Melting Behavior and Thermal Properties

of High Density Polyethylene

M. W. WOO," P. WONG, Y. TANG, V. TFUACCA,b
P. E. GLOOR," A. N. HRYMAK, and
A. E. HAMIELECd

McMaster Institutefor Polymer Production Technology

Department of Chemical Engineering
McMaster University
Hamilton, Ontario, Canada US 4L7
Thermal diffusivity of high density polyethylene (HDPE) was studied over a wide
range of temperatures (25 to 200C) by melting powdered HDPE in a cylindrical
mold at several pressures (101.3 to 5065 Wa gage) and recording the temperature
profiles at several radial positions. The energy equation was solved numerically for
cylindrical geometry. The thermal diffusivity of HDPE was fit as a function of
temperature, porosity, and pressure.
INTRODUCTION

lastic processing operations generally involve the

heating, melting, shaping, cooling, and solidification of polymer melts. Thus, a systematic study of
such operations involves the analysis of the prevailing fluid flow and heat transfer phenomena, with due
consideration to the various phase transitions (first
or second order) that occur during the process (1). In
recent years, a substantial amount of effort has been
devoted to the engineering analysis or mathematical
simulation of processes such a s extrusion, injection
molding, and blow molding. Most of these treatments
have involved solving the standard transport equations with appropriate boundary and initial conditions. In most cases, much work was done with the
assumption of constant transport properties, such as
the thermal conductivity of the material. In fact, thermal conductivity of polymer changes with temperature, especially during a phase change (2). Various
techniques for the measurement of thermal conductivity and thermal diffusivity are available (3-17).
Some data have been reported describing the effects
of temperature, molecular weight, orientation, crystallinity, and pressure on the thermal conductivity
and thermal diffusivity of polyethylene. Kamal, et aL
(91, measured the thermal conductivity of various
polyethylenes in the solid form. The thermal trans-

aCurrent address: Dept. of Chemical Engineering. College of Engineering.

Suncheon National University Suncheon, Cheonnam. 540-742, S. Korea.
bCurrent address: %he-Poulenc Industrialisation. Centre de Decines.
2 4 Av. Jean Jaures. 69151. Decines Charpieu Cedex. BP 166 France.
'Current address: S . C. Johnson Wax. 1525 Howe St.. Racine. W I 534035011.
*To whom correspondence should be addressed.

port parameters of polymer should be considered from

pellet (01- powder) to liquid state under typical
processing conditions. In this paper the thermal diffusivity of high density polyethylene (HDPE) was
studied, from powdered form (with different packed
porosities), over wide temperature ranges. One dimensional heat transfer was considered theoretically and
experimentally.
THERMAL PROPERTIES OF HDPE

Four thermal properties considered were: thermal

conductivity ( k p ) , density ( p p ) , heat capacity (Cp),
and heat of fusion ( A H J ) of the materials. Thermal
diffusivity is defined as

In the analysis of most extrusion problems, the thermal diffusivity of the melt is assumed constant (2);
however, thermal diffusivity is a strong function of
temperature, and a weak function of pressure.

Density Change of HDPE

The density of polymer changes with temperature, especially with a phase change (14, 15). The
reciprocal of density increases sharply at temperatures approaching the melting point from below
(approximately 135C)and linearly above the melting
point. The effect of pressure is relatively small compared with the effect of temperature (14). We have
determined the following correlations for the density

POLYMER ENGINEERING AND SCIENCE, JANUARY 1995, Vol. 35, No. 2

151

M.W. Wooetal.
of HDPE a s a function of temperature from literature
data [(14),(15) and Figs. 6-26 from (211:
1
-=

1.05exp(O.O0136T)

(TI 135C)

(2)

( T > 135C)

(3)

linear relationship between the thermal conductivity

and bulk density at a single temperature (23C).
In the range of p , / p , from 0.5 to 1.0, the data on
polyethylene can be approximated by:

