Chemical and Physical Blowing Agents in Structural

Polyurethane Foams: Simulation and Characterization

M. MODESTI, V.ADFUANI, and F.SIMIONI

University of Padova
Department of Chemical Process Engineering
Via M ~ l z o l o9,35131Padova, Italy

Physical blowing agents such as n-pentane and methyl formate and, for compari-
son, chemical blowing agents such as water were used to prepare structural poly-
urethane rigid foams of different densities by reaction injection molding. Experi-
mental runs were carried out with formulations based on oligomeric isocyanate and
a mixture of polyether polyols. The constitutive equations for the vaporization rate of
the two blowing agents and the polymerization kinetics data are reported. Experi-
mental results were compared with the prediction of a simplified theoretical model,
and they showed a satisfactory agreement in terms of temperatures and density
profile. All the specimens were characterized by physical-mechanical properties
such as hardness, impact strength, flexural strength and elastic modulus and the
results were reported in function of the densities. The best mechanical performance
were obtained with the physical blowing agents, due to a better density distribution
profile and a thicker skin layer.

RUTRODUCTION agents, with the employment of standard processing

equipment for Reaction Injection Molding (RIM). This
I n recent years, the production of polyurethane foams
has expanded greatly owing to their enormous and
increasing employment in several industrial fields, i.e.,
equipment makes it possible to prevent the capture
of air during the mixing process, a typical drawback
of manual mixing techniques. A method for obtaining
car manufacture, furniture, refrigeration, etc. This suc-
kinetic data will be developed from the experimental
cess is due to the intrinsic capability of polyurethane
temperature values in order to identifL which parame-
systems to change physical-mechanical properties as
ters are most effective for foam structure control. There-
soon as reactants or processes are varied.
after, a theoretical model based on previous works
The present work deals with structural polyure-
(1-7)is presented to simulate the temperature and
thane foams, polymers with low-density foamed cores
density profile inside the mold. Simulation data will
and high-density exterior skin to be used mainly as
be correlated with experimental results. Finally, previ-
wood substitutes. Owing to their peculiar "sandwich"
ous specimens will be tested to determine the effective
structure, these foams reveal good mechanical prop-
mechanical properties that may be compared at the
erties, such as flexural strength, tensile modulus, and
end.
elongation, which depend primarily on skin thickness
and density, while their lightness is related with the
ExPERmENTAL
foamed inner layer. A proper choice of blowing agents
is the main target of present research; new and alter- m d 8
native blowing agents must be discovered in order to
Glendion RM 601: a polyether polyol with aver-
replace traditional and well-known CFCs and HCFCs,
which have been banned because of their environmen- age functionality equal to 4.3,hydroxyl number = 395
tal impact. The aim of this paper is to compare the mg KOH/g, viscosity = 2700 m P a s at 25°C (Enichem
physical-mechanical properties of specimens prepared S.p.A.).
with different blowing agents, for the purpose of re- Tercarol 1: polyether polyol with average molec-
placing the above-mentioned dangerous compounds. ular weight equal to 1000,hydroxyl number = 168
In our experimental tests, n-pentane and methyl for- mg KOH/g, viscosity = 280 m P a s at 25°C (Enichem
mate are used as physical blowing agents, while, for S.p.A.).
comparison, water is employed as chemical blowing MDI V M 2085: oligomeric isocyanate of 4-4'bi-
agent. Several Merent structural foam specimens are phenyl methane diisocyanate of average functionality
prepared with the three above mentioned blowing = 2.85 and Vow NCO = 31 (I.C.I.).

