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Density Modeling of Polyurethane Box Foam: Polymer Engineering and Science July 2014
Density Modeling of Polyurethane Box Foam: Polymer Engineering and Science July 2014
Density Modeling of Polyurethane Box Foam: Polymer Engineering and Science July 2014
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Department of Biological Engineering, University of Missouri-Columbia, Columbia, Missouri 65211
A model based on about a dozen fundamental differen- between density and compressive strength [3]. Density
tial equations is used to evaluate and simulate the ure- impacts the thermal conductivity due to the lower thermal
thane reactions and physical processes of urethane
box foaming. This work focuses on quantitative model-
conductivity of the gas phase relative to the resin phase
ing of foam density for foams using water and physical [4]. Therefore, accurately predicting density during poly-
blowing agents. The final densities of foams range urethane foaming is both important in its own right and
from 30 to 90% of the density as projected with full uti- as a critical step to ultimately predict other physical prop-
lization of the blowing agent. The primary sources of erties of foams [5–7].
inefficient use of blowing agent are loss of the physical
blowing during open-air mixing and degassing—basi-
Baser and Khakhar [8, 9] carried out a detailed experi-
cally, physical blowing agents with boiling points mental study of chemical and physical blowing agents
between 25 and 80 C will evaporate and experience with measurement of both temperature and density
cell rupture in box foams. This loss of blowing agent changes during the foaming process. The theoretical
would not apply to in-line mixers used for commercial model was based on the hypothesis that the foam was
production and should be taken into account with
under a single pseudohomogeneous phase, and the varia-
scaling up box or cup foams commercial processes.
POLYM. ENG. SCI., 54:1503–1511, 2014. V
C 2013 Society of tion of density with time was obtained by applying
Plastics Engineers energy and mass balances along with the kinetic and ther-
modynamic relations. Later, Tesser et al. [10] developed
a mathematical model to simulate the temperature and
INTRODUCTION density of the foams with the evaluation of kinetics of the
reaction between polyol and isocyanate during the foam-
Polyurethanes (PU) play a significant role in global ing process with an emphasis on Flory–Huggins modeling
industry with over three-quarters of the consumption in of blowing agent activity.
the form of foams [1]. They are extensively used in the Gibson and Ashby [11] came up with an elastic modu-
field such as rigid insulations in the walls of refrigerators lus based on the relative density for closed-cell (cc) foam
and buildings, high-resilience and flexible foam cushions, taking into account of three components: the strut flexion,
and elastomeric wheels and tires. the stretching of the cell walls, and the gas pressure
Foams can expand from during polymerization if gases inside the cc. Saint Michel et al. [12] characterized the
or vapors are produced in concert with the polymeriza- influence of the density and compared the experimental
tion. A common mechanism for gas generation is the results with Gibson and Ashby [11] and Christensen et al.
chemical reaction between water and isocyanate forming [13] in the linear domain and then extended to the nonlin-
carbon dioxide. In addition, exothermic polymerization ear domain.
reactions can provide heat to evaporate volatile blowing Avalle et al. [14] tested several types of foams and
agents such as methyl formate (MF) and pentane. For performed a study based on the Gibson model and the
rigid foams, the physical properties of most interest are Rusch (of the phenomenological type) model [15–17]
density, compressive strength, and thermal conductivity. together with two other models namely a modified Gib-
Both cell size and cell number contribute to change of son model and a new phenomenological model to charac-
density and compressive strength [2]. For PU foam, to a terize the mechanical properties. Additionally, available
first approximation, there exists a linear relationship experimental data were used to obtain the relationship
between material density and model parameters.
These previous works illustrate the importance of
Correspondence to: Lu Shen; e-mail: lsc38@mail.missouri.edu
quantifying foam density in foam formulation. The work
Contract grant sponsor: United Soybean Board.
