Formation of Integral Skin Polyurethane Foams

Formation of integral skin polyurethane foams
INTRODUCTION
Integral skin foams are materials with a low density foamed core surrounded by a
nearly solid skin of the same material. In the case of rigid polymers, the skin
-core structure results in good flexural properties at low overall densities, an
d consequently such foams find wide application as structural materials. For exa
mple, polyurethane integral skin foams are used as structural elements in furnit
ure, and for making instrument housings and automobile dashboards. Good surface
finish, low thermal conductivity and ease of processing are additional advantage
s of such materials.
Properties of polyurethane integral skin foams depend strongly on the foam struc
ture in addition to the polymer properties. Several experimental and modeling st
udies (1-3) have shown the dependence of the foam mechanical properties on skin
and core thicknesses and densities. Analytical studies supported by experiments
(2, 4) have shown the existence of optimal structures and optimal density ratios
of skin to core at which the flexural strength is maximum. These studies clearl
y show the potential for achieving specific material properties, and minimizing
material usage by modification of the foam structure. Control of the foam struct
ure is possible by changing processing conditions, and it is important in this c
ontext to have a detailed understanding of the foam formation process to determi
ne the extent and range of such control. A comprehensive model for the foaming p
rocess would also be useful for the a priori determination of processing conditi
ons for a particular foam structure.
Polyurethane integral skin foams are made by the polymerization in a mold of a m
onomer mixture (polyol and isocyanate). Foaming occurs simultaneously as a resul
t of the vaporization of a low boiling blowing agent due to the exothermic heat
of reaction, and condensation of the blowing agent near the cool mold wall resul
ts in the formation of high density skins. A few previous works have focused on
models for this process, and we briefly review them here. Campbell (5, 6) In an
early work presented a simplified model for the process which gave reasonable qu
alitative trends. Yokono et al. (7) carried out a more detailed analysis of the
process, considering heat transfer, local density change and pressure increase d
uring foaming at constant total volume. The filling step, during which the monom
er mixture rises to fill the mold, was neglected. In spite of this, good agreeme
nt was obtained between experimental and computed values of maximum temperature,
maximum pressure, skin thickness, skin density and core density. Marciano et al
. (8) developed a more comprehensive model for the process, taking into account
the physico-chemical processes considered by Yokono et al. (7), and in addition
considered the initial filling step during which foaming occurs at constant pres
sure. The model predictions however, were not compared to experimental data to t
est its validity. The main objective of the work presented here is to obtain a d
etailed understanding of the process of integral skin formation by means of expe
riments and modeling, and thus to identify parameters most effective for control
ling foam structure. A theoretical model, based on previous works, is presented
in the next section together with an efficient computational technique for solvi
ng the model equations. Details of experimental studies carried out to test the
model are given next. Experimental and computational results are presented in th
e following section, and the conclusions of the study are given in the final sec
tion.
THEORY
We consider the foaming of polyurethane in a fiat plate mold. The foam rise occu
rs in a direction perpendicular to the mold surface as shown in Fig. 1. Because
of the heat generated by the exothermic polymerization reaction, a temperature p
rofile is developed with the maximum temperature at the upper free surface that
is furthest from the cooled mold wall. The polymeric mass begins to expand when
the boiling point of the blowing agent is reached and this time is called cream
time. The polymerizing mixture fills the mold at the rise time. At this time the
foam comprises an unfoamed skin near the lower wall, which is the region where
the temperature was always lower than the blowing agent boiling temperature, and
a foamed mass above the skin with a particular density profile. Until the rise
time the foaming occurs at constant pressure but with variable volume. After thi
s stage, the volume is constrained to be constant and the pressure inside the mo
ld increases due to the vaporization of blowing agent and a recondensation of bl
owing agent near the walls occurs. This leads to an increment in the thickness o
f the lower skin and the formation of the upper skin. Finally when all the polym
eric mass has gelled, the final structure is obtained. In the following sections
we first present the governing equations followed by the details of the transfo
rmations used to cast the equations in a form that simplifies the computations.
The dimensionless governing equations and the solution procedure is given in the
final part of this section.
