Processability and Thermal Properties of

Blends of High Density Polyethylene,

Poly(Ethy1ene Terephthalate), and Ethyl Vinyl
Acetate CompatibiIizer
C . CHEN and F. S. LAI

Department of Plastics Engineering

University of Massachusetts at Lowell
Lowell, Massachusetts 01854
Because of differences in chemical structure and rheological characteristics,
high density polyethylene (HDPE) and poldethylene terephthalate) (PET) are incompatible when blended during recycling of PET soft drink bottles. To improve
the properties of the blends, ethylene vinyl acetate copolymer (EVA) was used as a
compatibilizer. Based on torque rheometer tests, the higher the concentration of
PET in the blends, the higher the initial loading torque. Blends of 50% HDPE and
50%PET had the lowest equilibrium torque. Equilibrium torque was highest at 5%
EVA. The presence of EVA made only a slight difference in the glass transition
temperatures of HDPE/PET blends. Higher EVA content in the blend resulted in a
lower melting endotherm. Thermogravimetric analysis showed that thermal stability was independent of EVA content: but the more PET in the blend, the lower the
final weight loss.
INTRODUCTION

he wide variety of applications of plastics in industry and the continuing increase in household
plastics consumption has led to serious waste disposal problems. A good recycling program would not
only alleviate environmental pollution, but also reduce the cost of materials.
In recent years, use of PET soft drink bottles has
skyrocketed. Since poly(ethy1ene terephthalate) (PET)
has many good physical and chemical properties such
as high strength, good impact strength, light weight,
safe toxicology, and transparency, it is often selected
a s a container material. However, the round base
of the PET bottle is often made of high density polyethylene (HDPE), which is incompatible with PET.
Therefore, ethylene/vinyl acetate copolymer (EVA) is
usually used as a compatibilizer to increase the compatibility of HDPE and PET.
The main purpose of this research was to study the
processability and thermal properties of HDPE/PET
blends with and without EVA compatibilizer.The prccessability of the HDPE/PET blend was estimated
from the experimental results of the torque rheometer, from which the processing conditions for injection molding, extrusion, etc. could then be
determined.

472

Thermal analysis was used to characterize the miscibility and thermal stability of the blends, and the
effects of the EVA compatibilizer on them.
In many practical applications, miscible polymer
blends are not desirable: multi-phase blends are
among the most important commodities in the plastics industry ( 1 , Z ) . However, poor blending of two
immiscible polymers will cause poor morphology,
weak interfaces, and unacceptable properties. This
problem can be addressed with the use of additives
referred to as compatibilizers, which alter the interfacial conditions between the different phases. Practical
compatibility may be achieved even when, in a thermodynamic sense, two polymers are not miscible (3).
High crystallinity prevents compatibility with plasticizers, because they are unable to separate the polymer molecules sufficiently to penetrate between them
(4). Thus, copolymers are frequently used as compatibilizers since each different segment adheres better
to one or the other of the blend ingredients. This
behavior leds to sufficient compatibility in the polymer blend system.
Polymer blends consisting of two polymers that
show miscibility usually exhibit one Tg. An immiscible polyblend may show two separate Tgs and have
mechanical properties that depend in a nonlinear
way on the composition (3).The crystallinity of maPOLYMER ENGINEERING AND SCIENCE, MARCH 1994, Vol. 34, No. 6

Blends of HDPE, PET and EVA

terials can be evaluated by observing the melting

transition and calculating the enthalpy change. The
material's thermal stability is usually judged by its
decomposition temperature, which is obtained by
plotting weight loss against temperature.
EXPERIMENTAL APPROACH

Materials
Three materials were used in this research: high
density polyethylene (HDPE) sold by Dow Chemical
Co. under the designation 32060C; polfiethylene
terephthalate) (PET) manufactured by Eastman Kodak under the designation 9902; and ethylene vinyl
acetate (EVA) with 36%vinyl acetate content, manufactured by Du Pont as Elvax. Table 1 summarizes
rheological and thermal properties of HDPE and PET.