PP

1
_
-- 1.14 + 0.0009T
PP

(T in "C, p , in g/cm3)
Heat Capacity. Heat of Fusion, and Melting Point
of HDPE
The heat capacity ( C p ) , heat of fusion (AHf) and
melting point of the HDPE was measured by DSC
(DuPont 2000 series) according to ASTM standard
procedures [ASTM D3417-83, D3418-82 (16,17)l.The
heat of fusion was found to be 202(+4) J / g during melting, and the melting point to be 13% 5YC.
The heat capacity of HDPE is almost constant at
2.25 (J/g"C) from 50C to 200C. An effective heat
capacity ( Cp*),which includes the heat of fusion, can
be defined to assist in the numerical solution of
the energy equation. From the DSC results we fit the
following curve to describe the effective heat capacity
of HDPE.
Cp* = 2.25[ 1.0 + 5.5exp( - a(T- 135)121

THE HEAT TRANSFER EQUATION

Our apparatus consisted of a cylindrical mold (see

Fig. 1 ) and thus we shall consider a one-dimensional
heat transfer problem in cylindrical coordinates
(neglecting convection and radiation) that is described
bY
(8)

-dT
=o

( T I 135C)
(T>135C)

- 1 x 10-5T

k,

= 0.25 X

lo-'

p , - 0.90)

(9)

The heat of fusion term is only nonzero over the

melting region, and thus introduces a discontinuity.
An alternative approach is to use a n effective heat
capacity, Cp*, as in Eq 4 and include it in an effective
thermal diffusivity, a*. The heat transfer equation
becomes

(TI 135C)

(5)

dT

(T> 135C)

(6)

dt

where units of k , are (W/cmC), T are "C, and p , are

g/cm3. The thermal conductivity of solid HDPE
decreases with increasing temperature until melting point and remains nearly constant in the liquid
region.

Correction for Packed Powder

Compacted polymer particles have a lower bulk
thermal conductivity than that of the solid form,
owing to the presence of voids between the particles.
Yagi and Kunii ( 18) studied the effective thermal conductivities in packed beds in the absence of a phase
change, over the void fraction range of 0.25 to 0.65.
Langecker, et a1 (12). performed extensive measurements to determine the thermal conductivity of isotropically compressed polymeric powders and found a
152

at t = O

dT

Kamal, et a1 (91, show that the thermal conductivity can be different for different types of polyethylenes. Rauwendaal (2) presents the thermal
conductivity of HDPE as a function of temperature
and polymer density.

lo-' + 5 X

at r = R

dt

Thermal Conductivity of HDPE

= 0.17 X

T= Tsurfhce
T = To

where T is temperature, t is time, k , is bulk thermal

conductivity, r is coordinate of radial direction, and
R is the radius of the cylinder. If the variation in
thermal conductivity in the radial direction is small,
then Eq 8 can be rewritten as follows:

(Cp* in J/g"C, T in "C)

k,

at r = O

dr

(4)

where

a= 0.005
a = 0.05

where p b is the bulk density of the powder, and p p is

the density of the polymer (g/cm3), k , is the thermal
conductivity of the pure polymer, and k , is the effective thermal conductivity of the packed bed.

1 rlT

d2T

(10)

where
kb
a* = PPCP*

(11)

where, * denotes that the heat of fusion of HDPE

per degree Celsius is included. The experimentally
measured wall temperature (about 200C) was
used for the surface temperature boundary condition.
The one-dimensional partial differential equation
was solved by applying the finite element program
PDECOL (ACM algorithm), (19) which uses the GEAR
and G E M packages (20-22).
EXPERIMENTAL

The powdered HDPE, with a density of p p =

0.95 g/cm3, and melt flow index (MFI, 190C/5 Kg.)
POLYMER ENGINEERING AND SCIENCE, JANUARY 1995, Vol. 35, No. 2