Model Development
The physical assumptions used in the model development are similar to those of M
arciano et al. (8): We assume the foam to be a pseudo-homogeneous phase with var
iable density. The rate of mass transfer is assumed to be instantaneous so that
the concentration of the blowing agent at any point is simply equal to the equil
ibrium concentration (i.e., the solubility at the particular temperature and pre
ssure). Variations only in the foaming direction (z) are considered. However, th
e governing equations presented below are somewhat different since convection ef
fects are explicitly written down. Furthermore, an equation for the variation of
pressure in the mold due to foaming is obtained, which was not given in Marcian
o et al. (8).
The energy balance, taking into account the fact that the reaction occurs only i
n the liquid phase, is
[Mathematical Expression Omitted] (1)
where L and G are the weights of blowing agent per unit polymer weight in the li
quid and gas phases, respectively. The first term on the right hand side gives t
he rate of heat conduction, the second term gives the rate of exothermic heat ge
neration and the third term gives the rate of heat consumed by evaporation of th
e blowing agent.
The species balance equation for the concentration of limiting reactive end grou
ps (neglecting diffusion) is
[Delta]C/[Delta]t [v.sub.z] [Delta]C/[Delta]Z = [r.sub.A] (2)
Putting x = ([C.sub.0] - C)/[C.sub.0] the above equation reduces to
[Delta]x/[Delta]t [v.sub.z] [Delta]x/[Delta]z = -[r.sub.A]/[C.sub.0] (3)
where [C.sub.0] is the initial concentration of the functional groups. The above
balance equations require the velocity of the foam ([v.sub.z]), the rate of rea
ction ([r.sub.A]), the thermal conductivity (k ([Rho])) and the rate of evaporat
ion of the blowing agent (dL/dt) as inputs. We discuss the estimation of these f
unctions below.
The continuity equation based on the average density at a point ([Rho]) is
[Delta][Rho]/[Delta]t [Delta]/[Delta]z ([Rho][v.sub.z]) = 0 (4)
The velocity at any point can be obtained from the continuity equation as
using the condition that [v.sub.z] = 0 at z = 0.
Since the mass transfer is instantaneous, the weight fraction of blowing agent t
hat remains dissolved in the reacting mixture (L) is equal to the equilibrium va
lue ([L.sub.s](T, P)) after the cream temperature at the point is exceeded. The
rate of evaporation of the blowing agent is then
where
D/Dt = [Delta]/[Delta]t [v.sub.z] [Delta]/[Delta]z
is the material derivative. The evaporation is assumed to stop after the gel poi
nt, that is
dL/dt = 0 x [greater than] [x.sub.gel] (7)
where [x.sub.gel] is the conversion at the gel point. The weight fraction of the
blowing agent in the gas phase is then
G = [L.sub.0] - L
assuming no diffusion of the blowing agent, and the foam density is
[Rho] = 1 [L.sub.0]/(GRT/[PM.sub.bl]) (L/[[Rho].sub.bl]) (1/[[Rho].sub.P) (9)
where [L.sub.0] is the initial weight of blowing agent per unit polymer weight.
Volume change on mixing is neglected in the estimation of the density.
Thermal conductivity, which depends on the local foam density, is taken to be
[Mathematical Expression Omitted]
The above expression is identical to that used by Marciano et al. (8).
The general form for the rate of reaction is given by
where g(x) = 1.0 if x [less than or equal to] [x.sub.gel]. For the post-gel reac
tion an empirical expression for g(x) is used, which is determined experimentall
y together with the kinetic parameters.
The blowing agent used is n-pentane and an empirical equation for the equilibriu
m relationship for the solubility as a function of temperature and pressure is t
aken to be
The form of the above function is the same as that used by Marciano et al. (8),
however, the constants are obtained by fitting to experimental data for [L.sub.s
](T, P) obtained by Vaze (9) for the chemical system studied here. The experimen
tally obtained values of the constants (a, b, c, d, e and K) are given by Table
1, and the physical property data for the system is given in Table 2 (10).
