103.

CARBON FOAM

- ITS PREPARATION AND PROPERTIES

R. A. Mercuri, T. R. Wessendorf, and J. M. Criscione

.

Union Carbide Corporation

Carbon Products Division
P a r m a Technical Center
P a r m a , Ohio 44130

I.

INTRODUCTION

Light weight cellular carbons a r e widely used in many industrial

and aerospace applications a s h i g h t e m p e r a t u r e t h e r m a l insulators and a s
s t r u c t u r a l support m a t e r i a l s . The Carbon P r o d u c t s Division of Union
Carbide Corporation h a s for many y e a r s been engaged in the r e s e a r c h and
development of carbon foams made by means of the pyrolysis of thermosetting organic foam p r e c u r s o r s . This paper d e s c r i b e s the preparation and
properties of two types of carbon foams, one based on a phenolic foam and
the other on a polyurethane foam p r e c u r s o r . By varying the conditions of
preparing the p r e c u r s o r foams and a l s o t h e rate of pyrolysis, a v e r y broad
fange of product p r o p e r t i e s can be obtained.
11.

PREPARATION OF CARBON FOAMS

Many f a c t o r s determine the density and suitability of a n organic

foam a s a carbon p r e c u r s o r ; the density of the r e s i n s , the t e m p e r a t u r e and
r e s i n balance of the formulation, the molding procedures, and various post
curing operations a r e important example 8 . A typical foam formulation
contains four components: the resin; a surfactant to maintain c e l l integrity
during the foaming p r o c e s s ; a foaming aid t o obtain a smooth even foaming
action starting a t low t e m p e r a t u r e s ; and, finally, a catalyst, which is used
to initiate the r e s i n polymerization reaction.
i

The organic foam is converted to c e l l u l a r carbon by heating i n a

controlled environment. The heating r a t e depends on both the p r e c u r s o r
thickness and formulation. If the foam is heated improperly, the s t r u c t u r e may melt, rupture, o r even explode.
A.

PYROLYSIS O F PHENOLIC FOAM

The pyrolysis of the phenolic foam is accomplished in a nonoxidizing environment which may be provided by the product gases. Heating
r a t e s from l o to 200C/hour have been employed i n t h e pyrolysis of phenolic
foams. The rate depends on sample size, density, and the s t r e n g t h requirem e n t s of the products carbon. F o r example, samples of low density
(0. 05 g / c c ) phenolic foam with dimensions of 16" x 16" x 2'' may be heated
at a r a t e of 10O0C/hour t o 1000C to effect the conversion to carbon.
The p r e f e r r e d pyrolysis schedule f o r any starting foam r e p r e s e n t s
a compromise between product yield and properties. When 0.25 g / c c carbon
f o a m s were prepared from phenolic foam a t a heating r a t e which g a v e a
90 percent yield of c r a c k - f r e e pieces, the c o m p r e s s i v e strength ranged from
500 t o 820 psi. When the heating r a t e was extended over twice t h a t period of
time, the yield of c r a c k - f r e e pieces was i n c r e a s e d only slightly but the
compressive strength was nearly doubled, to 1000
1480 psi. On t h e other
hand, when the original heating rate was doubled, the yield was l e s s than
50 percent acceptable pieces.

'

104.

The weight and volume changes which occur during p y r o l y s i s vary

with the density of the p r e c u r s o r foam. The high density phenolic foams
l o s e 60 percent of t h e i r weight and 70 percent of t h e i r volume when heated t o
2600C. The shrinkage is anisotropic t o the extent that t h e change i n length
is usually 3 o r 4 percent g r e a t e r than t h e change i n diameter. Table I shows
t h e changes in weight and d e n s i t y f o r high density phenolic foam (0. 25 g / c c )
at various t e m p e r a t u r e s f r o m 100" t o 2600C. The cyclic behavior of the
density indicates t h a t the m a j o r weight and volume l o s s e s do not occur at
the s a m e temperatures. Most of the work was done with s e m i - c y l i n d r i c a l
phenolic foam s a m p l e s approximately 19" d i a m e t e r and 7" long; but the
t r e n d s have been verified with s a m p l e s as long a s 24". The r e s u l t s at
2000C and higher a r e a v e r a g e s of at least 30 semi-cylindrical s a m p l e s
19" diameter and 7" long. The lower t e m p e r a t u r e studies involved no fewer
than four samples.