2046 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2o00, Yo/. 40, No. 9
 Chemical and Physical Blowing Agents

Table 1. Material Properties Used in the Computation (8-10).

~~~~~~~~~~ ~~~ ~ ~ _ _

PB [91/cm3] h" [ c a w M, [glmole] TB.0 ["CI Flam. Limits [% Vol.]

N-pentane 0.6312 88.86 72.15 36 1.4+ 7.8
Methylformate 0.9742 1 13.038 60.05 31.7 5 + 22.7

DMCEA dimethylcycloexylaminacatalyst (Abbot). Polymerization Kinetics

Tegostab 8404:silicone surfactant (GoldsmidthAG).
Blowing Agents:
- water = a chemical blowing agent; the reaction
with MDI leads to the formation of CO,:
-R-NCO 7 H,O + -h!-h'HCOOH4 -R-h?FfZ + CO, T
- n-pentane = a physical blowing agent, nowadays
employed as a substitute for CFCs and HCFCs
(with O.D.P. = 0) in the production of low den-
sity rigid foams
- methyl formate = a physical blowing agent not
yet used, although it is less inflammable than
n-pentane. It may combine with water to pro-
duce formic acid, which reacts with isocyanate
itself (8).Because of the scarce humidity of the
system, we will onlit these reactions.
The physical and chemical properties of these blow-
ing agents are reported m Table I (8-10).
~ ~ ~Foam
F O I = I I L ~ and O M Preparation
Several different 'sandwich" polyurethane specimens
were prepared in a piloi; plant. This laboratory system
comprises two tanks,one for the polyol mixture (i.e.
polyols, surfactant, caulyst and blowing agent) and
one for the isocyanate. 'fie temperature in the tanks is
kept uniform and constant by means of a circulating
fluid and by a stirrer which also prevents the forma-
tion of crusts. The appropriately dosed reactants are
introduced into a high thermal capacity mold through
a high speed mixing-head, which assures utmost ho-
mogeneity. After preliminary thermostabilization at
28°C. the mold is filled with the mixture, closed and
set under a press.
The foam formulations used in these experiments,
where only the blowing agents are changed, are re-
ported in Table 2. The amount of blowing agent is cal-
culated in order to obtain density values in open
molds equal to 0 . 1 g/cm3, in accordance with indus-
trial formulations.
After having prepared all the specimens, structural
rigid foams are conditioned at 70°C for 24 hours be-
fore cutting them in order to test their physical-me-
chanical properties.
Adiabatic temperature rise is the method used to ob-
tain kinetic data, i.e. the reaction rate, activation en-
ergy E,, the frequency factor A, the heat of reaction
A&. and the order of reaction n.
The temperature variation with time is measured by
using copper-constantan thermocouple and it is
recorded using a data acquisition system. The ther-
mocouple is held in the middle of the mixture foaming
into an open box (base: 25 X 25 cm, height 30 cm).
The energy balance per unit polymer weight may be
expressed as:
- dT dx dL
(-AHr) -- U . ( T - TO)* S + h , . - (1)
c p ' z = dt dt
This equation takes into account the fact that the
temperature increase is the result of exothermic heat
generated by the chemical urethane bond formation
reaction (also urea bonds if water is used), of heat dis-
sipation through the mold and vaporization and con-
densation of solvents, if physical blowing agents are
involved in the structural foam production process.
Evaporation is assumed to start when the boiling
point of the blowing agent in the mixture is reached
(cream temperature TB), and terminating at the gel
point (Xgel).Under this hypothesis, the following con-
ditions may be described:
In addition, when T > TB: - = - * - dT where dL/
dt dT dt
dT is the gradient of the experimental curve, obtained
by relating the blowing agent mass fraction in the poly-
urethane mixture with the boiling temperature (TB) of
the same mixture. This can be calculated by preparing
different formulations with increasing initial amounts
of physical blowing agents (wB)and measuring the ini-
tial boiling temperature (1). The experimental curves
are shown in Flg. 1 and may be correlated with the
following equation:
n-pentane: w, = 0.0080 + 14.668 exp (-T("C)/6.516)
methylformate:
w, = 0.0031 exp (35.751/(T("C) - 20.236))

Table 2. Details of Formulation Used.

