Mechanics of Composite Materials, Vol. 39, No.

3, 2003

MECHANICAL PROPERTIES OF POLYETHYLENE

AND POLY(ETHYLENE TEREPHTHALATE) BLENDS

R. D. Maksimov,* R. Merii Meri,**

M. Kalnin,** and J. Zicans**

Keywords: polyethylene, poly(ethylene terephthalate), polymer blend, mechanical properties

The results of experimental investigation of mechanical properties in tension of polyethylene (PE) and
poly(ethylene terephthalate) (PET) blends are reported. Seven types of specimens with PE/PET weight ratios
of 100/0, 90/10, 70/30, 50/50, 30/70, 10/90, and 0/100 were examined. The data on the influence of blend com-
position on the yield stress, breaking stress, yield strain, and ultimate elongation are obtained. The features of
the effect of PE/PET ratio on the elastic properties of the blends are discussed.

Introduction

Mixing of polymers as a means of purposeful creation of materials with required properties is a very promising trend.
Recently, blend composites of poly(ethylene terephthalate) (PET) and polyethylene (PE) have attracted increased interest. For
example, in [1], the thermoviscoelastic properties of blends of PET with a high-density PE with PE/PET weight ratios of 75/25
and 25/75 were investigated. The main attention was paid to the determination of the efficiency of using special additives im-
proving the compatibility of blend components. The viscoelastic properties were examined by the method of forced mechanical
vibrations over a wide temperature range. These additives, which exhibit a high interfacial activity in relation to both compo-
nents of the blends, improve the dispersing ability and raise the interfacial adhesion.
The possibilities of orientational extrusion and the corresponding changes in the properties of PE/PET blends ob-
served during this process are discussed in [2]. The preforms obtained by extrusion were extended at a temperature of 130°C,
which corresponded to the endothermic peak of melting of the high-density PE used. The features of crystallization of PET ini-
tiated by deformation during extension were determined by the method of differential scanning calorimetry. The morphologi-
cal structure was investigated by scanning electron microscopy. The microphotographs obtained confirmed the formation of a
highly oriented fibrillar structure. It was found that, at rather small extensions, the elastic modulus and tensile strength in-
creased two- to threefold.
The urgency of investigating PE/PET blends is also caused by the problem of repeated use (recycling) of these poly-
mers. Of particular importance is the problem of recycling PET. The annual rates of growth of production and consumption of
PET in the world steadily increase and exceeded 10% in the last years [3]. The greatest part of PET in the world is used for the
production of fibers and filaments (to 65%) and various bottles (to 25%). The processing of PET into bottles and other dispos-
able vessels increases especially rapidly. In some regions (for example, in Northern America), almost half of the produced PET
*
Institute of Polymer Mechanics, University of Latvia, Riga, LV-1006, Latvia. **Institute of Polymer Materials, Riga
Technical University, Riga, LV-1048, Latvia. Translated from Mekhanika Kompozitnykh Materialov, Vol. 39, No. 3,
pp. 291-300, May-June, 2003. Original article submitted February 25, 2003.