Equipment and Experimental Procedure

Blends of HDPE and PET were prepared in ratios of
75/25, 50/50, 25/75. The EVA compatibilizer was
added to these blends in concentrations of 0.3, 5, 7 ,
and 10%.Because the PET and EVA were sensitive to
moisture, they were dried in a vacuum oven prior to
blending, to prevent hydrolyhc degradation of the
polymers. The PET is also sensitive to heat and the
melt temperatures of HDPE and PET differ greatly.
Thus, when HDPE and PET were blended in the
Haake Torque Rheometer, the processing temperatures were programmed in five steps: 1) processing at
250C for 7 min, 2) reducing the temperature to
200C over 2 min, 3) processing at 200C for 3 min, 4)
raising the temperature back to 250C over 2 min,
and 5) processing at 250C for 3 min.
The Haake Torque Rheometer was also used to
investigate the rheological properties of the blends.
The analysis was conducted with a System 40 software copyrighted by Haake Buchler Instruments, Inc.
Four different EVA contents, 0.2, 5, and 10%.were
blended with 50% HDPE and 50%PET to investigate
the effects of EVA content on the rheological properties of the blends. In addition, three rotor speeds, 40,
60, and 80 rpm, were studied.
For all blends, differential scanning calorimetry
(DSC) was used to study the melting behavior. In this
Table 1. Torque Behavior and Thermal Properties of
HDPE and PET.

research, the Du Pont DSC 2910 and Du Pont Thermal Analysis 2000 Controller were used. The cooling
system was supplied with liquid nitrogen which allowed investigation at temperature as low as - 170C.
The heating rate was set at lO"C/min and the temperature continuously increased from - 170 to
300 "C.
A Du Pont TGA 2950 and the Du Pont 2000 Controller were used to study the thermal stability of all
the blends. The heating rate was set at lO"C/min,
and samples were heated from room temperature to
800C.
RESULTS

AM)

DISCUSSION

Haake Torque Rheometer

To study the effect of EVA copolymer on the rheological properties of HDPE/PET blends, increasing
amounts of EVA were added to the HDPE/PET 50/50
blend. Based on the results of processing torque measurements by the Haake Torque Rheometer as shown
in Fig. 1 , it was determined that the equilibrium
torque increased from 0 to 5% EVA concentrations,
suggesting that specific interactions were created between the polymers. These interactions led to an increase of resistance to flow. At 10%EVA, the viscosity
decreased, probably due to increasing free volume.
Observation of initial loading torques,
2,
showed that they increased with increasing PET content. This was because the original PET material was
harder than the HDPE, leading to a high loading
torque created as high concentrations of PET in the
blend were put into the mixing chamber.
After processing for a couple of minutes, the torque
approached a stable and equilibrium value for all
blends. The equilibrium torque was lowest for the
HDPE/PET 50/50 blend. This result is shown in Rg.
3 and is consistent with the observation by Khelifi
and L a i (5)who used the capillary rheometer to measure the viscosities of similar blends with different
amounts of compatibilizers.
The higher rotor speeds led to higher torques since
the higher rotor speed was accompanied by a higher

m.

560
580

540

z
m

Torque Behavior
Loading torque (G-M)
Minimum torque (G-M)
Loading temperature ("C)
Minimum temperature ("C)

Thermal Properties
Glass transition temp. ("C)
Meltingtemp. ("C)
Melting Endotherm (J/g)
Onset decomposition temp. ("C)
Weight Loss (%)
Maximum weight loss rate
Wrnin)

HDPE
3369
1037
141
190

HDPE
125.1
185.0
408.1
99.2
23.4

PET

&

520

4045
96
247
272

500

480

Li
0
6-

460

PET

; 440

80.7
239.4
36.8
395.5
84.2
19.9

POLYMER ENGlNEERlNG AND SCIENCE, MARCH 1994, YO\. 34, NO. 6

f!
:
420
2
w

400

380

4
0

%EVA

Fig. 1 . Equilibrium torque of HDPE/ PET 50/ 50 as a func

tion of EVA content.

473

C. Chen and F. S. h
i
4600

2.85

4000

2.80

3400

2.15

10

3200
-1

3000

+.

2000

2.70

c0

2600

0"
%PET

IQg. 2. Initial loading torque as a function of PET content at

60 rpm rotor speed.

ioo

2.65

2.60

1.6

1.7

1.8

1.9

LogIRotor Speed lrprnll

650

625

Rg. 4. Log (torque) us. log (rotor speed, for HDPE/PET

blends with 5% EVA.