Melting Behavior and Thermal Properties of HDPE

0.27 (23), was used as provided by Novacor
(W50555-H). The experimental apparatus, shown in
Fig. 1, consists of a mold filled with HDPE and placed
under pressure using a Carver laboratory press. The
cylindrical aluminum mold dimensions were: 75 mm
o.d., 50 mm i.d., and 150mm length. The wall temperature of the mold was measured by a thermocouple
imbedded in the mold wall and controlled using a
2kW band heater with a temperature controller. Four
thermocouples (Thermo Electric, type T, 0.159 cm
diameter) were inserted into the polymer, from the
bottom of the mold, at equidistant radial locations
from the center to the wall. These locations were fmed
by passing the thermocouples through the holes in
the bottom of the mold. The temperatures were

recorded by computer. It was assumed that the polymer at the polymer metal interface is the same temperature as the wall, i.e., that the heat transfer is very
fast.
The HDPE powder was loaded into a mold, at room
temperature, packed around the thermocouples, and
placed under pressure. The mold was then heated to
the desired wall temperature within t l " C , except
for some overshoot during the initial heating period.
The temperatures were monitored until the center
line temperature approached the wall temperature.

RESULTS AND DISCUSSION

Equations 2, 3, and 4 were used to calculate the
polymer density, and the effective heat capacity. The
numerical solution of Eq 10 was used to fit the
experimentally observed temperature time profile for
solid polymer (previously melted in our apparatus) by
varying the coefficients of Eq 12 for thermal conductivity for the polymer. Thermal conductivity was fit,
instead of thermal diffusivity, since the effective heat
capacity and the polymer density could be obtained
from independent measurements. The equation of
best fit (by trial and error) is:
k , = 5.665 X

x
k,

FQ. 1 . Schematic of melting apparatus: 1) hydraulic press,

4thermocouples, 5 ) temperature controller, 6 ) data acquisition computer, 7)HDPE

sample.

2 ) pressure gage, 3 ) band heater,

- 0.870

lop2In(T+ 273.15)

= 0.435

(TI 135C)
( T > 135C)

(W/cmC) (12)
This correlation differs in form from E q s 5 and 6 in
that we did not account for the densities of different
polyethylenes since we were using a single HDPE
type. A correction in the thermal conductivity for
each porosity was introduced to match the temperature time profile at each pressure. The temperature
profiles are shown in Figs. 2 through 6 along with

210

190
170
150

101.3 Kpa pressure

130

0.0

110
I

30

wall

70

50

0.64
1.27
1.91

90

--

model

r
0

20

40

60
minutes

80

100

120

Q. 2. Melting projle at various radial positions. 101.3 KPa pressure (gage). Points are measured temperatures, solid lines are
model predictions. The solid line for the wall temperature was not predicted but used by the model.

POLYMER ENGINEERING AND SCIENCE, JANUARY 7995, Vol. 35, No. 2

153

M. W. Woo et al.
210

190
170
150

130
110

90
202.6 Kpa pressure

70

......... experimental data

-model

50

30
10

!
0

60
80
100
120
minutes
Fig. 3. Melting projle at various radial positions. 202.6 KPa pressure (gage). Broken lines are measured temperatures, solid lines
are model predictions. The solid linefor the wall temperature w a s not predicted but used by the model.

210

20

40

190

170
150

7 30
110

90
303.9 Kpa pressure

70

......... experimental data

-model

50

30
I

20

40
60
80
Minutes
Fig. 4. Melting projle at various radial positions. 303.9KPa pressure (gage).Broken lines are measured temperatures, solid Lines
are model predictions. he solid line for the wall temperature was not predicted but used by the model.
0

the solution of the energy equation. The overshoot

for the 5065 KFa case (Fig. 6) was severe, because of
a poorly tuned controller, but a n average wall temperature was used for the numerical calculations. The
model follows the experimental data reasonably with
some deviation, especially near the center line, possibly due to convection or end effects, which were not
included in the model equation. Some small error
may have been introduced in the radial position by
deflection of the thermocouples, which were fixed at
the bottom of the mold only.
Figure 7 compares the observed variation in thermal conductivity with porosity to that predicted by
Eq 7. The relative thermal conductivity is the observed
thermal conductivity relative to that for zero porosity.
Figure 8 shows the variation of apparent thermal
154