0191-5665/03/3903-0189$25.00 © 2003 Plenum Publishing Corporation 189

is currently used for these purposes [3]. That is why the suitability of secondary PET for recycling is being investigated in-
tensely. One of the ways of utilizing polymer wastes is the production of composite materials based on them and subsequent
(secondary) processing of these materials into articles. Examples of successful realization of this method in producing blend
composites from secondary PET and PE are well known [4-6].
Of special interest is the study [4], in which results of creating blend composites from a low-density PE and secondary
PET (finely divided bottles) self-reinforced with PET microfibrils are presented. The reinforcement was realized by forming
microfibrils in situ during extrusion. The components were mixed in the melted state at 255°C. The rods obtained by extrusion
were cooled to 85°C, extended to a stretch ratio of 4-5, and granulated. The granules were molded at a temperature below
200°C, i.e., between the melting points of PE (110°C) and secondary PET (220-240°C). It turned out that, under such molding
conditions, the PET microfibrils formed during the preliminary extension were still retained. The resulting composite material
consisted of an isotropic polyethylene matrix reinforced with chaotically oriented short PET microfibrils of nanosize diameter
(100-300 nm) and an average length-to-diameter ratio of about 100, which is quite sufficient for the development of a consider-
able reinforcing effect. As a result, when PE is doped with a secondary PET in amount of 30%, its elastic modulus and tensile
strength increase almost ten- and twofold, respectively. These indices are close to the values of elastic modulus and strength of
the same PE reinforced with short glass fibers at the same coefficient of filling.
In the known studies, the properties of PE/PET blends, as a rule, were investigated on only two to three composition
variants, which did not allow one to judge the laws of changes in the properties of compositions over all the range of component
ratios. Therefore, the purpose of this study is to create, by using primary PE and PET of particular trademarks, blend compos-
ites of considerably different compositions (with an excess of PE or PET and intermediate ones) and to examine their tensile
mechanical characteristics in relation to the ratio of PE and PET components over the entire range of possible compositions.

Materials and Methods of Investigation

The blend composites were made from a high-density polyethylene of trademark Lupolen 6031 M (BASF AG corpo-
ration) and poly(ethylene terephthalate) of trademark Polyclear T 86 (Hoechst corporation). Blends with different contents of
the components were prepared by mixing in the melted state in a Haake Rheomex double-screw extruder with a granulator. Flat
dumbbell specimens with a 2.5 ´ 3 mm cross section of the working zone were molded at 270°C on an LM-type unit. Speci-
mens of seven compositions with the following weight ratios of the components were prepared: PE/PET = 100/0, 90/10, 70/30,
50/50, 30/70, 10/90, and 0/100.
The mechanical properties in tension were determined on a PU-7 unit at 20°C and a constant velocity of the moving
clamp of 1 mm/min, which corresponded to the initial strain rate of 5 × 10–2 min–1. Since the loading rate in determining tension
diagrams was small, the elastic modulus was found from results of several tests: the specimens were loaded in steps, the strains
were measured, and the load was removed immediately. The time of one loading–unloading cycle was approximately 2 s. The
strain specified in this case did not exceed 0.5%. The strains of specimens in loading and unloading were roughly the same, i.e.,
we did not observe any noticeable residual strains. The elastic modulus was determined as a ratio between the applied stress and
the measured strain.

Results and Discussion

The tension diagrams s( e ) of the materials examined are given in Fig. 1. The initial sections of the diagrams up to a
40% deformation are shown in Fig. 1a. In this figure, for a greater obviousness, the deformation curves of composites with dif-
ferent compositions are shifted relative to each other. Figure 1b shows the diagrams up to failure of specimens.
First of all, we should note that, under the test conditions adopted (extension velocity and temperature), a neck formed
on all specimens. However, a great distinction in the behavior of materials with different PE/PET ratios was discovered. Ini-

190
 s, MPa
60
à
50

40

30

20

10 1, 2, 3, 4, 5, 6, 7
e+k, %
0 10 20 30 40

60 s, MPa

50
b
40 7
30 1
4 5 6 2
20

10 3 e, %
0
0 50 100 150 200 250 400 600 800 1000

Fig. 1. Stress-strain curves in tension for PE/PET blends with weight ratios of
their components of 100/0 (1), 90/10 (2), 70/30 (3), 50/50 (4), 30/70 (5),
10/90 (6), and 0/100 (7): a — initial sections of the diagrams; for clarity, curves
2, 3, 4, 5, 6, and 7 are shifted horizontally to the right by a value k equal to 2, 4,
6, 8, 10, and 12%, respectively; b — ultimate elongation..