2
m

600 -

'1

575

550

525

$
LI

500
4

* 415
LT

450

425

400

2
0

50

25

15

%PET

FUJ. 3. Equilibrium torque as a function of PET content at

different rotor speeds.

shear rate. This can be explained by the power law

behavior commonly observed for polymer melts:
T=

Kj"

(1)

where T is the shear stress, y is the shear rate, and

K and n are the power law parameters.
With a few assumptions, Blyler and Daane o b
served and derived an equation which is similar to Eq
1 (6.7):
M

C( n) KS"

tained, and the slope of the plot gave the power law
index n Different blends had different power law
indices. This result was not in accordance with the
observation by Blyler and Daane (6) and Abraham,
et aL (7).This phenomenon may be explained by the
immiscibility of HDPE/PET blends and the effect of
EVA. Higher PET contents resulted in a larger power
law index. This illustrated the effect of rpm on the
equilibrium torque, increasing with increasing concentration of PET in the blends with compatibilizers.
It is important to predict general processing conditions for processing equipment. In this study, specific
parameters such as the screw speed, melt temperature, and barrel temperature, in recycling PET soft
drink bottles, might be estimated from the results
measured by the torque rheometer. Also, energy consumption was calculated from the area under the
curve of torque us. time. Thus cost of manufacturing
could be reduced if the proper processing conditions
were selected.
The energy required to process plastic materials at
a given temperature and a given shear rate may be
calculated from the following formula (7,8):
W= 2 ~ n ~ ' ~ M d t

(2)

where

where

= equilibrium torque
n = power law index
C( n) = a function which appears to be weakly dependent on n
K = constant in the power law shear stress/shear
rate relationship
S = rotor speed

n = the number of revolutions of the rotor

t, = the initial time
t2 = the final time
M = the torque

Figure 4 shows the plot of log torque us. log rpm for
various blend compositions. Straight lines were o b
474

(3)

Table 2 shows the energy required to process the

blends of HDPE and PET with 5%EVA. These calculations demonstrate that higher rotor speeds and
greater process stable torques would require more
energy.
POLYMER ENGINEERING AND SCIENCE, MARCH 1994, Vol. 34, No. 6

Blends of HDPE, PET and EVA

Differential Scanning Calorimetry (DSC)

It was difficult to detect the glass transition temperature of HDPE because of complications that are
introduced by crystallinity. The glass transition temperature of HDPE is usually reported to be between
- 120 to -20C.
In HDPE/PET 75/25 and 50/50 blends, the glass
transition temperatures of PET could not be detected
by DSC, because the amount of PET in the blends
was too small, and the location of the PET glass
transition was affected by the HDPE melting curve.
However, the glass transition temperature of PET at
75% PET was readily observed, as shown in Table 3,
and was almost the same as that of pure PET. This
indicated that HDPE and PET remained immiscible,
even after addition of EVA.
The melting endotherms of the blends are a measure of the degree of crystallinity of the polymers in
the blend. The decrease in degree of crystallinity of
HDPE and PET implies that there is some interaction
created by the EVA copolymer. Fig 5 illustrates that
higher concentrations of EVA in blends resulted in
lower heats of fusion, suggesting increased EVA prcr
duced interaction between the materials, causing the
crystallinity to decrease. However, this does not mean
that increasing the EVA content in the blends would
necessarily produce better properties. Since EVA acts
like a plasticizer, it might increase the impact properties but reduce the modulus and the ultimate
strength. The determination of compatibility of blends
in industry is dependent upon the properties needed
for each end use. The EVA content in the blend for
each specific use would be determined by a combination of processability, thermal properties, and mechanical testing.

position temperatures (9-1 1) of all blends were near

that of PET. In addition, Table 5 shows that the final
weight loss of PET was less than that of HDPE, and
the EVA compatibilizer had little effect on final weight
loss.
CONCLUSIONS

The addition of EVA caused a change in rheological

properties of the HDPE/PET blends, suggesting that
it affected the specific interaction between the polymers. As the concentration of EVA increased from 0
to 5%, the equilibrium torque increased. However,
when the EVA content increase to 10%of the blend,
the torque decreased. Again, probably due to the fact
that EVA acted like a high molecular weight plasticizer, creating more free volume and thus reducing
the viscosity of the blend.
An increase in the rotor speed led to an increase in
process torque because of the resistance to shear.
Also, it was found that a higher PET concentration
caused a higher initial loading torque. The HDPE/PET

