Density Modeling of Polyurethane Box Foam: Polymer Engineering and Science July 2014

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Density Modeling of Polyurethane Box Foam

Article  in  Polymer Engineering and Science · July 2014


DOI: 10.1002/pen.23694

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Density Modeling of Polyurethane Box Foam

Lu Shen,1 Yusheng Zhao,1 Ali Tekeei,1 Fu-Hung Hsieh,2 Galen J. Suppes1


1
Department of Chemical Engineering, University of Missouri-Columbia, Columbia, Missouri 65211

2
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

POLYMER ENGINEERING AND SCIENCE—2014


TABLE 1. Specifications of methyl formate (MF).
TABLE 2. Specifications of RUBINATE M isocyanate and three dif-
MW 60 ferent polyols.
Physical state Liquid
Boiling point ( C) 31.5 Product: RUBINATE M
Fn 2.70
Pc (bar) 60.075
Tc (K) 487.2 Sp. gravity @25 C 1.23
Ai 26.99601 % NCO 31.2
Bi 0.89328 Eq. wt. 135
Ci 22.52294 Viscosity cps @25 C 190
Product OH number
Di 23.16636
Poly G76–635 635
Voranol 360 360
Jeffol R315x 315
physical processes and (b) this work evaluates sources of
blowing agent loss in addition to solubility of blowing
agents in the resin phase.
This work builds on the work of Zhao et al. [18] on xi cPsat
i 5yi P (4)
modeling the foaming process using a series of ordinary
It is assumed that the carbon dioxide and vapor-phased
differential equations with Arrhenius constants and
MF are ideal with fugacity equaling to 1. Deviation from
enthalpy parameters. Although the emphasis of Zhao’s
ideality is accommodated by modifying the activity coef-
work was the prediction of polyol mixture performance in
ficient. Mass balance equations are solved under the con-
formulations, the emphasis of this work is the modeling
straint of Raoult’s law to determine the extent to which
and simulation of foam height (density).
MF evaporates. During analysis of the data, performance
at an activity coefficient of 1.0 is compared to 15 to eval-
EXPERIMENTAL DESIGN uate the extent that actual foam density varies from the
ideal model.

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.

1504 POLYMER ENGINEERING AND SCIENCE—2014 DOI 10.1002/pen


TABLE 3. Foaming formulation of rigid polyurethane foam. 1. Polyols, water, blowing catalyst, gelling catalysts, and sur-
factant (B-side components) were added and stirred in a
Weight/g Equivalents plastic cup. The B-side component was weighed and set
aside in a second plastic cup. About 2 min were allowed
B-side materials for degassing.
Poly G76–635 13.84 0.1569
2. The B-side components were mixed and stirred with A-
Voranol 360 15.68 0.1008
Jeffol R315x 4 0.0225
side for 15 s.
Dimethylcyclohexylamine 0.12 3. The mixtures were quickly poured into the cardboard box
(gelling catalyst) (designated at t 5 0 s) located on the balance. The foam
Pentamethyldiethylenetriamine 0.32 (foam reaction only) was allowed to rise and sit at ambient conditions during
(blowing catalyst) curing.
Momentive L6900 0.6 4. Residual masses in the mixing cup and stirrer were meas-
TCPP 2 ured (by mass differences) and recorded for subsequent
Distilled water (blowing agent) 1.04 (foam reaction only) 0.08 mass balance calculations.
A-side material
RUBINATE M 61.548 0.4559

RESULTS AND DISCUSSION


4. Thereafter, preweighed isocyanate (A-side material) was
added and mixed at the same speed for 7–10 s.
5. The reacting mixture was then quickly poured into a box Foaming Height Studies
with aluminum foil lining, and the foam was allowed to
rise and sit at ambient conditions (25 C) during curing. Figure 1 demonstrates the effect of water content on
the height of PU foams. Increasing water content leads to
All the B-side chemicals were added in the foam reac- increasing height of the box foam and decreasing density.
tion, whereas water and blowing catalyst were not added A doubling of the water content resulted in an approxi-
in the gel reaction. mate doubling of the height.
A high-speed mixer blade attached to a floor-model As a physical blowing agent, MF does not react with
drill press was used to mix the chemicals. LabVIEW soft- isocyanate; it provides an additional degree of freedom to
ware was used to monitor the temperature of the gel or control foam volume. Because of a lower boiling point
foam reactions for the first 15 min with a type-k thermo- and volatility, MF volatilizes and dissolves in polymer
couple attached through a National Instruments SCB-68 phase and consequently bubbles inside the foams come
box to a National Instruments PCI 6024E data acquisition into being. Figure 2 illustrates how more MF produces
card. more vapor which contributes to the volume increase.
Based on inspection, water appears to be more effective
Mass Loss Test. Experiments were also performed to in forming cells; the subsequent discussion pursues a
evaluate the amount of mass loss during box foaming. A quantification and insight into the differences.
cardboard box containing the reacting foam mixture was Increased amounts of both water and MF provide
placed on a digital balance accurate to 0.01 g. The fol- lower foam densities. These trends are qualitatively con-
lowing sequence describes the manner in which mass was sistent with the mechanisms of Eqs. 2 and 4. Figure 3
balanced and measured: compares performances to what the ordinary deferential