DOI 10.1002/pen.23694
of this article differs in two ways from this other work:
Published online in Wiley Online Library (wileyonlinelibrary.com). (a) the current work is based on over a dozen fundamen-
C 2013 Society of Plastics Engineers
V tal ordinary differential models for the reactions and
Blowing Agents
Materials
As a chemical blowing agent, water reacts with isocya-
nate (RNCO) and produces carbamic acid (RNHCOOH) The isocyanate and petroleum-based polyols used in
which further decomposes into carbon dioxide and thus this study were RUBINATE M isocyanate, Poly G76–
generates gas bubbles in the resin according to reaction 635, Voranol 360, and Jeffol R315x from Huntsman
Schemes 1 and 2 forming an amine (RNH2). Company and Dow Chemical Co. and their specifications
are shown in Tables 2. N,N-dimethylcyclohexylamine and
RNCO 1H2 O ! RNHCOOH (1) N, N, N0 , N000 , N00 -pentamethyldiethylenetriamine were
RNHCOOH ! RNH2 1CO2 1HEAT (2) used as gelling catalyst and blowing catalyst, respectively.
Momentive L6900 was used as the surfactant for rigid
MF serves as a physical blowing agent that does not foams, Tris (1-chloro-2-propyl) Phosphate (TCPP) was
rely on any chemical reactions. Table 1 summarizes phys- used as fire retardant, and distilled water was use as
ical properties of MF. The MF is initially soluble in the chemical blowing agent.
mixture of isocyanate and polyol at ambient temperature.
Equation 3 is used to estimate the vapor pressure of
MF as a function of time [19]. Experimental Procedure
Gelling and Foaming Experiment. Experiments were
Psat
ln i
5ð12xÞ21 ðAi Þx1ðBi Þx1:5 1ðCi Þx3 1ðDi Þx6 performed to create polyurethane gels as well as rigid
PC polyurethane foams. The gel reactions were used as a
(3) control to assist in interpreting the data for the foam reac-
tions. Table 3 provides the control formulation used in
x 5 1—T/Tc where Tc is critical temperature in Kelvins, these studies. The amount of water and MF in this formu-
Psat
i is vapor pressure, in bars, Pc is critical pressure, in lation was used as parameters to better understand the
bars, Eqs. 3 and 4 are valid at the temperature range of foaming process.
220–487.2 K. The following steps were used in both the gelling and
The vapor pressure is used in the modified Raoult’s foam experiments.
Law (Eq. 4) equation which is used in combination with
heat and energy balances to estimate the amount of MF 1. Polyols, water, blowing catalyst, gelling catalysts, and sur-
that evaporates from the resin phase and proceeds to form factant (B-side components) were added into a plastic cup
bubbles/cells. It should be noted that because the resin successively.
phase is comprised of macromolecules, mass fraction was 2. These B-side components were mixed for 10–15 s.
used instead of mole fraction. 3. The mixture was allowed to degas for 2 min.
FIG. 1. Foaming height with different water content. Symbols “w”, “䊊”, and “D” represent two repeated
samples containing 2.4 g MF with 1.0, 0.75, and 0.5 g water, respectively.
equation model predicts for extreme cases of the activity were conducted that evaluated the mass of the foam dur-
coefficient equal to 1 and 15. Even in the extreme case of ing the foaming process.
high activity coefficients, the actual foam height is much
less than what is projected by the model. Temperatures in
the foam exceed 100 C during curing, and as such, little Mass Loss Studies
MF remains in the liquid even if high activity coefficients The box used to contain the rigid foam during the
impacted performance. The model trends show that the foaming process was placed on a digital balance accurate
activity coefficient predominantly has an impact during to 0.01 g to monitor weight loss during the foaming reac-
foam rise when the temperature ranged from MF’s boiling tion. Possible sources for weight loss are (1) air’s buoyant
point to about 40 C greater than MF’s boiling point. force applied by the increasing volume of the foam, (2)
Actual foam height only attained about 63% of what rupture of foam cells (bubbles) with collapse of the cell
was projected with full use of the blowing agents and or replacement of the vapors by new vapors, and (3)
ideal gas law calculation of the gas volume. Possible fac- evaporation/escape of MF, water, or carbon dioxide along
tors leading to the inconsistency are low-efficiency water- the upper surface of the foam.
isocyanate reaction, the rupture of carbon dioxide and MF Figure 4 illustrates the mass loss for a sample that
gas cells, and higher internal pressure. Further studies used only MF blowing agent and distinguishes between
FIG. 3. Experimental height versus modeling height. Symbols “䉫” and “w” represent two repeated samples
with 0.75 g water and 2.4 g MF. The smooth and dash lines represent MATLAB Simulation with 100%
water and MF when c equals to 15 and 1, respectively.
buoyant force and true weight loss. The volume caused ume of displaced air and the rupture of blowing agent
by buoyancy was calculated using Eq. 5. characterized as Dm2 and Dm3 in Fig. 4. Afterwards, no
expansion occurred in the system, and all the mass loss
Vb 5DV qa 5 Vo 2Vexp qa (5) was attributed to the escape of gases in the cells.