~~~~~~~~ ~~~~ ~ ~~~

Polyol mixture [g] Isocyanate [g] Catalyst [g] Surfactant [g] Water [g] N-pentane [g] Methylformate [g]
Test 1 100 118 1.5 0.8 1 I I
Test 2 100 101 3 0.8 I 4 I
Test 3 1 00 101 3 0.8 I I 3.4

POLYMER ENGINEERIMG AND SCIENCE, SEPTEMBER 2000, Vol. 40, No. 9 2047
 M.Modesti, V. Adriani andF. Sirnwni

0.04 \

0.03 -

0.02-

0.01 -

30 35 40 45 50 55 60 65 70

T ("C)
Fig. I. Eqerimental curves relating the massfmction of physical blowing agents in the polyurethaneformdatm'nwrsustheboiling
temperature.

The energy balance (Eq 1) for adiabatic conditions is related to the three different systems prepared with
reduced to: water, n-pentane and methyl formate. The results are
reported in Table 3.
dTd dx dL
- (-AH,) - + h,.-
-
Cp'- (2) dx
dt dt dt -= k.(l-X)"
dt (5)
By integrating Eq 2, the resulting equation using the
limitsT = Toat t = 0 a n d T = Tadat a general time t,
we obtain the adiabatic temperature profile with time
from the experimental one.

U'* (T- - To) * dt For these calculations, an average value of = 0.427

where: U' = Us S/Cp
The heat of reaction (--A%) is given by the following
expression, where the evaporation of the blowing agent
is also taken into account:
Ultimately, by using the general form for the reaction
rate (Eq 5), from Eq 2 we obtain the final expression
(Eq 6),which carry out all kinetic parameters (Ea,
A, n)
cal/g "C is assumed, in agreement with values given by
(3) the Modem Plastics Encyclopedia (11)for cast polyure-
thane materials.
The value of 'n' is chosen to be equal to 2,because
when the left side of Eq 6 is plotted against 1/T, a
fairly straight line is obtained (within a satisfactory
temperature range) for all the blowing agents.
The value of conversion at gel point (Xgd)is obtained
experimentally. m e 2 shows the variation of con-
version X with time, which may be easily calculated
by using the well-known general form of the kinetic

Table 3. Therrnodvnarnic and Kinetic Data.

~~ ~~~~

T, ["Cl rc1
U' [s-'1 experirn. calculated (-AH,) tcallgl A [Ilrnol s] E, [callg] Xgel
Water 3.1 x 10-4 129.8 149.2 49.1 32298.3 563.2 0.39
N-pentane 3.1 X 10-4 127.8 149.1 31.6 5345.1 122 0.41
Methyl formate 4.5 x 10-4 106.7 125.7 43.5 100.5 97.7 0.42

2048 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2O00, Vol. 40, No. 9
 Chemical and Physical Blowing Agents

1.o

0.9

0.8
0.7
X 0.6

-
c
.-0 0.5
!!!
a, n-pentane
> 0.4
C
methyl formate
8 0.3
--A-

0.2
0.1

0.0
100 200 300 400 500 600
time [s]
Rg, 2. Variatirln of conversionX with time infree-rise tests: comparison between d i i i e n t blowing agents.