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.

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2014 1505


FIG. 2. Foaming height with different MF content. Symbols “w”, “䊊”, and “D” represent two repeated
samples contain 1.04 g water and 2.4, 1.5, and 0.5 g MF, 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.

1506 POLYMER ENGINEERING AND SCIENCE—2014 DOI 10.1002/pen


FIG. 4. Mass change during box foaming process. Symbols “w” and “䉫” are corresponding to the mass
value prior to and during the foaming process. 1, 2, 3, and 4 represent the stage of degassing, stirring, foam
rising, and after complete rise. Dm1 is mass loss prior to expansion of foam cells, Dm2 is buoyancy weight
adjustment, Dm3 is mass loss during foam growth, and Dm4 is mass loss after the maximum foam height is
attained.

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.

TABLE 4. Results of mass loss of different samples.

Dm from Efficiency Efficiency


Dm Dh Dm from blowing of blowing calculated by
Foam type (g equivalent) (cm) buoyancy agent agent (%) height (%)

Foam only with MF 1 2.13 8.83 0.57 1.38 42.4 40.0


Foam only with MF 2 2.12 8.48 0.52 1.42 41.0 33.2
Foam only with water 1 2.22 12.47 1.72 0.50 80.2 80.1
Foam only with water 2 2.26 11.61 1.78 0.48 81.1 82.7
Gel 1 0.38 2.02 0.10 0.28 – –
Gel 2 0.29 1.54 0.11 0.18 – –

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2014 1507


FIG. 5. Samples with 4.0 g MF. Symbols “䉫” and “D” represent two repeated samples with 4.0-g MF
blowing agent. Smooth and dashed lines symbolize MATLAB Simulation with 30 and 100% efficiency of
MF.

V5Vi 2Vp 2VS 2Rb (6) Rb 5k2 ð12ccÞ (7)

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.

1508 POLYMER ENGINEERING AND SCIENCE—2014 DOI 10.1002/pen


figure illustrates that while k2 is close to a, the best fit is
not with them equal. Furthermore, the data illustrate that
the primary cause for them not being equal is the concen-
tration of data at a nonzero limit as cc approaches 1.
For foam cells to expand, they must have a pressure
greater than the surroundings. For foams with nearly
100% cc content, the strength of the resin to preserve cell
integrity is at its greatest relative to foam with an open
cell nature, weak cell walls, and respective low cc con-
tent. The conclusion is that the internal pressure is signifi-
cant, is a function of cc, and is likely near a value of
2.02 atm at 100% cc content.
The lower dashed line of Fig. 7 represents a linear rela-
tion for internal cell pressure. Within the standard deviation
FIG. 7. Linear correlation for Eq. 9. Symbols “䉫” represent experi- of the data, the linear model (solid line) as represented by a
mental data between 1/qo 2 1/q and close cell content. Smooth line rep- combination of the two dashed lines is substantiated.
resents the modeling line characterizing 1/qo 2 1/q 5 20.0846* Future work on this area would include several topics
cc 1 0.0967. “--” line is displayed as trend of internal bubble pressure in
of interest, including: (a) development of fundamentally
which pressure reaches highest at 2 atm when close cell content c is
close to 100%. “-.-” line stands for k2 5 2a. based (not simple linear equations) for the relations of
cell pressure and release to cc., (b) acquiring more accu-
1 1 rate data, and (c) developing fundamentally based models
2 5k2 cc1a (9) that can predict cc based on the properties of the reagents
qo q
used to make the foam and the foaming formulation.
Figure 7 summarizes this trend for density versus close Figure 8 displays the comparison between modeling and
cell content data collected as summarized by Table 5. The experimental density, which presents slight deviation