In addition to the above, we require the following boundary conditions for the t
emperature:
T = [T.sub.w] z = 0 (12)
Table 1. Fitted Values of Constants for Solubility of n-pentane in
Polymer Solution Equation 11.
a -3.30 x [10.sup.-4]
b 2.09 x [10.sup.4]
c 67.5
d 8.69 x [10.sup.4]
e 1.01
K 35.8
[TABULAR DATA FOR TABLE 2 OMITTED]
[Delta]T/[Delta]Z = 0 z = [z.sub.max] [z.sub.max] [less than] h (13)
T = [T.sub.w] z = [z.sub.max] [z.sub.max] = h (14)
Thus until the top surface touches the surface of the mold there is no heat flux
from it, and afterwards the temperature is equal to the wall temperature. The i
nitial temperature of the reactants is assumed to be uniform so that
T = [T.sub.0] t = 0 (15)
The position of the free surface ([z.sub.max]) is obtained from
[m.sub.t] = [integral of] [Rho](z) dz between limits [z.sub.max] and 0 (16)
where [m.sub.t] is the total mass per unit area in the mold, which remains const
ant. The parameter [m.sub.t] can be obtained from the initial density ([[Rho].su
b.0]) and the initial height of the liquid layer ([h.sub.0]) as
[m.sub.t] = [[Rho].sub.0][h.sub.0] (17)
and
[[Rho].sub.0] = 1 [L.sub.0]/([L.sub.0]/[[Rho].sub.bl]) (1/[[Rho].sub.P]) (18)
using equation (9).
The position of the free surface must satisfy the constraint
[z.sub.max] [less than or equal to] h (19)
and for [z.sub.max] [less than or equal to] h, further increase in temperature r
esults in increase in pressure inside the mold. The time variation of the pressu
re in the mold is obtained by differentiating Eq 16 with respect to time after p
utting [z.sub.max] = h as
d[m.sub.t]/dt = [integral of] [([Delta][Rho]/[Delta]t).sub.z] dz = 0 between lim
its h and 0 (20)
which on expansion and assuming no pressure variation inside the mold gives
This completes the formulation of the model.
The process can be divided into three stages [ILLUSTRATION FOR FIGURE 1 OMITTED]
. In the first stage no foaming occurs so that [v.sub.z] = 0, L = [L.sub.0], G =
0, [Rho] = [[Rho].sub.0], and [z.sub.max] = [h.sub.0]. During this stage we nee
d to solve only Eqs 1 and 10. In the second stage, the material foams and the de
nsity decreases: the pressure, however, remains constant so that P = [P.sub.0].
During this stage we require the entire set of equations with the exception of E
q. 21. In the third stage the density profile readjusts at constant total volume
([z.sub.max] = h) as the pressure increases with time. The local density become
s constant once x [greater than] [x.sub.gel]. In this stage the entire set of eq
uations are required for solution of the problem.
Solution of the governing equations numerically is difficult because of the movi
ng boundary and convective effects, hence we transform the equations to a more c
onvenient form.
Transformation of the Governing Equations
We consider a transformation of the distance (z) to a new variable
m = [integral of] [Rho]dz[prime] between limits z and 0 (22)
In physical terms m is the total mass (gas liquid) per unit mold area up to the
height z. The partial derivative of any quantity [Theta] with respect to time ke
eping m constant is thus
Using Eq 22 and Eq 5, we obtain
Equation 23 thus simplifies to
so that the partial derivative with respect to time at constant m is equivalent
to the material derivative. This is expected since the mass in any material volu
me is conserved even though the density may be changing.
In the transformed coordinates the balance equations are:
[([Delta]x/[Delta]t).sub.m] = -[r.sub.A]/[C.sub.0] (27)
and the boundary conditions are
T = [T.sub.w] m = 0 (28)
[Delta]T/[Delta]m = 0 m = [m.sub.t] [z.sub.max] [less than] h (29)
T = [T.sub.w] m = [m.sub.t] [z.sub.max] = h (30)
The rate of evaporation of blowing agent is given by
and the time variation of the pressure is given by
The position of the top surface is given by
[z.sub.max] = [integral of] dm/[Rho] between limits [m.sub.t] and 0 (33)
Solution of the transformed equations gives T, L, x and [Rho] etc. as functions
of t and m. Transformation of the results in terms of the spatial coordinate is
straight forward using
z = [integral of] dm/[Rho] between limits m and 0 (34)
The advantages of the transformation are two-fold: (i) The convective terms that
involve evaluation of local velocity are eliminated, and (ii) a moving boundary
problem is reduced to one with a fixed domain. Both these result in simplificat
ion of the computational procedure.
