Journal of Materials Processing Technology 162163 (2005) 9095

The influence of extrusion variables on the interfacial

adhesion and mechanical properties of recycled
PET composites
A.L.F. de Moura Giraldi, R. Cardoso de Jesus, L.H. Innocentini Mei
Department of Polymer Technology, College of Chemical Engineering, State University of Campinas,
P.O. Box 6066, 13081-970 Campinas, SP, Brazil

Abstract
The interfacial adhesion and mechanical properties of injection-molded recycled poly(ethylene terephthalate) with glass fibre has been
studied as a function of two variables involved in the extrusion process: screw speed and screw torque. The composites properties studied
included DMTA, flexural strength, Youngs modulus and impact strength. The Youngs modulus and impact resistance of the composites
increased with the addition of glass fibre in recycled PET matrix. A factorial experimental design (FED), based on the screw speed and
torque of the double screw extruder used, was done to get the best thermo-mechanical properties versus processing conditions. Screw speed
at the high level (200 rpm) was significant to increase Youngs modulus. It was shown that screw torque on its high level (60%) was the
significant factor to increase Impact strength of these composites. The results of these preliminary studies showed clearly the positive effect
on the interfacial adhesion between matrix-fibre for some processing condition and also showed the best mechanical properties.
2005 Elsevier B.V. All rights reserved.
Keywords: Processing; Adhesion; Glass fibre; Recycled PET

1. Introduction
The problem of polymeric waste recycling is not solved on
satisfactory level yet. Usually, only 30% of polymeric waste is
recycled. Recently environmental, legislative and consumer
pressures have led to an increase of interest in polymers
reuse [1]. One of the reasonable ways to treat the waste from
commodity polymers, such as polyolefines (HDPE, LDPE,
LLDPE, PP) or poly(ethylene terephthalate) (PET), is the
material recycling, mainly from industrial scraps, which are
relatively easy to deal because their contamination is usually
negligible.
The potential application of recycled polymers is often
limited by their poor properties. One of the most important
question for recycled materials is to find a new application.
Efforts to recycle plastics are mostly concentrated on sorting,
separation and reprocessing of a single polymeric material

Corresponding author. Tel.: +55 19 378 839 35; fax: +55 19 378 83 938.
URL: lumei@feq.unicamp.br (L.H.I. Mei).
0924-0136/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2005.02.046

[2], being recycled PET one of the most explored for new
applications.
Poly(ethylene terephthalate) is a very important polymer
for industrial applications, particularly PET fibres that account for ca. 70% of all synthetic fibres, which are employed in tire cords, composites, belts, and textiles. The postconsumer poly(ethylene terephthalate) material of soft drink
bottles, approaching 5 million tons/year worldwidecannot
be used again for the same purpose. This is banned not
only by the hygienic requirements, regulated by consumer
protecting acts, but also because of the substantial degradation in molecular structure. This degradation is reflected in
a reduction of the melt viscosity and mechanical strength
[3,4].
However, the flammability of PET limits to a certain extent
its wide possibility of applications [5]. Semicrystalline PET
also presents good thermal and mechanical properties, such as
high melting temperature (ca. 250 C), and is also used a reinforced plastics [6]. De Paoli and Spinace showed that the mechanical properties and crystallinity degree of PET changed

A.L.F. de Moura Giraldi et al. / Journal of Materials Processing Technology 162163 (2005) 9095

