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Mechanical properties evaluation of

PVC/plasticizers and PVC/thermoplastic
polyurethane blends from extrusion
processing
ARTICLE in POLYMER TESTING JULY 2002
Impact Factor: 2.24 DOI: 10.1016/S0142-9418(01)00122-2

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Polymer Testing 21 (2002) 545550

www.elsevier.com/locate/polytest

Material Properties

Mechanical properties evaluation of PVC/plasticizers and

PVC/thermoplastic polyurethane blends from extrusion
processing
V.J.R.R. Pita a, E.E.M. Sampaio b, E.E.C. Monteiro
a

a,*

Instituto de Macromoleculas, Professora Eloisa Mano Universidade Federal do Rio de Janeiro, CP 68525, Rio de Janeiro,
21945-970, Brazil
b
Campus regional da UERJ, Nova Friburgo, RJ, Brazil
Received 17 July 2001; accepted 16 October 2001

Abstract
Mechanical and processing properties of blends of poly(vinyl chloride) (PVC) with di-isodecyl phthalate (DIDP) and
thermoplastic polyurethane (TPU) were compared with di-2-ethylhexyl phthalate (DOP). The influence of processing
conditions on the mechanical properties was studied by changing the content of the additives and using different twin
screw speeds. The mechanical properties (tensile strength, modulus, and energy) of PVC/DIDP presented the same
behaviour as PVC/DOP at all concentrations. The mechanical characteristics of PVC/DOP and PVC/DIDP show that
these systems are probably affected by the speed of the twin screw. Polyurethane blends exhibit better structural
properties compared to the other plasticizers. The twin screw speed exhibited no influence on the stressstrain property
profile of the PVC/TPU blends. The results indicate a minor influence on the decrease of PVC properties when the
plasticizer used is a TPU. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: PVC/plasticizers blends; Mechanical properties; Extrusion processing

1. Introduction
Poly(vinyl chloride) (PVC) plays an important role in
the plastic industry and is one of the most versatile
thermoplastics, but it must be combined with a number
of additives before processing.
Low-molecular-weight plasticizer is one of the major
additives used in PVC compounding. The addition of
plasticizers to a PVC formulation decreases many mechanical properties of the PVC product (hardness, tensile
strength, modulus, etc.); however, low-temperature
flexibility, elongation, and the ease of processing are all

* Corresponding author. Tel.: +55-21-495-2861; fax: +5521-270-1317.

E-mail address: ecermel@ima.ufrj.br (E.E.C. Monteiro).

improved. The most widely used low-molecular-weight

plasticizer is di-2-ethylhexyl phthalate (DOP) [1].
These types of blends present serious problems of high
migration (permanence) and consequent loss of blend
properties. One alternative to this kind of problem is the
use of polymeric plasticizers. Polyester/PVC miscibility
studies [2,3] have shown that some polymeric polyesters
are to some extent miscible with PVC, and other studies
have shown that some polyurethanes are also miscible
with PVC.
Polyester-based thermoplastic polyurethane (TPU) is
commonly blended with plasticized PVC resulting in a
PVC blend with improved abrasion and fatigue resistance [1,4,5]. However, as with most PVC/thermoplastic
blends, they are difficult to process on conventional PVC
processing equipment because of their high melt viscosity and limited heat stability [6].
The addition of TPU plasticizers to PVC to form a

0142-9418/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 4 1 8 ( 0 1 ) 0 0 1 2 2 - 2

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polymer blend can be accomplished in several ways [7].

Twin screw extrusion is one of these. In this way, the
rheological properties can be observed and related to the
mechanical properties obtained under different conditions of processing [8].
This work is part of a programme concerned with the
effects of plasticizer type, and involves the relationships
between PVC/plasticizer properties and the processing
characteristics of the PVC compound. This study evaluates the mechanical properties of PVC/TPU blends and
the alternative compounds PVC/di-isodecylphthalate
(DIDP) and compares them with the traditional formulation PVC/DOP. All of the blends were prepared in a
twin screw extruder. Their mechanical behaviour is compared under different processing conditions.
Fig. 1.

2. Experimental
2.1. Materials
The commercial PVC used in this study was a suspension polymerized homopolymer, molecular weight distribution=2.6, supplied by Tryken Company (Brazil) and
designated as Norvic SP 1100 HP. Vulcan Company
(Brazil) supplied the PVC stabilizers UBZ 790, Ba/Zn
type, and commercial DOP and DIDP. COFADESociedade Fabricadora de Elasto mero Ltda, Sa o Paulo, Brazil, supplied the TPU used [1,4-butanediol 15.3%,
poly(1,4-butylene adipate) 35.1%, and MDI 19.6%].
2.2. Sample preparation and characterization
Before processing the PVC, 4 parts of stabilizer were
added to 100 parts of PVC by using a Haake laboratory
twin screw extruder TW 100 Rheocord 9000. The composition of these blends is reported in Table 1. The thermal profile was 140150160170 C for all blends. The
screw speeds were 30, 60 and 100 rpm.
The mechanical tests were carried out by means of a

Stressstrain curves of PVC/DOP extruded at 30 rpm.

model 4204 Instron universal-testing machine. All

measurements were conducted using a crosshead speed
of 25 mm/min and a gauge length of 50 mm as indicated
in ASTM D882-96 [9]. The dumb-bell test specimens
were obtained from the extruded sheet.