Dimensionless Equations
The dimensionless variables are defined in Table 3, where
[A.sub.0] = A exp (- E/R[T.sub.0]) (35)
Using these dimensionless variables, the balance equations and boundary conditio
ns in dimensionless form are:
with
The reaction rate in dimensionless form is
and the solubility of the blowing agent is
with
G = [L.sub.0] - L (47)
Equation 36 is obtained by substituting for dL/dt in Eq 26. The underlined terms
in the equations are zero if [Mathematical Expression Omitted] or x [greater th
an] [x.sub.gel] and [Mathematical Expression Omitted] if [z.sub.max] [less than]
1.
Solution Method
The governing equations are solved using an explicit forward-time centered-space
finite difference scheme. A second order Runge-Kutta method is used for the tim
e integration. A check on the accuracy of the computation is the error [Mathemat
ical Expression Omitted] during the third stage of the process. Because of numer
ical errors, [Mathematical Expression Omitted] is always slightly different from
1.0, and this error increases with time. To take this into account we consider
the small variation in [Mathematical Expression Omitted] due to computational er
ror. From Eq 44 we get
Substituting [Mathematical Expression Omitted] in the above equation and expandi
ng, gives upon simplification
where
Thus a small increment in pressure [Mathematical Expression Omitted] for a time
increment [Mathematical Expression Omitted] is given by
where [Mathematical Expression Omitted]. In this way the pressure in the mold is
adjusted to maintain [Mathematical Expression Omitted].
For stability [Mathematical Expression Omitted] must be small enough where
and [Mathematical Expression Omitted] is the spatial step and [Mathematical Expr
ession Omitted] is the time step. This limits the maximum size of the time step
possible, for a given [Mathematical Expression Omitted]. Since gradients in temp
erature are sharpest near the walls, a spatially non-uniform discretization is u
sed with smaller values of [Mathematical Expression Omitted] near the walls.
EXPERIMENTAL STUDIES
Materials
The specifications of the materials used in the experiments along with their sou
rces are given in Table 4. All materials are used as supplied excepting the poly
ol, which is degassed to remove moisture. The degassing is carried out by heatin
g to 100 [degrees] C under vacuum for 4 h.
Preparation of Foam
Experiments are carried out to study the effect of variation in blowing agent co
ncentration ([L.sub.0]) and wall temperature ([T.sub.w]), on skin density and th
ickness, and core density. To ensure that the chemical composition is constant f
or a given set of experiments, the experimental study is carried out in three di
fferent batches, each containing different amount of blowing agent. The formulat
ions used for the preparation of the foams are given in Table 5. For each batch
the wall temperature of the mold is varied in the range 26 [degrees] C to 38 [de
grees] C. Three experiments are performed for the same conditions in order to ch
eck the repeatability of the experimental results. The overall density of the fo
am, determined by the shot weight, is kept constant at [[Rho].sub.all] = 485 kg/
[m.sub.3].
TWo different molds are used in the experiments: an aluminum mold of dimensions
18.4 cm x 18.3 cm x 1.2 cm and a steel mold of dimensions 17.9 cm x 7.7 cm x 0.6
cm. The aluminum mold is used for all the parametric studies reported, and the
steel mold, which is fitted with a pressure transducer, is used for studying the
variation of pressure and temperature in [TABULAR DATA FOR TABLE 5 OMITTED] the
mold with time. Both molds have channels for cooling water to maintain the mold
wall temperature at a specified value.
Weighed amounts of the mixture containing polyol, catalyst, surfactant and n-pen
tane from a particular batch and MDI are mixed using a high speed stirrer for 15
seconds. The mixture is poured into the cavity of the mold and the two halves o
f the mold are tightly clamped to ensure that there is no leakage. In some exper
iments, the variation of temperature at a particular height inside the mold is m
easured using a thermocouple, and the variation of pressure with time is measure
d using a pressure transducer; both are recorded using a data acquisition system
.
Polymerization Kinetics
Kinetic parameters (A, n, E, [Delta]H, g(x)) are obtained from adiabatic tempera
ture rise experiments (11). In experiment 29.4 g of degassed polyol, 0.02 g of c
atalyst and 27.4 g of MDI is stirred for around 30 seconds. This mixture is pour
ed into a foamed polystyrene cup, and the temperature variation with time is rec
orded using a data acquisition system. The data is used to determine the paramet
ers of interest by least square fit following the procedure briefly given below.