drastically after several reprocessing cycles. An increase in

the melt flow index and carboxylic groups concentration indicated certain degree of mechanochemical degradation [7].
Virgin PET exhibited a ductile behaviour (>200% of elongation at break), whereas post-consumer PET bottles exhibited a brittle one (<10% of elongation at break), as shown by
Zanin and Mancini [8]. This was attributed to the difference
in crystallinity caused by the presence of impurities in the recycled PET and the different thermal and mechanical history
of the virgin and recycled materials. Other papers discuss that
the number of carboxyl end groups increased by three times
after five recycling steps PET recycling by injection and the
crystallinity was enhanced, going from 23 to 37%, which explains the alterations in the elasticity modulus, elongation at
break and impact resistance [9].
Following the technological development, the industry is
searching for materials with better strength to weight ratio,
higher stiffness, and faster productivity to meet the demands
of structure design and economic benefit. Among them, plastic material is the one that cannot be ignored. To extend
their area of application, reinforced plastics are being developed by adding glass fibre as one of the best options [10]
to get a thermoplastic composite with good mechanochemical and thermal properties. In this field, the recycled PET
reinforced composites is being an interesting option to be
explored.
Since composite materials are increasingly replacing
metallic materials in mechanical structures, their dynamic,
thermal and static characteristics should be considered. Specially, the impact and tensile behaviours of composites are
very important if the composite is to be employed in automobile or train structures [11,12]. Many studies dealing with this
subject have been reported in short-fibre reinforced engineering plastics, such as poly(ethylene terephthalate) [1315],
polycarbonate [16] and polyamides [17,18].
Few papers show the importance of processing variables on mechanical properties of reinforced thermoplastics. Kim et al. [19] studied the effect of the morphology and mechanical properties of injection molded articles
made of poly(butylene terephthalate) (PBT) and glass fibrereinforced. Velasco and Arencon [20] correlated microstructure, mechanical properties and processing conditions of
short glass fibre reinforced PET composites for injection considering three variables: mold temperature, holding pressure
time and closed mold time.
The main purposes of the present study are as follows: (1)
use the software Statgraphics 2.0 program to determine the
significant factors and levels, with 95% of confidence, for the
factorial experimental design (FED) in the extrusion process
of PET + glass fibre composites, to find the optimal processing condition versus mechanical properties. (2) Utilize the
dynamic mechanical thermal analysis (DMTA) to characterize the thermomechanical behaviour of fibre reinforced recycled PET and estimate the interfacial adhesion between the
glass fibre and the polymeric matrix, according the method
of Kubat et al. [21].

91

2. Experimental
2.1. Materials and processing
A commercial grade (PC 70) of recycled PET manufactured by Recipet (M&G) has been employed. The E grade
chopped glass fibre (GF) used was pricked 183 F, supplied
by Owens Corning, having an initial length of 4,5 mm, diameter of 11 m and silane treated, recommended for polyester
resins. 0.5 wt.% antioxidant (Irganox B 900) has been incorporated to the composites.
In order to avoid as much as possible the degradative effect
of hydrolysis caused by moisture, pellets of recycled PET
were dried at 130 C for 6 h. The glass fibre 30 wt.% was
used as reinforcing agents.
Recycled PET, antioxidant and glass fibre were mixed in
a Theysohn twin-screw extruder, with L/D ratio equal to 40.
The process was carried out with the following temperature
profile: 260, 270, 270, 280, and 290 C. A factorial experimental design 22 + 1 was used for the processing variables:
screw speed (100 and 200 rpm) and screw torque (40 and
60%), as shown in Table 1. The central point was settled between the intermediate levels of these factors. The processing
conditions for recycled PET without glass fibre (GF) were
fixed at 200 rpm and torque of 60% (Table 1, experiment 4).
The pellets produced were used for feeding an Arburg
injection molding machine, model 320 K. The basic process
parameters were: melt temperature of 270 C and cooling
time of 4050 s) to obtain specimens tests. The impact tests
were performed according to ASTM D 256-93a, method E.
Tensile tests were conducted according to ASTM D 638-95,
specimen dimension type I.
2.2. Sample characterization
DMTA measurements were performed in a DMA
2980TA Instruments at a frequency of 1 Hz and a heating
rate of 2 C min1 by flexion mode. The temperature range
of measurements was from 150 to 200 C. These analysis
were used to evaluated the interactions between the matrix
and fibre, according to the method detailed for Kubat et al.
[21].
The impact resistance tests were performed with notched
specimens, according to ASTM D 256 (Charpy method), using a Custom Scientific Instruments. The modulus of elasticity and the strain at break were determined using a Tensile
Tester Machine; model TestStar I, according to ASTM D 638.
Table 1
Processing conditions of recycled PET/glass fibre composites
PET recycled + glass
fibre (30%)
Rotation (rpm)
Torque (%)