tially, the s( e ) dependence of pure PET specimens was almost linear with a gradual transition toward lower values of ds de.
Then, abruptly, a neck with a sharply expressed local narrowing of the specimen was formed. At this moment, a typical
so-called yield drop appeared at s y = 59 MPa and e y = 6.7% in the s( e )diagram. The neck propagated steadily over the whole
length of working zone of the specimen, after which the specimen deformed uniformly up to failure. In this case, a considerable
increase in stiffness was observed, which is usually called the deformational hardening. The failure of PET specimens was
quasi-brittle. In their destroyed part, broken fibrous formations in the form of tension bars were seen.
For PE specimens in tension, a different pattern was observed. The maximum of the s( e ) curve was reached without
appearance of a local neck. The subsequent decrease in the load, contrary to its drastic drop in the PET specimens, proceeded
gradually up to strains of about 60%. At this stage, the narrowing of the specimen was characterized by a great radius of curva-
ture, i.e., it was small in magnitude and propagated over a considerable part of specimen length. As a result of development of
such a poorly expressed neck, a smeared maximum appeared in the diagram s( e ). The strain corresponding to this maximum
was 11.4%, which was 1.7 times higher than that for PET specimens. A visible neck with a rather smooth transition to the nar-
rowed part of the specimen arose at 60-70% strains. When the development of the neck was completed, the specimen continued
to elongate with a gradual increase in stiffness up to limiting strains exceeding 900%. In this case, the material transformed into
an oriented state with a typical fibrillar structure. This was confirmed by the type of failure, which was accompanied by intense

191
 s, MPa e y, %
60 12
1 e b, %
10 1000

40 2 8 800

6 600
3
20 4 400
4
2 200
PET
0 0 0
0 0.2 0.4 0.6 0.8 1.0
PE
1.0 0.8 0.6 0.4 0.2 0

Fig. 2. Yield stress s y (1), yield strain e y (2), breaking stress s b (3), and ultimate strain
e b (4) as functions of the volume content of components in the PE/PET blends.

TABLE 1. Yield Stress s y , the Corresponding Strain e y , Breaking Stress s b ,

and Ultimate Elongation e b of PE/PET Blends

PE/PET ratio
s y , MPa e y ,% s b, MPa e b,%
By mass By volume
100/0 100/0 21.5 11.4 27.0 940
90/10 93/7 24.6 10.8 24.4 760
70/30 77/23 29.0 8.8 19.1 180
50/50 59/41 36.4 7.6 23.4 130
30/70 38/62 45.0 7.0 28.9 130
10/90 14/86 55.3 6.8 31.1 170
0/100 0/100 59.0 6.7 51.0 280

longitudinal splitting and fluffing of the specimen; the bundles of fibrous formations were disrupted at different places along
the destroyed part of the specimen. With appearance of damages on the final stage of deformation, a gradual decrease in the
load began. This process continued for a rather long time. The strain increment on this incubatory stage of failure process
reached 100% in relation to the initial working length of the specimen. The fluffiness arising on the specimen surface as a result
of numerous ruptures and separations of fibrils in the surface layers of the material also pointed to the accumulation of dis-
persed damages.
From all the blend composites tested, a stable development of the neck and subsequent hardening were observed only
in the PE specimens doped with 10 wt.% PET. The blends with a content of PET from 30 to 90% lost their ability for
deformational hardening and failed at the stage of an incompletely formed neck (see curves 3-6 in Fig. 1b). With increased con-
tent of PET, the fracture surface of specimens became less developed. However, the failure was not truly brittle since, at the

192
 E, MPa

1500

2 1
1000
3

500 PET
0 0.2 0.4 0.6 0.8 1.0
PE
1.0 0.8 0.6 0.4 0.2 0

Fig. 3. Elastic modulus E as a function of the volume content of components in the

PE/PET blends. Dots — experimental data; 1 — the Hashin–Shtrikman fork calculated
from Eq. (1); 2 and 3 — curves obtained from Eqs. (2) and (3), respectively.