The general form for the rate of reaction in the pre-gel period is given by
The energy balance for adiabatic conditions reduces to
After the integration of above equation using the limits T = [T.sub.0] at x = 0
and T = [T.sub.max] at x = 1 we get
[[Rho].sub.P][C.sub.P] (T - [T.sub.0]) = (-[Delta]H) [C.sub.0]x (56)
And
x = (T - [T.sub.0]/[T.sub.max] - [T.sub.0]) (57)
Using Eqs 54 and 57, Eq 55 becomes
Based on the above development, the kinetic parameters (A, n, E, [Delta]H) are o
btained as follows. [T.sub.0] and [T.sub.max] are directly read from the experim
ental temperature versus time data, and ([Delta]H) is obtained using Eqs 56 and
57. The experimental data is first smoothed using a first degree least squares w
ith five point technique. After smoothing the temperature versus time data, dT/d
t is calculated using Douglas-Avakin method (12). The left hand side of Eq 58 is
plotted against - 1/T for various values of T until the gel point, and a straig
ht line is fitted using a least squares technique with different values of n inc
reasing from 1.0 to 3.0 with an increment of 0.05. The value of n chosen is the
one which gave the smallest mean square error. The gel point is obtained experim
entally by periodically moving the thermocouple during the reaction and noting t
he time at which the mixture seems solid. Several experiments gave the value [x.
sub.gel] close to 0.50. An empirical expression for g{x) is obtained for the pos
t-gel reaction by comparing the calculated dT/dt data using the kinetic paramete
rs with the experimental data as follows
g(x) = (1 - B Bx/x) (59)
where
B = [([(dT/dt).sub.EXPERIMENTAL]/[(dT/dt).sub.CALCULATED]).sup.1/n] (60)
It is expected that each batch has a slightly different rate of reaction due to
small variation in catalyst concentration. Thus for each batch the heat of react
ion and kinetic data were determined using adiabatic temperature rise data. All
these results are presented in the Tables 6-8. The term g(x) in the general equa
tion for the rate of the reaction is also determined for each batch and is given
below.
Batch 1: [Mathematical Expression Omitted]
Testing Procedure
The following measurements were carried out to characterize the molded integral
skin polyurethane foam samples.
Skin thickness: The upper and lower skins were obtained by cutting out a rectang
ular piece of the skin along with part of the core. The low density material cor
responding to the core was removed by abrading with emery paper. The thickness o
f the skin was measured using a micrometer screw gauge. Clearly there is a quali
tative element involved in determining the skin-core boundary. The transition be
tween these regions is quite sharp hence the error in measurement is small.
Skin density: The skin density was measured by stuffing a specific gravity bottl
e with small pieces of the skin approximately 2-3 mm in length. Water was then a
dded to the specific gravity bottle so that it filled the void spaces. The skin
density was calculated by using the following relationship.
[[Rho].sub.s] = [[Rho].sub.w] ([w.sub.1] - [w.sub.b])/[[Rho].sub.w][v.sub.b] - (
[w.sub.2] - [w.sub.1]) (61)
where [w.sub.b] is the weight of empty bottle. [w.sub.1] is the combined weight
of bottle and sample, [w.sub.2] is the combined weight of bottle, sample and wat
er, [v.sub.b] is the standard volume of the specific gravity bottle and [[Rho].s
ub.w] is the density of water.
Core density: A molded sample with a surface area of around 4 cm x 5 cm was take
n and upper and lower skin of the foam were removed. The mass and volume of this
core were measured and the density of the core was calculated.
RESULTS AND DISCUSSION
Computational Results
We first present computational results for a typical polyurethane system using n
-pentane as blowing agent. As a check of the computational technique, computatio
ns were first carried out for the parameter values used by Marciano et al. (8).
All the reported results of the paper could be reproduced and are given in (13).
Figure 2 shows the variation of temperature with height inside the mold at diff
erent times. The temperature increases with time, and during the first stage the
temperature is maximum at the top surface. After the first two stages the mixtu
re fills the mold and the temperature profile has a maximum value in the core an
d the lowest value (wall temperature) near the walls. Initially there is a sharp
change in the temperature near the walls, but the temperature is nearly constan
t in the core. This is because the thermal conductivity of the core is very low
and the heat generation in the core is nearly adiabatic. At later times the regi
on of constant temperature decreases and eventually disappears due to heat condu
ction to the mold walls. A similar trend as that in temperature is obtained for
the variation of conversion with height inside the mold at different times [ILLU
STRATION FOR FIGURE 3 OMITTED].