constant (as a function of E, and A) or by integration period of cure time. In this way the resolution of the
of Eq 5, respectively, if the reaction order n is chosen equation presented below is greatly simplified. Also
equal to 2. molecular diffusion is neglected because of the low
value of diffusion coefficient (< cm2/s) (7).Thus
Experiments in C l o d Molds the mass transfer equation is reduced to the kinetic
term. The actual mathematical model is able to predict
By using the same kirietic parameters of the previ-
the temperature change in the mold with isothermal
ous open-mold tests, as a n equal amount of blowing
and adiabatic boundary conditions. As known, a large
agent is employed and the reactants are unchanged,
amount of heat is generated in a short time during
we may obtain the profi.le of kinetic constant k and
structural foam polyurethane reaction. Therefore, a
conversion X in closed-mold experiments. At first, the
temperature gradient will exist inside the mold, with
temperature variation in the center of the mold is
the temperature near the mold walls differing from the
recorded by means of a copper-constantan thermo-
temperature in the foamed core, where the influence of
couple inserted through the side hole into the high ca-
heat conduction is not so strong. A s a matter of fact,
pacity aluminum flat mold measuring 210 mm X 130
the difference of temperature between the inner and
mm X 10 mm, and used for all the experimental stud-
the exterior layer of foamed material is an essential
ies reported. The mixture containing polyols, catalyst,
element for the formation of the high skin density. As
surfactant and blowing agents is mixed with isocya-
it seems to be convenient to define a differential mate-
nate (using the same pilot plant) and poured into the
rial control volume of thickness &, the heat conduc-
cavity of the mold, which is locked into position and
tion equation could be written as:
set under a press.
The results are reported in R g . 3, which shows the
variation of conversion X with time for the three differ-
ent blowing agents. In closed molds, the maximum
value of X is about 20% lower than the X values ob-
tained in open molds because of the choice of a lower
initial temperature (28°C vs. 32°C) and a smaller
From this equation it is quite simple to realize that
amount of reactants poured in the mold.
in any volume element, the temperature changes are
the result not only of exothermic polymerization and
Model Dwdopment
blowing agent evaporation but also of heat conduction
The mathematical model developed in this paper is with neighboring layers. In this case, we consider only
a simplified model similar to that proposed by Broyer the temperature gradient perpendicular to the main
and Macosko (7). Here, convection effects are ignored mold walls as significant (foaming direction 2). For
because in most of polymer reaction moldmg processes simplicity, the specific heat cp, the thermal conductiv-
the filling time is very little compared to the whole ity A, the reaction heat and the density of the system

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER2000, Yo/. 40, NO. 9 2049

 M.Modesti, V. Adrian& a n d F . Simwni

1.o

0.9 I
0.8 -

- n-pentane

-.- I I I I I I
100 200 300 400 500 600
time
Fig. 3. Variation of conversion X with time in closed-mold tests: comparison between dizzrent blowing agents.

are assumed to be reasonably constant. Actually,

thermal conductivity A, according to equation reported
by Marciano (3).changes with foam density. We will
assume an average value (equal to cal/cm s "C)
for A related to the average foam density equal to 0.4
g/cm3. It is also assumed that the mold wall tempera-
ture is constant, because of the great thermal capac-
ity of the mold.
The energy balance is solved using an implicit finite
difference method, according to which Eq 7 is ex-
panded to Eqs 8 and 9 The boundary conditions are defined as follows:
dT -
_
- (%,+I - Tmn)
(8) T,, = To for n = 0 and rn = 1, ......,M +1
dt At T,+,,, = To for rn = M + 1 and n = 0,.......N

d2T - Tmn+1 + Tm-1, n + l ) The system of linear equations, written as a matrix,

- - (Tm+l.n+l- 2 '
(9)
dz2 Az2
The whole time period (t - to)is divided in N little
steps equal to A t = (t - to)/N and the distance be-
tween the center and the wall of the mold (the mold
is assumed to be totally symmetrical) is divided in M
steps equal to Az = 0,5/M. Az is considered constant
because we have ignored the convective effects in the
heat balance equation. In this way, the index n is re-
lated to the time coordinate and the index rn to the
spatial coordinate. A general solution of the differential
equation will be the generic temperature T(z,t) = TtmAz,
nAt). We employ the implicit form (the 2nd order deriv-
ative is written as a function of the (n 1)th and not+
the nth time coordinate) in order to choose the inte-
gration steps Az and A t independently. The temporal
and spatial derivatives written in the above form, if
substituted into the energy balance equation, lead to
a system of linear differential equation:
will be solved with the Gauss method, in particu-
lar with the Thomas algorithm, by using an iterative
technique: the mth temperature value is calculated by
backward substitutions from T ,
+ to T
,,,+ with
rn = M, ...,1 and the unknowns obtained from previ-
ous iteration are substituted into the equations in the
subsequent step.
At the gel time we have also calculated the foam
density distribution inside the mold according to the
equation reported below (3):
The blowing agents in the vapor phase are supposed
to act as an ideal gas. Then, the value of pressure,
which appears in Eq 11, is assumed to be equal to the
blowing agent vapor pressure corresponding to each