Figures 5 and 6 compare actual to model heights
Vb is volume of the buoyancy, qa is density of the air, where the model heights are for no loss of blowing agent
Vo is initial volume before the growth of the foam, which versus losses as summarized by Table 4. The results sub-
corresponds to the total volume of isocyanate, polyols, stantiate that a primary mechanism for the inefficiency of
water, and MF, Vexp is experimental volume of the foam. blowing agent is the loss of blowing agent through the
For the foam of Fig. 4, Vo592.5 cm3 and Vexp5572.7 upper surface of the foam through cell rupture (convec-
cm3 resulting in an equivalency of 0.57 g of buoyancy. It tion) or through the surface evaporation. Loss from the
is presented from Fig. 4 that the total amount of loss is top surface could be through diffusion straight from the
2.13 g, which indicates 1.38 g of mass loss attributed to resin to the air or it could be from cells/bubbles that rup-
the inefficiency of blowing agent (much of which is ture through the top surface.
attributed to the box-foaming technique rather than the
blowing agent).
Table 4 summarizes the buoyancy forces and mass
Modeling Loss of Blowing Agent Efficacy
loss of several foams. Dm and Dh are total mass loss
from experiment and height decrease associated with the Possible sources of inefficacy of blowing agents
release of the blowing agents. The foam in Fig. 4 stopped include: (1) higher than atmospheric pressure in cells, (2)
expanding at 75 s because an increase of viscosity facili- solubility of blowing agent in the polymer phase, and (3)
tated the rigidity of the foam that did not allow further release of blowing agent through the upper surface. The
expansion. During the first 75 s, the mass loss was impact of these is summarized by Eq. 5 in terms of gas
resulted from the buoyancy applied by the increasing vol- volume.
Vi is ideal volume of the foam without the gas rupture, Two assumptions to simplify this model are assuming
Vp is volume loss due to the pressure, VS is volume loss ideal gas behavior and assuming that only MF partitions
due to the solubility of the MF, Rb is release of the blow- in the resin phase. Substituting Eq. 6 to 8, where n1 and
ing agent. n2 are moles of MF and carbon dioxide, and S1 is the
This approach does not distinguish between the sus- fraction of MF that is in the resin (soluble).
ceptibility of MF versus carbon dioxide to these mecha-
nisms. Under the assumption that the pressure buildup ðn1 1n2 ÞRT n1 RT
V5 2 S1 2k2 ð12ccÞ (8)
has a minor contribution, Vp is cancelled out in Eq. 6. P P
Closed cell content is a property commonly measured
By setting Vo equals to the first two terms of the three
in rigid foam. A reasonable hypothesis is: if the final
on the right-hand side of Eq. 8 and expressing volume in
foam has a high cc content, the foam would have main-
term of density, Eq. 8 can be represented as a linear equa-
tained a high cc content during the entire foaming pro-
tion where the extent to which a varies from k2 provides
cess; and cc’s correlate this low release of blowing agent.
a point of discussion. Equation 9 displays a relationship
The Eq. 7 is an example correlation that can be tested
between density and close cell content used to interpret
with data where cc is close cell content (%).
the data.
FIG. 6. Samples with 1.0 g water. Symbols “䉫” and “D” represent two repeated samples with 1.0 g water.
Smooth and dashed lines symbolize MATLAB Simulation with 80 and 100% efficiency of water.
TABLE 5. Experimental and modeling density from samples displayed in Fig. 7 with comparison of efficiency, close cell content and quantities of
blowing agent.
Close cell content (%) Efficiency (%) Density exp (g/ml) Density model (g/ml) Quantities of MF (g) Quantities of Water (g)