Figure 4 shows the variation of density with height in the mold at different tim
es. Skin formation, indicated by high density regions near the mold walls, is ev
ident relatively early in the foaming process (t = 60 s). The skin densities are
close to the polymer density, and there is a sharp change in density at the ski
n-core boundary. With increasing time, the core density decreases slightly and t
he skin thicknesses increase. At t = 100 s the equilibrium structure is reached
even though most elements have not gelled.
Figure 5 shows the variation of pressure with time inside the mold. The pressure
increases very sharply when the reacting mixture Just fills the mold, and then
more slowly to reach a steady value of about 3.8 bar at about 100 s. Beyond this
time there is negligible evaporation of the blowing agent, and this result is c
onsistent with the variation of the density profile with time.
Comparison with Experimental Results
The experimentally measured values of the skin thickness are reported in Figs. 6
and 7, together with the values predicted by the model. The symbols show the me
an value of thickness obtained from 3 separate molding experiments, and the erro
r bars give the standard deviation. The lower skin thickness decreases while the
upper skin thickness increases with increase in wall temperature. With increasi
ng wall temperature there is an increase in the amount of blowing agent evaporat
ed from the lower wall, and consequently there is an increase in upper skin thic
kness at the expense of lower skin thickness. Increasing [L.sub.0], keeping othe
r operation conditions constant, leads to an increase of the skin thickness [ILL
USTRATION FOR FIGURES 6 AND 7 OMITTED]. This results from the fact that pressure
reaches higher values after the rise time, which favors the condensation of the
blowing agent. The above trends are consistent with the theoretical results pre
dicted from the model. However, the experimental values for the lower skin thick
ness are higher (5%-15%) while that of upper skin thickness are lower (20%-30%)
than the corresponding values predicted from the model. The agreement is very go
od considering that all parameters of the model are independently obtained.
The discrepancy between theory and experiment can be attributed to two factors.
Firstly, the presence of fine air bubbles, which are dispersed during the mixing
, results in a lower initial density of the reactant mixture. An estimate of the
number density of the initially dispersed bubbles is given in (14). More recent
ly, experimental determination of initial bubble size distributions has revealed
that foaming results from growth of initially dispersed bubbles, and nucleation
is virtually nonexistent (9). Secondly, there is uncertainty in the value of th
e thermal conductivity used. The empirical equation for thermal conductivity [k(
[Rho])] used in the model corresponds to the case when R-11 is the blowing agent
. Since pentane has a significantly higher thermal conductivity than R-11, the t
hermal conductivity for the present system should be higher.
The amount of initially dispersed air depends on the viscosity of the reaction m
ixture, the surfactant concentration and the stirring speed among other factors
(9). Here we take this to be a fitting parameter so that the density at any time
is
where G[prime] is the initial mass of the dispersed air bubbles per unit polymer
mass. The initial density in the case is
and the initial height of the foaming mixture is [Mathematical Expression Omitte
d]. The initial thermal conductivity is taken to be a second fitting parameter.
Taking the initial density to be 30% lower and the thermal conductivity 51% high
er gives slightly better agreement with experimental results (dashed lines in [I
LLUSTRATION FOR FIGURES 6 AND 7 OMITTED]). The effect of the modification of the
initial condition on density predictions is much more significant as we show be
low.
The experimentally measured values of the core and skin densities are reported i
n Figs. 8, 9, and 10, together with the values predicted by the model. The core
density increases with increasing wall temperature [ILLUSTRATION FOR FIGURE 8 OM
ITTED] because with increasing wall temperature there is an increase in the amou
nt of blowing agent evaporated near the walls, causing the formation of a higher
density core. There is insignificant change in the core density with increasing
[L.sub.0] [ILLUSTRATION FOR FIGURE 8 OMITTED]. The model predictions describe t
he trends well, though the experimental values are higher (5%-45%) than the pred
icted values. The experimental study shows that there is a decrease in the lower
skin density [ILLUSTRATION FOR FIGURE 9 OMITTED] and a small increase in the up
per skin density [ILLUSTRATION FOR FIGURE 10 OMITTED] with increasing wall tempe
rature. The skin densities are nearly independent of the blowing agent concentra
tion [L.sub.0]. While the model predictions show that the skin densities are ind
ependent of the blowing agent concentration, there are significant differences b
etween theoretical and experimental results. The model, in all cases, gives skin
densities that are close to the polymer density, whereas experimental results g
ive densities which are 50% lower.