2050 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2oO0, Vol. 40, No. 9
 Chemical and Physical Blowing Agents

7!5
205 sec
70 -

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5
Thickness [cm]
Fig. 4 . Varintion of terrperafure with thickness at di@rent times related to water-blownsystem

temperature values at gel time. In this paper, ppol. is
assumed to be equal to 1.16 g/cm3 and this is the
same value of skin density assumed for the outer liner.
RESULTS AND DISCUSSION
Figures 4, 5 and 6 s:how the simulation results of
temperature distribution with the three different blow-
ing agents. At 50 s the temperature profile is fairly flat
while, after this time, a temperature gradient appears
and a maximum value is reached at the foamed inner
core (z = 0). In order to check the validity of the model
applied here, we need to compare analyt~calresults with
experimental data: Figs. 7.8and 9 show the tempera-
ture increasing at the core, where the experimental
values were recorded. The correspondence between
real data and values predicted by the model is satis-
factory (especially if we keep into account the fact that
mean values were assumed for most variables), par-
ticularly in relation to the methyl formate blown speci-
men test. A three-dimensional graph is also reported

CI

0
Y

3
L
+
E
a,
r
a,
I-

-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5
Thickness [cm]
Fg. 5. Variation of temperature with thickness at &@rent times related to n-pentane-blown system

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2000, Vol. 40, No. 9 2051
 M.M o d e s t i V. Adriani, and F. Simwni

75 ,
70 1 150 sec

65 -1
60
5
e
a,

t 45
ia?, 40
I-

2 5 ~ . I . 1 . 1 . 1 . 1 ~ 1 . 1 . 1 ~ ~
-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 I 5
Thickness [cm]
Fig. 6. Variation of temperature with thickness at &@rent times related to methylformate-blown system.

as an example (Fig. lo), showing the temperature pro-
file as a function of temporal and, at the same time,
spatial coordinates.
With the solution of Eq 11, the density distriiution at
gel time is represented in Flg. 11. Density profiles are
only related to tests prepared with physical blowing
agents, because Eq 11 is not valid for water-blown sys-
tems. Considering the temperature and density distri-
bution inside the mold, the specimens obtained with
n-pentane and methyl formate as blowing agents re-
veal similar behavior with good skin thickness and high
skin density: at the moment, from these tests, methyl
formate, like n-pentane. appears to be a satisfactory
alternative blowing agent.
Then, in order to verify these density values pre-
dicted by the model, the skin and core density values
are measured by cutting out a r e c t a n w piece of the
skin (1 mm thick) and one of the inner layer (5 mm

J
I I I I I I I I
25 50 75 100 125 150 175 200 225
time [s]
FYg. 7. Variation of ewperimental and theoretical temperature with time at z = 0 related to water-blown system

2052 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2000, Vol. 40, No. 9
 Chemical and Physical Blowing Agents