3. Results and discussion

The stressstrain curves in tension of PVC/DOP
blends prepared at 30 rpm are shown in Fig. 1. These
results are typical for hard and brittle materials for blends
with 10 phr of DOP, soft and tough for mixtures with
50 and 90 phr. These profiles were the same for DIDP
blends extruded at this screw speed. Fig. 2 exhibits the
results obtained when the speed was changed to 100 rpm.
The mechanical tests profile show a hard and strong
characteristic for blends with 10 phr of low-molecularweight plasticizers, and present unchanged behaviour at
50 and 90 phr.
The stressstrain curves of PVC/TPU blends are

Table 1
Composition of investigated blend
Sample

Composition (phr)

PVC/DOP
PVC/DOP
PVC/DOP
PVC/DIDP
PVC/DIDP
PVC/DIDP
PVC/TPU
PVC/TPU
PVC/TPU
PVC/TPU

100/10
100/50
100/90
100/10
100/50
100/90
100/10
100/30
100/50
100/100
Fig. 2.

Stressstrain curves of PVC/DOP extruded at 100 rpm.

V.J.R.R. Pita et al. / Polymer Testing 21 (2002) 545550

Fig. 3.

Stressstrain curves of PVC/TPU extruded at 100 rpm.

shown in Fig. 3. PVC/TPU systems mixed at 10 phr TPU

showed a profile characteristic of hard and strong
material that becomes hard and tough at 30 and 50 phr
TPU. When the TPU content achieves 100 parts per hundred or resin the behaviour changes to soft and tough.
The curves obtained on changing the screw rotation
showed the same pattern as that depicted in Fig. 3. These
behaviours suggest a potential plasticizer effect of TPU
on this kind of blend.
Figs. 46 showed that Youngs modulus for
PVC/DOP, PVC/DIDP and PVC/TPU blends decreased
with the second component content. As expected, the
addition of low-molecular-weight plasticizer to a PVC
formulation decreases the modulus of the PVC product.
However, differences were noted between DOP and
DIDP blend behaviour. This suggests that the preparation
of the blend in a twin screw extruder at 30 rpm is not
affected by the molecular structure differences that exist
between DOP and DIDP.
Similarly, Youngs modulus for PVC/TPU systems
decreases. Values for Youngs modulus for the

Fig. 4. Dependence of Youngs modulus on second component content for blends with PVC, processed at 30 rpm.

547

Fig. 5. Dependence of Youngs modulus on second component content for blends with PVC, processed at 60 rpm.

Fig. 6. Dependence of Youngs modulus on second component content for blends with PVC, processed at 100 rpm.

PVC/TPU blends are shown in Figs. 46 as a function

of the TPU content at three different screw speeds. However, the profiles were slightly different, the decrease
was much slower and consequently the PVC loss property was also much slower. It seems that these profiles
are not influenced by the rotation speed of the screw. Of
course, some influences that are attributed to the high
molecular weight of TPU are expected on the mechanical
properties. When the molecular weight changes, some of
the properties also change; this is a function of the
increase in entanglement number. Therefore, it is clear
that PVC does not lower the modulus level in the same
way when mixed with TPU as it does by the addition
of low-molecular-weight plasticizers, but the plasticizer
effect of TPU can be observed.
Fig. 6 suggests that Youngs modulus of the PVC
blends was not significantly affected by the preparation
in a twin screw extruder at 100 rpm. The molecular
structure difference between DOP and DIDP does not
affect the blend modulus profile when extruded at this
screw speed.

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V.J.R.R. Pita et al. / Polymer Testing 21 (2002) 545550

Figs. 79 show the effects produced by TPU, DIDP

and DOP on the yield stress of the blends. It can be seen
that the low-molecular-weight plasticizer blends
presented the lowest yield value. This behaviour could
be explained by considering the concentration effect of

Fig. 7. Dependence of yield stress on second component content for blends with PVC, processed at 30 rpm.

Fig. 8. Dependence of yield stress on second component content for blends with PVC, processed at 60 rpm.