Taking into account the modification in initial density and thermal conductivity
discussed above gives good predictions of the core density, and reasonable valu
es of the lower skin densities (dashed lines in [ILLUSTRATION FOR FIGURES 8 AND
9 OMITTED]). The predicted upper skin densities are still somewhat higher than e
xperimental values. The reasons for this discrepancy are not clear; a possible c
ause could be the rise of bubbles from the core into the skin region that is not
considered in the model.
Figure 11 shows the temperature versus time profiles at fixed position in the mo
ld. There is reasonable agreement between theory and experiment though the maxim
um value of the temperature predicted from the model is higher than the correspo
nding experimental value. One of the difficulties of this comparison is that the
precise location of thermocouple is very difficult to determine. Figure 12 show
s the variation of pressure with time for a specific operating condition. The pr
essure inside the mold increases sharply with time after a time delay (rise time
), achieves a maximum, and after falling for some time becomes constant. The red
uction in pressure after the maximum point could be due to cooling of the materi
al near the upper surface resulting in condensation of the blowing agent. There
is reasonably good agreement between theory and experiment, though the maximum v
alue of the pressure predicted from the model is higher than the corresponding e
xperimental value. The rise time (time at which the pressure suddenly rises) is
well-predicted by the model. The significant decrease in the measured pressure a
fter the maximum value is achieved could be due to small leakages from the mold
that are difficult to avoid and shrinkage, which is not accounted for in the mod
el. The predictions of the temperature and pressure using the modified initial c
onditions are lower than the original theory, and the maximum values obtained ar
e in good agreement with experiment.
CONCLUSIONS
An experimental and theoretical study of the formation of polyurethane integral
skin foams is presented. Two of the important parameters of the process - the bl
owing agent concentration and mold wall temperature - are varied to study their
effect on the foam structure. The overall density of the foam is held fixed at [
[Rho].sub.all] = 485 kg/[m.sup.3]. The experimental results show that an increas
e in the wall temperature results in a significant decrease in the lower skin th
ickness and a small increase in the upper skin thickness. Increase in the blowin
g agent concentration results in an increase in both skin thicknesses. Increasin
g the mold wall temperature produces small increases in the core density and the
upper skin density, and a small decrease in the lower skin density. Blowing age
nt concentration, however, appears to have little effect on skin and core densit
ies. While the changes in densities and thicknesses obtained by varying the oper
ating parameters are relatively small, they could have a significant effect on t
he mechanical properties of the integral skin foam produced, since the propertie
s are quite sensitive to changes in the skin thickness and density (3, 4).
A mathematical model for the formation of integral skin foams is presented, base
d on the model of Marciano et al. (8). An efficient numerical technique for the
model computations involving a moving boundary and spatial and temporal variatio
ns is given. A detailed comparison of the prediction of the model and experiment
al results for the final foam structure, as well as a limited comparison of the
variation of temperature and pressure in the mold are presented. All parameters
of the model are independently estimated with the exception of the density depen
dent thermal conductivity [(k([Rho]))], which is obtained from (8). There is rea
sonably good quantitative agreement between theory and experiments for all measu
red quantities except for the skin density. The model predicts that the skins ar
e always solid polymer ([Rho] = [[Rho].sub.0]) whereas experiments reveal the sk
in density to be lower. An empirical correction of the initial density to accoun
t for air bubbles dispersed during mixing, and using a higher value of the therm
al conductivity gives better quantitative agreement between theory and experimen
t. The theory with the modified initial condition also gives better predictions
of the maximum temperature and pressure in the mold.
ACKNOWLEDGMENT
Financial support by the Department of Science and Technology through grant no.
DST-III.4(1)/93-ET is gratefully acknowledged. We are grateful to OSi Specialiti
es for supply of the surfactant.
NOMENCLATURE
[z.sub.max] = Pre-expontial factor.
C = Concentration of end groups.
[C.sub.0] = Initial concentration of end groups.
[c.sub.bg] = Specific heat of blowing agent in gas phase.