TABLE I
Heat T r e a t m e n t of 0.25 g / c c Phenolic Foam

Temperature
"C
100
200
300
400
500
600
700
800
900
1000
2000
2200
2400
2600

Weight

Loss, 70
2.7
5.6
14. 1
26. 8
44.2
50. 0
54.9
54.4
56..0
56. I
60
61.

61
61

Density
Change,

70

- 1.4
.6
- 4.7

.t

2.9
-12.8
8.2
4.2
1.2
0.9
0.1

3.0

- 1
t 18
t26

The d a t a i n Table I a r e characteristic of phenolic foam o v e r the

e n t i r e range of d e n s i t i e s ; however, low density foam tends to s h r i n k slightly
m o r e at treatment t e m p e r a t u r e s above 700C.

/I

B. PYROLYSIS OF URETHANE FOA'M

The heat t r e a t m e n t of the urethane foams involves a two-step oxidation p r i o r to p y r o l y s i s i n an inert atmosphere. The specific t e m p e r a t u r e and
dwell t i m e used in the polymerization-oxidation s t e p v a r i e s with t h e s i z e and
density of the urethane p r e c u r s o r . Typically, t h e foam is held at 150C and
again at 250C for 24 h o u r s t o prevent fusion during pyrolysis. The weight
and volume changes which o c c u r during p y r o l y s i s t o 1000C a r e about 55 and
60 percent respectively. T h e r e i s a density i n c r e a s e of about 10 percent for
rhe iow density, and 10 p e r c e n t for t h e high density carbonized urethane
foam.
Union Carbide h a s patents ( 2 ) granted and pending which'describe i n
d e t a i l the preparation of o r g a n i c p r e c u r s o r carbon foam.

105.

111.

PROPERTIES OF CARBON FOAM

The physical p r o p e r t i e s of the product carbon foams a r e dependent

on the type, quality, and t r e a t m e n t of the p r e c u r s o r . The m a j o r apparent
difference among the types of organic p r e c u r s o r is the average c e l l s i z e of
the product carbon ( s e e Table 11). The c e l l s i z e of the carbonized urethane
foam i s 8 to 32 m i l s for the 0. 05 g / c c density and approximately 8 to 16 mils
f o r the 0.25 g / c c density; the phenolic p r e c u r s o r carbon has a 2 to 6 m i l
c e l l size in the low density foam and approximately 1 t o 3 m i l s i n the high
density material.
TABLEII

Cell Size of Carbon Foam

Foam
Precursor
Urethane
Phenolic

'

Density

Cell
Diameter

0.05 g / c c
0.25 g / c c

8-32 m i l s
8-16 m i l s

0.05 g / c c
0.25 g / c c

2-6 m i l s
1-3 m i l s

The c e l l s t r u c t u r e s of these carbon foams a r e shown i n Figure 1.

The cells a r e football shaped with the m a j o r a x e s p a r a l l e l t o the foaming
directions. The pyrolyzed foams a r e psuedomorphs of t h e parent fqam.
The compressive strengths, defined as the point a t which a change^
i n slope of the s t r e s s - s t r a i n curve occurs, of properly p r e p a r e d 1000C
carbon foam f r o m phenolic and urethane p r e c u r s o r s a r e given i n Figure 2,
for foams in the density range of 0. 15 to 0. 35 g/cc. The strength of the
phenolic p r e c u r s o r carbon v a r i e s from 500 to 1900 p s i over the density
range; the strength of urethane p r e c u r s o r carbon is about one-half these
values.
The ultimate c o m p r e s s i v e strength of the 0.35 g / c c phenolic prec u r s o r carbon foam i s usually above 3000 psi. The strength of low density
foam exhibits a g r e a t e r degree of anisotropy than high density foam. The
strengths of 0.05 g / c c carbon perpendicular and p a r a l l e l t o the foaming
direction are 30 and 50 psi, respectively. Subsequent heat t r e a t m e n t of
carbon foam t o 2800C r e s u l t s i n no change i n strength for the phenolic
p r e c u r s o r carbon but does r e s u l t i n a s much a s a 7 0 % reduction in strength
for urethane p r e c u r s o r .
The t h e r m a l conductivity of the foam, determined by the Fitch
method, is quite low, approximately 0. 1 and 0.2 B T U / f t - F " - h r for 0. 05
and 0.25 g / c c carbon, respectively. The high te
e r a t u r e t h e r m a l conductivity was determined by the cyclic phase shiflPP) technique for a sample
of 0.27: g / c c density phenolic p r e c u r s o r carbon foam. The data a r e shown
in Table HI. The t h e r m a l conductivity p a r a l l e l to foaming is 10 to 25 percent
higher than the conductivity perpendicular t o foaming: In the direction of
high thermal conductivity, the range i s 0.5 to 0.8 B T U / f t - F " - h r i n the
temperature range of 1400" t o 2100C. Other properties of m a t e r i a l from
the same sample a r e shown i n Table III.