places of rupture, formations of tension-bar type were clearly seen, which pointed to the manifestation of plastic deformation in
the region of failure of the material.
The basic characteristics of mechanical properties in tension are shown in Table 1 and Fig. 2 as functions of the vol-
ume content of blend components. With increased content of PET, the yield stress s y linearly increases, and the strain e y cor-
responding to this limit monotonically decreases, whereas its dependence on the blend composition is nonlinear. The type of
nonlinearity confirms that the PET greatly affects the development of a neck in the blend materials. As was already mentioned,
e y of PET is considerably smaller than that of PE. In addition, contrary to PE specimens, in PET specimens, the neck appears
spontaneously with a sharp local transition to the narrowed part of the specimen. In the blend material, this leads to an acceler-
ated decrease in e y upon addition of rather small amounts of PET to PE. For blends with excess PET, the value of e y varies in-
significantly and only slightly differs from that of pure PET.
The tensile strength s b (in conditional stresses) proved to be higher than the yield stress s y only for the specimens of
pure PE. Over a wide range of compositions (at a content of PET from 30 to 90%), the PE/PET ratio only slightly affected the
ultimate tensile strain e b . The specimens of these blends failed at strains which were somewhat smaller than e b of pure PET.
Of special interest is the dependence of the elastic modulus E on the blend composition. The experimental values of E
averaged over the results of seven parallel tests on specimens of each blend variant, as well as the root-mean-square deviations
characterizing the scatter of experimental data, are shown in Fig. 3 and Table 2.
We should point to the unusual type of nonlinearity of E as a function of PE/PET. Traditionally, the matrix of hetero-
geneous binary polymer blends with greatly different concentrations of components is identified with the phase whose volume
fraction is dominant [7, 8]. This phase to a great extent determines the elastic properties of the blend composite as a whole.
Therefore, at a small concentration of the disperse phase having a greater stiffness, the elastic modulus of the blend usually in-
creases rather slowly. This modulus starts to grow faster only when inversion processes arise and interpenetrating structures
originate [7-9]. It is obvious that the relationship between the experimental values of E and the blend composition, Fig. 3, does
not correspond to such a concept. Upon introduction of small (to 20 wt.%) amounts of PET, the elastic modulus of the blend at
first increases sharply and then grows practically linearly with PET concentration.

193
 TABLE 2. Experimental and Calculated Elastic Moduli E of PE/PET Blends

E, MPa

Hashin–Shtrikman bound- Averaging according

PE/PET ratio by volume
Experiment aries to

Upper Lower Voigt Reiss

100/0 730 ± 62 730 730 730 730
93/7 1160 ± 111 782 774 797 760
77/23 1280 ± 83 904 882 951 840
59/41 1290 ± 110 1056 1021 1124 952
38/62 1510 ± 73 1254 1214 1325 1127
14/86 1620 ± 61 1515 1490 1556 1427
0/100 1690 ± 80 1690 1690 1690 1690

Let us note that the elastic properties of polymer blends depend not only on the properties of the initial components
and their concentration, but also on the blend morphology. The morphology of heterogeneous two-phase blends, as a rule, is too
complicated for an exact mathematical analysis and prediction of mechanical properties. The bounds of possible variations in
the elastic characteristics of a two-phase isotropic medium can be estimated approximately from the expressions determining
the so-called Hashin–Shtrikman variational fork [10]

v2 ( K 2 - K 1 ) v1 ( K 1 - K 2 )
K1 + £K £K2 + ,
1+ v1 R1 ( K 2 - K 1 ) 1+ v2 R 2 ( K 1 - K 2 )

(1)
v 2 (G2 - G1 ) v1 (G1 - G2 )
G1 + £ G £ G2 + ,
1+ v1Q1 (G2 - G1 ) 1+ v 2 Q2 (G1 - G2 )

3 6( K i + 2Gi )
where R i = , Qi = , K is the bulk modulus, and G is the shear modulus; i = 1, 2 are phase indices,
3K i + 4Gi 5Gi ( 3K i + 4Gi )
where 1 and 2 refer to the phases with a low and high values of the modulus, respectively, and v i is the volume content of an ith
phase.
The boundaries of the blend modulus E calculated according to Eq. (1) and the known dependence for isotropic media

9KG
E=
3K + G

are presented in Fig. 3 and Table 2. Since the experimental values of the elastic modulus of PE and PET differ only 2.3 times,
the elastic modulus of PE/PET blends, according to Eq. (1), must lie within a very narrow interval. A comparison between the
calculation and experimental results shows that the calculated relationship between E and the blend composition differs consid-
erably (both quantitatively and qualitatively) from the experimental one.
For comparison, Fig. 3 shows the curves calculated by the formulas for parallel and series arrangements of components