[c.sub.bl] = Specific heat of blowing agent in liquid phase.
[c.sub.P] = Specific heat of polymer.
E = Activation energy for chemical reaction.
G = Mass of blowing agent in the gas phase per unit polymer mass.
g(x) = Factor taken to slow down the reaction after gelation.
[h.sub.0] = Initial height of the reaction mixture,
h = Height of the mold.
[Delta]H = Heat of reaction.
L = Mass of blowing agent in the liquid phase per unit polymer mass.
[L.sub.0] = Initial mass of blowing agent in the liquid phase per unit polymer m
ass.
k = Thermal conductivity of polymer.
[M.sub.bl] = Molecular weight of blowing agent.
[M.sub.n0] = Molecular weight of polymer mass.
m = Total mass (gas liquid) per unit mold area up to the height z.
[m.sub.t] = Total mass of reaction mixture per unit mold area.
n = Order of reaction.
P = Pressure inside the mold.
[P.sub.0] = Ambient pressure.
[r.sub.A] = Rate of reaction.
R = Universal gas constant.
[R.sub.A] = Dimensionless rate of reaction.
T = Temperature in mold.
[T.sub.0] = Initial temperature of the reaction mixture.
[T.sub.cr] = Cream temperature in.
[T.sub.w] = Temperature of the wall of the mold.
t = Time.
[t.sub.c] = Cream time.
[t.sub.g] = Gel time.
[t.sub.t] = Thickness of lower skin.
[t.sub.r] = Rise time.
[t.sub.u] = Thickness of upper skin.
[v.sub.z] = Velocity of the free surface of foam.
x = Conversion of end groups.
[x.sub.bl] = Mole fraction of blowing agent in liquid phase.
[x.sub.bl0] = Initial mole fraction of blowing agent in liquid phase.
[x.sub.gel] = Conversion at the gelation.
z = Position of material element measured from the bottom of the mold.
[z.sub.max] = Height of free surface of foam.
p = Density of foam at any time.
[[Rho].sub.0] = Initial density of reaction mixture.
[[Rho].sub.bl] = Density of blowing agent.
[[Rho].sub.c] = Density of core.
[[Rho].sub.t] = Density of lower thickness.
[[Rho].sub.P] = Density of polymer.
[[Rho].sub.u] = Density of upper thickness.
[Lambda] = Latent heat of vaporization of blowing agent.
REFERENCES
1. J. M. Lifshitz, Polym. Eng. Sci., 23, 144 (1963).
2. M. Iida, M. Gotoh, and H. Yokono, Polym. Eng. Sci., 26, 701 (1986).
3. N. Y. Vaidya and D. V. Khakhar, J. Cellular Plast., 33, 587 (1997).
4. K. V. Joseph and D. V, Khakhar, Polym. Eng. Sci., 34, 726 (1994).
5. G.A. Campbell, J. Appl. Polym. Sci., 16, 1735 (1972).
6. G.A. Campbell, J. Appl. Polym. Sci., 16, 1387 (1972).
7. H. Yokono, S. Tsuzuku, Y. Hira, M. Gotoh, and Y. Miyano, Polym. Eng. Sci., 25
, 959 (1985).
8. J. H. Marciano, M. M. Reboredo, A. J. Rojas, and R. J. J. Williams, Polym. En
g. Sci., 26, 717 (1986).
9. N. Vaze, PhD thesis, Indian Institute of Technology-Bombay (1997).
10. N. B. Vargaftik, Handbook of Physical Properties of Liquids and Gases, pp. 2
55-60, Hemisphere Publishing Corporation, India (1975).
11. C. W. Macosko, RIM Fundamentals of Reaction Injection Molding, Hanser Publis
hers, Munich, Vienna, New York (1989).
12. R. H. Perry and C. H. Chilton, eds., Chemical Engineer's Handbook, 5th Editi
on, McGraw-Hill Book Co., New York (1976).
13. V. K. Gupta, M. Tech. dissertation, Indian Institute of Technology-Bombay, I
ndia (1997).
14. S. A. Baser and D. V. Khakhar, Polym. Eng. Sci., 34, 632 (1994).
COPYRIGHT 1999 Society of Plastics Engineers, Inc.
COPYRIGHT 2008 Gale, Cengage Learning

Formation of Integral Skin Polyurethane Foams

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