.
70 -

60 -

50 .-

-.--+
Experimental temperature
Theoretical temperature
20 -* I I 1 I
30 60 90 120 1
time Is]
Fg 8. Variation oj’ewperimentdand theoretical temperature with time at z = 0 related to n-pentant-blown system

thick). The results reported in Table 4 show that there
is good agreement between experimental and theoretic
data for physical foaming agents. As foreseeable, the
use of H,O as a foaminj; agent provided foams with a
lower skin density, thus greatly affecting the physical-
mechanical properties of the specimens.
Characterization of Structural PU Foams
In the final part of this work, the mechanical be-
havior of structural foams was examined. As known,
the mechanical properties of these materials depend
quite strongly on their density. So a number of differ-
ent ’sandwich” polyurethane specimens were prepared
with the pilot plant by changing the pouring time in
order to obtain foams with different densities.
9 Superficial Hardness
In accordance with ASTM D 2240 standards, a Shore
D instrument was used to measure surface hardness;
this instrument comprises a conic tip that penetrates

70 -

60 -

40
-
- Experimental temperature
Theoretical temperature
30 -
I I I I I I
20 40 60 80 100 120 140 1
time [s]
F Q . 9. Variation of expimental and theoretical temperature with time at z = 0 related to methgl formate-blown system

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2000, YO/. 40, NO. 9 2053
 M. M o d e s t i V.Adrian&and F. Simioni

s (m,
m.10. ?tidimensionalprom of temperatureversus time and distance related to methylformate-blown system (half thickmess).

0.2 -
1 ' 1 ' 1 . 1 ' 1 . 1 . ~ ' ~ . ~ '
-0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 ( 5
thickness [cm]
Flg. 1 I . Variationof density with distanoe related to n-pent- and to methylformnte-blown system,

2054 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2000, Vol. 40, No. 9 ~
 Chemical and Physical Blowing Agents

Table 4. Experimental Values of Skin and Core Density of Prepared Specimens.

Skin density Core density Average density [g/cm3]
Blowing agent [g/cm31 [g/cm31 (whole specimen)
N-pentane 0.816 0.345 0.444
Methyl formate 0.817 0.362 0.452
Water 0.651 0.354 0.460

into the surface of structural foams more or less deeply Impact Test
depending on the hardness and compactness of the
skin layer. The superficial hardness reported in Fig. 12 This test is carried out in accordance with ASTM D
256 Standards: measurements of impact strength are
is an average value calculated after having tested about
made on a Charpy pendulum. The results obtained by
ten different areas on the same specimen. m e 12
changing specimen density are reported in Fig. 15. This
shows the clear inferiorily of water-blown systems, at-
chart shows that water is a poor blowing agent when
tested as known by a lower skin thickness. Instead
compared to n-pentane and methyl formate; the latter
n-pentane and methyl formate reveal a satisfactory
agents managed to reach greater performance ratings,
outer layer thickness, testified by the fairly high sur-
in accordance with previous tests.
face hardness values.

9 Flexural Strength and I Z b t i c Modulus CONCLUSIONS

Specimens are cut into a rectangular shape and
with a particular size in accordance with ASTM D 790
standards. The results <ofthe test are shown in Figs.
13 and 14. In the first E'igure, flexural strength values
versus average density iue reported, while the second
Figure shows elastic modulus. k o m these diagrams,
n-pentane and methyl formate turn out to be excellent
blowing agents because the rate of increase of the me-
chanical properties with respect to average density is
much greater than foarris obtained by using H,O.
In this paper, a study of the effects of employing
new blowing agents, as alternatives to hannful CFCs
and HCFCs, is presented. With the determination of
kinetic data, based on the Marciano model, the most
important kinetic parameters for the formation of poly-
urethane integral skin rigid foams are calculated. A
simplified numerical computation, which involves spa-
tial and temporal variations, is also carried out. The
distribution of temperature and the density profile
through the mold thickness obtained by this theoretical

80 *

water
n-pentane X / ,.--

methylformate -.---

0.20 0.25 0.30 0.35 0.40 0.45 0.50

Density [g/cm3]
Fig. 12. Values of hardness data versus awmge density.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2000, Vol. 40, No. 9 2055
 M. Modesti, V.Adriani and F.Simioni

v --------
18 - x - n-pentane
----
16 -

12 -
10 -

0.20 0.25 0.30 0.35 0.40 0.45 0.50

Density [g/cm3]
Fig. 13. Values offlenuzll strength versus average density.