106.

TABLE I11
P r o p e r t i e s of 0 . 2 7 g / c c Phenolic P r e c u r s o r Carbon Foam

Direction
Perpendicular

Property
Density. lb/ft3
Compressive Strength, p s i
Shear Strength, p s i
. Thermal Conductivity,
BTU/ft-Fa - h r
R T -100C
1400C
1800G
210OOC

Direction
Parallel

0.27 g / c c
1,350
725

0.27 g / c c
2, 150
570

0. 18
0.47
0.45
0.60

0.20
0.'53
0.57
0.75

Of particular i n t e r e s t is t h e high s h e a r strength which d e m o w t r a t e s . t h a t

when the m a t e r i a l is used a s a n insulator, it can be firmly bonded to the
s u r f a c e to be insulated.
The p e r m e a b i l i t i e s of various carbon foams a r e shown i n Table I V
along with the p e r m e a b i l i t i e s of graphite and PC-45 a high density porous
carbon. The best c o m m e r c i a l g r a d e s of graphite with densities i n the
range of 1.6 t o 1.73 g / c c have permeabilities i n t h e range of 0.5 to 0. 02
Darcy's. The permeability of phenolic carbon foam is i n the range of 1.9
to 0.36 Darcy's. roughly a n o r d e r of magnitude g r e a t e r than t h a t of graphite;
the permeability of the urethane p r e c u r s o r carbon foam is i n the range of
22.6 to 71.5 Darcyls. two o r d e r s of magnitude g r e a t e r than that of graphite.
Porous carbon, PC-45, h a s a porosity a l m o s t identical with that of the high
density urethane p r e c u r s o r carbon, approximately 22 Darcy's.
TABLE IV
P e r m e a b i l i t y of Carbon Foam

Precursor
Material
1000.C T r e a t

Density,
glcc
'

Urethane
Urethane

0. 05
0.30

Phenolic
Phenolic

0.30

PC-45
ATL Graphite

1.04
1. 78

0.08

Permeability i n Darcy's
Parallel
Perpendicular
to Foam
to Foam
71. 5
24.3
1.9
0.95

20
0.068

31. 0
22.6
1.1
0.36
20
0.064

In summary. c a r b o n foam is a light weight, h i g h strength m a t e r i a l

which is stable above 2800OC. It may be used a s a n insulator, filter, o r
s t r u c t u r a l support m a t e r i a l and i s presently available in s i z e s a s l a r g e a s
14" diameter by 18" long.

,f

107.

Figure 1
CARBON FOAM 1 0 0 0 C HEAT-TREAT

The upper row i s phenolic p r e c u r s o r carbons i n both directions

of 0.05 and 0 . 2 5 g / c c density. T h e lower row i s corresponding urethane
p r e c u r s o r carbons.

108.

Figure 2

COMPRESSIVE STRENGTH VS. DENSITY

FOR CARBON FOAM

2000 I

I800

1600
1400

I200
IO00

800
600

400

200
0
0.15

0.20

0.25

0.30

0.35

I
0.40

DENSITY GMSKC

/ I

References
(1)

iij

" M e a s u r e m e n t s of T h e r m a l D i f f u s i v i t y and T h e r m a l C o n d u c t i v i t y of
G r a p h i t e with C a r b o n A r c I m a g e F u r n a c e , M. R. N u l l a n d W. W.
L o z i e r , 5th T h e r m a l Conductivity C o n f e r e n c e , Denver, C o l o r a d o ,
O c t o b e r 20, 1965.

U. S. P a t e n t 3 , l Z i , 0 5 0 ; E. S. P a t e n t 3 , 3 0 2 , 999; ii. S. P a t e n t
3 , 3 8 7 , 940.
I,