E = E1 v1 + E 2 (1- v1 ), (2)

194
 E1 E 2
E= , (3)
E1 + v1 ( E 2 - E1 )

where E1 and E 2 are the elastic moduli of PE and PET, respectively, and v1 is the volume content of PE. Dependences
(2) and (3) are known as the Voigt and Reiss averagings, respectively. Over the whole range of blend compositions, the experi-
mental values of E exceed the upper bound determined by the Voigt averaging. So, the use of elastic characteristics of pure PE
and PET alone does not allow us to obtain a satisfactory agreement between calculation and experimental results. We must take
into account not only the morphological features of the blend, but also the probable changes in the elastic properties of its com-
ponents as a result of their interference during mixing and processing.

Conclusions

The blends of PE and PET of the trademarks examined in this study are sufficiently processible. The specimens of
blend composites with different PE/PET ratios, obtained by pressure molding, get deformed under the specified test conditions
(temperature and extension velocity) with formation of a neck. With increasing content of PET, the yield stress grows linearly,
according to the law of additivity. The yield strain depends on the blend composition nonlinearly, and the type of the
nonlinearity indicates that the PET greatly affects the neck formation in the blend material. Although blends with 30 to 90%
PET lose their ability for deformational hardening and fail at the stage of neck propagation, the limiting strains reached in this
case are rather high (above 100%). The addition of relatively small (to 20 wt.%) amounts of PET to PE at the beginning leads to
a sharp increase in the elastic modulus, but thereafter the modulus grows practically linearly with PET concentration. The re-
sults of the analysis show that the use of elastic characteristics of pure PE and PET alone for calculating the elastic modulus of
PE/PET blends does not allow us to obtain a satisfactory agreement between calculation and experimental results. We must
also take into account the probable changes in the elastic properties of components caused by their interference during their
mixing and processing.

This study was financially supported by the Latvian Council of Science.

REFERENCES

1. A. Galeski, “Dynamic mechanical properties of crystalline polymer blends. The influence of interface and orientation,”
e-Polymers, No. 026, 1-29 (2002).
2. P. Sambaru and S. A. Jabarin, “Properties and morphology of oriented ternary blends of poly(ethylene terephthalate),
high-density polyethylene, and compatibilizing agent,” Polym. Eng. Sci., 33, No. 13, 827-837 (1993).
3. E. M. Aizenshtein, “World production and consumption of polyester fibers and filaments,” Khim. Vol., No. 2, 3-11
(2002).
4. M. Evstatiev, S. Fakirov, B. Krasteva, K. Friedrich, J. A. Covas, and A. M. Cunha, “Recycling of poly(ethylene
terephthalate) as polymer-polymer composites,” Polym. Eng. Sci., 42, No. 4, 826-835 (2002).
5. D. V. Noskov, G. P. Ovchinnikova, and S. E. Artemenko, “Evaluation of recyclability of secondary polymers,” Plast.
Massy, No. 8, 45-46 (2002).
6. M. Pluta, Z. Bartczak, A. Pawlak, A. Galeski, and M. Pracella, “Phase structure and viscoelastic properties of
compatibilized blends of PET and HDPE recyclates,” J. Appl. Polym. Sci., 82, 1423-1436 (2001).
7. D. R. Paul and S. Newman (eds.), Polymer Blends, Acad. Press, New York (1978).
8. J. A. Manson and L. H. Sperling, Polymer Blends and Composites , Plenum Press, New York (1976).

195
 9. R. D. Maksimov, J. Zicans, T. Ivanova, S. N. Negreeva, and E. Plume, “Elastic and thermophysical properties of
poly(vinyl chloride) and chlorinated polyethylene blends,” Mech. Compos. Mater., 38, No. 2, 141-148 (2002).
10. Z. Hashin and S. Shtrikman, “A variational approach to the theory of the elastic behavior of multiphase materials,” J.
Mech. Phys. Solids, 11, 127-140 (1963).

196