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)

87.55 54.29 33.00 21.43 2.40 1.04


90.30 53.64 33.90 21.76 2.41 1.02
91.66 69.16 33.36 26.55 2.42 1.06
94.06 69.12 28.50 24.75 2.45 1.01
94.63 58.05 42.22 26.76 2.39 0.76
91.96 57.27 52.50 34.24 2.40 0.50
95.46 50.80 57.20 33.12 2.48 0.50
94.40 66.21 44.85 35.17 2.47 0.51
94.31 71.16 33.31 26.83 1.51 1.01
98.20 58.72 42.09 28.81 1.53 1.05
99.66 67.48 39.80 27.31 1.50 1.04
93.99 62.89 44.79 29.96 0.52 1.01
89.10 56.32 43.63 27.01 0.50 1.07
98.80 63.79 40.03 27.12 0.50 1.04
94.84 62.00 48.60 30.14 0.00 1.05
97.76 71.20 39.59 30.58 0.00 1.04
83.22 54.48 27.05 18.32 2.35 1.53
73.16 50.21 24.59 16.26 2.29 1.97
93.39 59.68 32.32 21.83 2.20 1.03
71.80 50.67 31.5 17.19 2.40 1.50
56.83 44.32 25.72 12.63 2.30 2.00
94.96 55.33 34.76 18.60 2.32 1.02
90.27 60.88 41.32 26.67 2.33 1.03
74.62 50.00 36.87 28.42 2.25 1.00
78.70 50.00 32.76 27.01 2.20 0.98
91.36 55.33 36.32 21.14 2.42 1.05
97.63 63.79 36.10 23.59 2.40 1.06
97.67 67.26 32.91 24.58 2.42 1.05
98.53 64.16 33.37 22.39 2.41 1.05
98.53 64.37 30.99 21.10 2.41 1.06
96.78 68.61 33.36 24.92 2.41 1.05

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2014 1509


FIG. 8. Linear relationship between ideal and experimental density. Symbols “䉫” represent experiment
density versus modeling density. Smooth line represents the modeling line.

caused by higher internal bubble pressure and potential MF methyl formate


experimental error. It is predictable to estimate the density ODE ordinary deferential equation
with the aid of MATLAB Simulation when we have the MW molecular weight
foaming formulation. Fn functionality
Eq. Wt equivalent weight
CONCLUSIONS c solubility
The measuring of mass and height in combination with R ideal gas constant (L atm/K mol)
computer-based simulation of the foaming process pro- T temperature (K)
vided a closure of the mass balance of blowing agents P pressure (atm)
used to make rigid box foams. The results indicated that t time (s)
evaporation losses during the mixing and degassing steps V volume (ml)
leads to a loss of efficacy of the blowing agent. This con- q density (g/ml)
clusion would broadly apply to blowing agents that rely m mass weight (g)
on low boiling points which form gas cells in urethane h height (cm)
foams at temperatures between 30 and 80 C. Tc critical temperature (K)
The primary sources of inefficient use of blowing Pc critical pressure (bar)
agent are loss of the physical blowing during open-air Psat vapor pressure (bars)
mixing and degassing. This loss of blowing agent would Vb volume of the buoyancy
not apply to in-line mixers used for commercial produc- qa density of the air
tion and should be taken into account with scaling up box Vo initial volume before the growth of the foam
or cup foams commercial processes. Vexp experimental volume of the foam
Although previous modeling work that was able to cor- Vi ideal volume of the foam without the gas rupture
relate inefficiency with Flory–Huggins parameters Vp volume loss due to the pressure
appeared to exaggerate the impact of activity coefficients, VS volume loss due to the solubility of the MF
the activity coefficients considered in this were reason- Rb release of the blowing agent
ably close to 1.0. A correlation relates to lack of efficacy
of blowing agents to both closed cell (cc) content and the ACKNOWLEDGMENT
buildup of pressure in the cells. The implication is that if
cc content is able to be simulated from a foam recipe, The authors thank the United Soybean Board for finan-
increasingly accurate estimates/simulations of density can cial support of the experimental studies used to validate the
also be attained. This was a major finding of this study as modeling work. Thanks to FSI Company providing foam
it identifies that the modeling of cell formation and rup- formulas and technology support.
ture is critical to accurately model foam density.
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DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2014 1511

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