Mechanisms of Adhesive Failure at the Crack-
Tip: Regions I, II, III
v*
Region II: diffusion to crack tip
Region III:
stress
controlled
G
Th
Region I: stress-dependent
chemical reaction
Crack Driving Energy, (J/m )
I
Crack Driving Energy, (J/m )
I
II
L
o
g

C
r
a
c
k

V
e
l
o
c
i
t
y
,


v

(
m
/
s
)

Crack Driving Energy,
G
(J/m
2
)
I
III
Increasing
Aggressiveness of
Environment
C
r
a
c
k

V
e
l
o
c
i
t
y
,

v

(
m
/
s
)

Crack Driving Energy, G (J/m
2
)
Region II
Application of Sub-Critical Adhesion Testing: Residual
Stress (
r
) in Coatings
E
v h
Z
r
) 1 (
2

=
o
G

r
arise due to
CTE mismatch or processing
G
Th
L
o
g

C
r
a
c
k

V
e
l
o
c
i
t
y
,


v

(
m
/
s
)

Crack Driving Energy, (J/m )
v

(
m
/
s
)

(J/m
v

(
m
/
s
)

G
(J/m
2
T
E
r
A A

= o
v
o
) 1 (
Data from wedge test
Constant-Load Subcritical Blister Test
4/40 screw
wire
nut and washer(s)
epoxy sealant
wafer substrate
adhesive film
weight
4/40 screw
wire
nut and washer(s)
epoxy sealant
wafer substrate
adhesive film
weight
Constant load Constant load
3 / 4 3 / 1
4
16
1
|
.
|

\
|
|
.
|

\
|
=
a
P
Eh t
G
i i
i i
t t
a a
v

=
+
+
1
1
*
Measure debond easily with micrometer!
Borofloat
glass substrate
P
1.
Kapton PSA pre-crack
2. Spin coat PMMA
3. RT cure epoxy adhesive and Kapton backing
Fire Resistive Coating
Cold Rolled Steel
Substrate
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1 10 100 1000
debond energy (J/m
2
)
d
e
b
o
n
d

v
e
l
o
c
i
t
y

(
m
/
s
)
Epoxy DCB
Screening Tool for Different Coatings
Bonded to Cold Rolled Steel at 100% r.h. & RT
A SLBT
B SLBT
A DCB
D
C
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.0 10.0 100.0
debond energy (J/m
2
)
d
e
b
o
n
d

v
e
l
o
c
i
t
y

(
m
/
s
)
Soft vs. Hard Coating,
low humidity vs. high humidity
Hard coating performs better than Soft coating!
Coatings perform better at low humidity
High (95%) RH
Low (1%)
RH
FRC DCB :
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
1.0 10.0 100.0 1000.0
debond energy (J/m
2
)
d
e
b
o
n
d

v
e
l
o
c
i
t
y

(
m
/
s
)
Increase humidity and reduced residual stress
Tensile Residual Stress is reduced by moisture absorption
Reduction in residual stress leads to improved durability
FRMs.
Modern Adhesion testing methods can give
LRFD parameters.
These parameters are environmentally
sensitive.
(increasing RH can either increase or decrease performance.)
What about Temp and UV? Rate effects?
What about the existing test methods?
Can we modify existing test methods?
Adhesion Tests: Ideal
Ideal Adhesion Test:
Simple, cheap, fast, easy to perform
Grounded in fundamental mechanics and material
science- LFRD guidance
Includes modes- opening, in-plane shear, torsion, mixed,

Could include environmental and rate dependence.

How far are the test from idea?
Current FRM Standards:
ASTM E759 (Effect of Deflection)
12 Ft
Deflect 1/120 or 1 inch.
ASTM E760 (Effect of Impact)
12 Ft
Concrete
60 lb from 4 ft.
ASTM E736 (Cohesive/Adhesive)
Current Empirical Methods:
Advantages:
Quick, easy, Cheap
Practical
Pass/Fail guidance
Disadvantages:
Highly dependent on sample preparation
Specific to situation tested (geometry, speed, etc)
Little or no design guidance

Quantitative Adhesive Test Methods:
Beam, JKR and Peel Measure G and E
JKR Test
2 / 1
2
3
3 6 3
1

(
(

|
.
|

\
|
+ + + =
P
WR
P
WR
P
WR
K
PR
a
t t t
At equilibrium G =W
A
P
P
a
) 4 6 5 ( 2
) 2 3 2 ( 2
8
3
2 2 4 2 2 4 2 2
2 2 4 2 2 4 2 2
4
3 2
h th t th BwEE h E w t E B
h th t th BwEE h E w t E B
w a
BEt
a a
a a
+ + + +
+ + + + A
= G
Beam Test, ex. Wedge Test
Blister Test
2
4
1
a
Pw
t
= G
P
w
2a
P
Peel Test(s)
w
P
= G
Fundamental Mechanics
Advantages:
Link to fundamental mechanics and material science
properties G
Results are independent of geometry/sample
preparation.
Gives LFRD guidance
Disadvantages:
Expensive
Require equipment
Time consuming
Current Methods:
Fundamental Mechanics

DCLB

Peel Tests


Blister Tests

JKR

Empirical, Practical
Pull off

Lap Shear

Impact


Deflection
A
P
P
a
P
w
General Approach:
Simple Test,
Fast, easy, inexpensive to perform
Calibrate.
Can be calibrated against fundamental
mechanics and material science
Rate, strain and environmental dependence
Round robin
Prototype:
Steel
FRM
Bending, twisting, stretching will
produce known strains at the
interface (different modes)
Stress can be calculated from first
principles and calibrated with known
adhesion geometries.
Visually evaluated, or calibrated.
Can give both rate and environmental
performance.
Never have to touch the
material
Summary
Current methods for evaluating the adhesion
performance are pass/fail.
Modern adhesion testing methods present the
ability to give design guidance for FRMs.
It appears possible to build a close to ideal
adhesion test for FRMs.
Simple, cheap, fast, based in mechanics, calibrated by
NIST.