diffusivity with temperature, for the ambient pressure case. These values are in general agreement
with those published by Tan (24). From these results
one can say that the assumed thermal conductivity
equation is a reasonable one, based upon the comparison between simulation and experiment.
Using this experimental method to measure temperature profiles and comparing them to Eq 10 gives
a n estimate of the thermal diffusivity. Using the independent measurements heat capacity and density,
one can estimate the thermal conductivity. Although
this method is not a s accurate as some other method
for measuring thermal conductivity, it does give indications of the values for packed powders as a function of porosity. Moreover, these experiments show
that these equations and parameter values are appliPOLYMER ENGINEERINGAND SCIENCE, JANUARY 7995, Vol. 35, No. 2

Melting Behavior and Thermal Properties of HDPE

200
180
160
v1

'5

3
v)

a,

0)

a,

140

120
100

80

2532.5 Kpa pressure

.........experimental data

60

-model

40
20

40
minutes

20

60

80

Flg. 5. Melting projile a t various radial positions. 2532.5 KPa pressure (gauge). Broken lines are measured temperatures, solid
lines are model predictions. The solid linefor the wall temperatures was not predicted but used by the model.

220

..,.
.. ..

200
180
0

160

-"

140

$
2?

120

.-3

100
80

5065 Kpa pressure

experimental data
model

60

40

20

!
0

20

40
60
80
minutes
Fig. 6. Melting proJile a t various radial positions. 5065 KPa pressure (gage). Broken lines are measured temperatures. solid lines
are model predictions. The solid line for the wall temperatures was not predicted but used by the model.

cable for modeling the temperature behavior of HDPE

over the melting region.

at the McMaster Institute for Polymer Production

Technology, McMaster University.

CONCLUSIONS

NOMENCLATURE

Equations to describe the thermal conductivity and

thermal diffusivity of HDPE during melting have been
developed and compared with experimental data. The
thermal conductivity of a packed bed of HDPE powder
increases with pressure because of the decreased
porosity and is adequately represented by the equations presented in this work,

a = A coefficient in Eq 4 .
C p = Heat capacity of polymer (j/$C).
Cp*= Effective heat capacity of polymer including
heat of fusion (j/g"C).
k, = Thermal conductivity of polymer (W/cmC).
k, = Thermal conductivity of packed bed (W/crnC).
R = Radius of the cylinder (cm).
r = Radius (crn).
T = Temperature PC).
t =Time (s).

ACKNOWLEDGMENTS

Dr. Woo would like to thank the Korea Science

Foundation for their partial support during his stay

POLYMER ENGINEERING AND SCIENCE, JANUARY 1995, Vol. 35, No. 2

155

M . W. Wooetal.
0.75
0.73 -

o
.-c

0.71

.g
>

0.69

0.67

0.63

0.57

.c

I-

-Equation 7
+

b
P

Observed

0.78

0.8

0.82

Density Ratio
Fg. 7. The efect of bulk density on the relative thermal
conductivity. Relative thermal conductivity is de3ned as is
the observed bulk thermal conductivity relative to the thermal
conductiviQ of the polymer.

4.OE-03
h

ln

3.OE-03

0
v

.?
.-

2.OE-03

ln

3
c

75 1.OE-03

:O.OE+OO

40

80
120
160
Degrees Celsius

200

Fg. 8. Thermal diffusiuity us. temperature. The thermal d@

fusiuity includes the heat o f h i o n ouer the melting region.

Greek Letters
a

a*

Thermal diffusivity of polymer (cm2/s).

Thermal diffusivity of polymer including the
heat of fusion (cm2/s).

pp = Density of the polymer (g/m3).

156

=Bulk.
=Polymer.

REFERENCES

0.76

N
<

Subscripts

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Received Januay 13, 1993

POLYMER ENGINEERING AND SCIENCE, JANUARY 1995, Yo/. 35, No. 2