100

50

TaMe 2. The Energies Requiredto Processthe Blends of

HDPE and PET with 5% EVA at Different Rotor Speeds,
and to Processthe Blends of 50 HDPEISO PET With
and Wrthout EVA at 60 rpm.
Energy Required (Joules)
25 HDPEI
75 HDPEl
50 HDPEl
50 PET
75 PET
25 PET

40 rpm
60 ipm
80 rpm

1919
3302
4886

EVA

0%

2%

5%

10%

50HDPE/50PET

2482

2686

2986

2302

1617
2986
4479

1651
3025
4675

Table 3. Glass Transition Temperaturesof PET in

HDPE/PET 25/75 BlendsWith and Without EVA.

T-

PC)

t:

26

25

L 21

8 EVA

The ThermogravimetricAnalyzer (=A) was used to

characterize the thermal stabilities of the blends of
HDPE and PET. Table 4 shows that the initial decom-

EVAConc.

Thermogravhetric Analysis (TGA)

Rotor
speed

,
HDPE
x : PET

0%

3%

5%

7%

10%

80.9

80.5

79.9

80.4

79.9

POLYMER ENGINEERING AND SCIENCE, MARCH 1994, Vol. 34, NO. 6

Flg. 5. Melting endothem of HDPE and PET as afunction of

%EVA in 50 H.DPE/ 50 PET blends.

Table 4. Onset Decomposition Temperatures in "C of HDPE

and PET Blends With and Without EVA.
(Onset Decomposition Temperature of pure PET 395.VC.)
EVA Conc.

0%
3%
5%
7%
1 0%

75HDPE
25 PET

50HDPE
50 PET

25HDPE
75 PET

395.5
395.2
395.8
398.3
397.6

395.8
395.2
395.9
396.5
395.6

396.4
394.9
394.4
395.0
395.0

Table 5. Weight Loss (%I of HDPE and PET Blends With

and Without EVA. (Temp. Range: Room Temp. to SOOT.)
EVA Conc.

75HDPE
25 PET

50HDPE
50 PET

25HDPE
75 PET

0%
3%
5%
7%
10%

96.4
96.3
96.5
97.3
97.3

92.3
93.2
93.2
93.7
93.3

87.8
90.0
89.5

88.8
88.6
475

C . Chen and F.S. Lai

50/50 blend had the lowest equilibrium torque, requiring less energy for processing.
Increasing EVA content in the blends led to decreased melting endotherms, indicating lower degree
of crystallinity of the blends.
EVA had little effect on thermal stability. The main
factor affecting thermal decomposition was the
HDPE/PET ratio.

ACKNOWLEDGMENT

The authors would like to express their special

thanks for Dr. R D. Deanin of the Department of
Plastics Engineering at the University of Massachusetts Lowell for his invaluable help and useful
suggestions.
REFERENCES
1. J. A. Brydson, Plastics Materials, Butterworth Scientific,
Boston ( 1982).

476

2. L. A. Utracki, Polymer Alloys and Blends-Themody

namics and Rheology, Hanser, New York (1990).

3. M. Kryszewski. in Polymer Blends M. Martuscelli and

R. Palumbo, eds., Plenum Press, New York (1980).
4. R D. Deanin, Polymer Structure Properties and Applications,Cahners, Boston (1972).
5. A. Khelifi and F. Lai, SPE ANTEC Tech Papers, 34, 1824
(1988).
6. L. L. Blyler and J . J . Daane, Polyym Eng. Sci., 7 , 178
(1967).
7. D. Abraham, K. E. George, and D. J. Francis, Eur. Polym
J.,26 (2). 197 (1990).
8. Z. Bartha, P. Erdos, and J . Matis, Int Polyym Sci. Tech
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9. M. E. Brown, Introduction to Thermal Analysis Teck

niques and Applications, Chapman and Hall, New York

( 1988).

10. W. W. Wendlandt and P. K. Gallagher, in Thermal Characterization of Polymeric Materials, E. A. Tun,ed., Academic Press, New York (1981).
11. W. W. Wendlandt, ThermalAnalysis, John Wiley & Sons,
New York ( 1986).

POLYMER ENGINEERING AND SCIENCE, MARCH 1994, Vol. 34, No. 6