the second component on the blends. At low concentrations, the second component formed the dispersed
phase in a predominantly PVC continuous matrix. As the
mechanical properties of PVC were known to be dependent on the degree of dipolar interaction, any disruption
of this interaction would be harmful to the material property. The addition of DOP or DIDP, because of its
strong interaction with PVC, caused disruptions to the
PVC interchain attraction by acting as specific barriers
between PVC chains. This disruption caused the lowering of the mechanical properties in the blends. Hence,
when the DOP or DIDP content in the blend increased,
more disruption to the PVC interchain interactions
resulted, causing further reduction in the yield stress
value. The action of TPU is different. At low concentrations, the effect is very similar, but the addition of
TPU does not disrupt the PVC interchain contacts with
the same intensity, because its interchain interactions are
much stronger than the PVCTPU interactions. Obviously, the TPU chains form barriers between PVC
chains, but they maintain other kinds of links between
the chains, such as PVCTPU interactions and
entanglements. Hence, as the TPU content in the blend
increased, the level of disruptions to the PVC interchain
interaction was not the same, causing a much smaller
decrease in the modulus and yield stress values than with
DOP or DIDP.
Table 2 shows the influence of the additive content on
the toughness of the systems. At elongation of 300%, the
PVC/TPU toughness is higher than for PVC/DOP and
PVC/DIDP blends. These results confirm the different
kind of behaviour between the two types of systems. The
addition of TPU considerable improves the toughness of
PVC. The structural properties of these systems were
more efficiently maintained with the TPU addition, as
compared to DOP and DIDP. From the data it seems
likely that the toughness property is affected by the
screw speed.
Figs. 1012 present the elastic energy absorbed at
yield stress in the systems. Again, the constructive property of the PVC/TPU blends can be seen. The energy
absorbed up to the yield point by PVC/TPU is much
higher than that observed for the low-molecular-weight
plasticizer systems. Of course, if this energy is much
higher, the system needs a stronger network to produce
the effect. This suggests that this strong network is being
produced by the interactions between PVC/TPU, because
when the TPU content is higher than 50 phr the network
starts to disrupt and then collapses.

4. Conclusions

Fig. 9. Dependence of yield stress on second component content for blends with PVC, processed at 100 rpm.

The mechanical property profile of the systems studied

showed unexplored features of the mechanical behaviour
of the two types of materials added to PVC. The increase

V.J.R.R. Pita et al. / Polymer Testing 21 (2002) 545550

549

Table 2
Toughness of blends at 300%
System

Composition (phr)

Speed (rpm)

Toughness (J/m3)

PVC/DOP

100/90
100/90
100/90
100/90
100/100
100/100
100/100

30
100
30
100
30
60
100

10.7
11.8
15.7
14.1
25.7
42.9
34.3

PVC/DIDP
PVC/TPU

Fig. 10. Dependence of energy on second component content

for blends with PVC, processed at 30 rpm.

Fig. 11. Dependence of energy on second component content

for blends with PVC, processed at 60 rpm.

in plasticizer content in PVC compositions where the

plasticizer is a low-molecular-weight compound promotes a rapid modification of the PVC characteristics.
On the other hand, the increments of TPU content have
a smooth effect on the initial PVC properties, but do not

Fig. 12. Dependence of energy on second component content

for blends with PVC, processed at 100 rpm.

avoid the plasticization process. These facts suggest that

the structure of PVC/TPU mixtures could be maintained
more efficiently up to 50 phr TPU content. In general
terms, the PVC/TPU systems presented higher elastic
energy absorption. Therefore, small changes in the TPU
content could easily promote the desired properties for
selected applications. However, mixtures plasticized
with DOP and DIDP showed significant alteration on the
product property profile, even at low concentration
changes. The results also showed that the stressstrain
curves of PVC/TPU blends are not affected by changes
in the blend processing conditions. However, it is possible that the toughness data are affected by the screw
speed. The use of TPU as a plasticizer can also achieve
new horizons considering the large number of possibilities for variation in the polyurethane chain structure.

References
[1] Y.V. Ovchinnikov, B.Y. TetelBaum, A.J. Maklakov,
Effects of aging and temperature on changes in the states
of poly(vinylchloride)plasticizer systems, Vysokomol.
Soedin. Ser. A 13 (11) (1971) 24222428.

550

V.J.R.R. Pita et al. / Polymer Testing 21 (2002) 545550

[2] S. Parnell, G. Suppiah, M. Kyonsuku, in: Proceedings of

the 57th Annual Technical Conference (ANTEC/SPE)
Society of Plastic Engineers, Brookfield, 1999, pp. 3625
3629.
[3] J.J. Ziska, J.W. Barlow, D.R. Paul, Polymer 22 (1981) 919.
[4] J. Piglowski, W. Laskawski, Compatibility of poly(vinyl
chloride)/polyurethane blends, Angew. Makromol. Chem.
82 (1979) 157170.
[5] J. Piglowski, T. Skowronski, B. Masiulanis, Properties of
poly(vinyl chloride) modified with thermoplastic polyurethane elastomers, Angew. Makromol. Chem. 85 (1980)
129136.
[6] C. Lavalle e, M. Carmel, L.A. Utracki, J.L. Szabo, I.A.

Keough, B.D. Favis, Thermal and viscoelastic behavior of

polyurethane/polyvinylchloride blends, Polym. Eng. Sci. 32
(22) (1992) 17161726.
[7] Y.Q. Zhu, Y.J. Huang, Z.G. Chi, The compatibility of the
blends of PUs with PVC and the adhesion behavior of PU
to PVC, J. Appl. Polym. Sci. 56 (1995) 13711379.
[8] C.S. Ha, Y. Kim, W. Lee, W. Cho, Y. Kim, Fracture toughness and properties of plasticized PVC and thermoplastic
polyurethane blends, Polymer 39 (20) (1998) 47654772.
[9] ASTM Standard D 882standard test methods for tensile
properties of thin plastic sheeting. American Society for
Testing and Materials, 1994.