model is in good agreement with experimental values,
which reveal the presence of a satisfactory skin thick-
ness when physical blowing agent foamed systems are
used (i.e. n-pentane and methyl formate). These data
are confirmed by the physical-mechanical character-
ization of specimens. Every test reveals the highest
mechanical properties for the two above mentioned
systems, when compared to water-blown foams, that
are closely connected with an outer skin layer forma-
tion. This indicates the fact that methyl formate, here
tested as a blowing agent for integral skin polyure-
thane foams, shows as good qualities as the better-
known n-pentane, but it is characterized by a lower
flammability level.

Density [g/cm3]
Fig. 14. Values of elastic &us data versus average density.

2056 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2Oo0, Vol. 40, No. 9
 Chemical and Physical Blowing Agents

Density [g/cmS
Fig. 15. Values of impact strength data versw average dens$.

NCNTATION x, =molar fraction of blowing agent in liquid

A = frequency factor [l/mole.s] phase
-
= average specific heat [cal/gK] X = conversion
CP
= activation energy [cal/gl z = spatial co-ordinate [cml
Ea
latent vaporization heat of physical blowing h = average thermal conductivity of foamed
h, =
polymer [cal/ cm.s. "C]
agents per unit polymer mass [cal/gl -
p = average density of foamed polymer [g/cm3]
AHr = heat of reaction per unit polymer mass
pPl, = density of the liquid solution without
[~/gl blowing agent [g/cm3]
LB = pondered ratio of liquid blowing agent
pB = density of physical blowing agent [g/cm3]
k3.r = pondered ratio of liquid blowing agent at
REFERENCES
LB.0 = initial pondered ratio of liquid blowing agent 1. A. J. Rojas, J. H . M a r c i a n o , and R. J. J. Williams,
MB = molecular weight of blowing agent [g/mole] Polyyn Eng. Sci, 22, 840 (1982).
n = order of reaction 2. J. H. Marciano. A. J. Rojas. and R. J. J. Williams, Po@-
P = pressure in the mold [atml mer, 23. 1479 (1982).
3. J. H. Marciano, M. M. Reboredo, A. J. Rojas, and R. J.
R = gas constant [cal/mole.K] J. Williams, Polym Eng. Sci,26, 717 (1986).
S = heat transfer specific area [cm2/gl 4. L. J. Lee and C. W. Macosko, lnt. J. Heat M a s s lhmsfer,
t = temporal co-ordinate Is] 23, 1479 (1980).
T = experimental temperature [K] 5. V . K. Gupta and D. V. Khakhar, Polym Erg. Sci, 3B,
164 (1999).
Tad = adiabatic temperature [K] 6. H. Yokono, S. Tsuzuku, Y. Hira. and M. Gotoh, P o b m
TB = boiling temperature of blowing agent in the Eng. Sci. 25, 959 (1985).
mixture [K] 7. E. Broyer and C. W. Macosko. AIChE J..22, 268 (1976).
= boiling temperature of pure blowing agent at 8. M. Modesti, N. Baldoin. and F. Simioni, Eur. Po@mJ..
TB.O
34, 1233 (1998).
Pam [Kl 9. Handbook of Chemistry and Physics, 53rd Ed.. tables
To = ambient temperature [K] (2-407. C-304, D-167. D-157 (1972-73).
-
- - To 10. M. Modesti, F. Simioni, and S . A. Rienzi, International
U = global heat transfer coefficient [cal/cm2.s.K] Confeence: CFCs,7he D a y After, p. 811, Padova, Italy
U' = u.s/cp [s-ll (1994).
11. J. Agranoff, Modern Plastics Encyclopedia, 52, 488,
wB,O = initial pondered fraction of blowing agent McGraw-Hill, New York (1975-76).

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