Processing conditions
1

100
40

100
60

200
40

200
60

150
50

92

A.L.F. de Moura Giraldi et al. / Journal of Materials Processing Technology 162163 (2005) 9095

The composites incineration was done using extra specimens for tensile-strain tests to obtain the fibre volume fractions. To take information about the fibre average length in
the composites, an overall fibre length distribution was determined for each composite after extrusion and granulation
process. The fibres were separated from the PET composites
by dissolving the granules in a solvent mixture of phenol and
1,1,2,2-tetrachlorethane (6:4 wt.%) followed by filtration of
the solution. Then, they were scattered over a glass plate, photographed with a Leica optical microscope and the average
length evaluated using a software program Image Pro-Plus
3.0.
Fig. 1. Fibre length distribution data for condition 5 (PET + GF).

Em (1 + )
1

3. Results and discussion

Ec =

3.1. Effects of the processing variables on mechanical

properties

In the above equations, Ec , Ef and Em are the elastic modulus

of the composite, fibre and matrix, respectively, whereas l
and o are the efficiency factors of fibre length and orientation, respectively. The first factor (l ), has been calculated
using Eq. (3) that follows [23]:

As expected, Youngs modulus values increased after the

addition of glass fibres. Values of the tensile and impact
strength characteristics are summarized in Table 2.
The analysis of variance ANOVA was used (software Statgraphics 2.0) to determine the significant factors and levels,
with 95% of confidence, for the factorial experimental design
in the extrusion process of PET glass fibre reinforced composites (see Table 1). It was shown that screw torque on its high
level (60%) was the significant factor to increase the Impact
strength of these composites. While screw speed was the
significant factor on its high level (200 rpm) to increase the
Youngs modulus. Factors interaction between screw speed
and screw torque was significant for the Youngs modulus,
decreasing it, but no interaction factor was found for the Impact strength.
This divergent behaviour of the processing variables,
screw speed and torque, on the mechanical properties is still
being analysed considering shearing effects of the twin screw
extruder in the mixing zone (kneading discs).
The theoretical Eq. (1) and the Halpin and Pagano [22] Eq.
(2) were used to predict the Youngs modulus of the studied
composites.

Ec = l o Ef + Em (1 )

(1)

l = 1

(2)

tan h(1/2)l
(1/2)l

(3)

where is given by Eq. (4):

1/2
2Gm
=
Ef r 2 ln(R/r)

(4)

Gm is the matrix shear modulus (1.12 GPa), r the fibre radius

and R is the half spacing between fibres [24]. In the Halpin
equation, is the fibre aspect ratio (l/r) and is defined by
Eq. (5) as:
=

(Ef /Em )l
(Ef /Em ) +

(5)

All studied composites showed similar fibre length distribution patterns (Fig. 1). Although some fibre degradation
is expected to occur during the injection process, the main
cause of fibre breakage was found in the compounding process, since the fibre passed through kneading blocks into the
extruder, causing its milling. This was the reason to follow
this study focusing on the influence of extrusion variables on
the mechanical properties of glass fibre recycled PET composites.

Table 2
Average values (standard deviations) for mechanical properties of recycled PET and its glass fibre (FG) composites
Sample
Composites of recycled PET + 30% FG

Recycled PET
Recycled and processed PET

1
2
3
4
5

Impact strength (J/m)

Tensile strength (MPa)

Strain at break (%)

Youngs modulus (GPa)

83.1 (7.2)
76.9 (2.9)
104.2 (10.7)
108.9 (10.3)
107.9 (12.1)

87 (1.1)
98 (1.6)
113 (0.7)
103 (0.7)
83 (0.9)

3.7 (0.2)
3.5 (0.3)
3.3 (0.3)
3.4 (0.4)
3.4 (0.4)

7.8 (0.5)
8.1 (0.9)
9.2 (0.9)
8.3 (0.5)
6.1 (0.7)

63.7 (13.1)
75.9 (20.9)

60 (2.3)
58 (2.2)

>120
>122

2.8 (0.4)
2.6 (0.3)

A.L.F. de Moura Giraldi et al. / Journal of Materials Processing Technology 162163 (2005) 9095

93

Fig. 2. Theoretical predictions and experimental values for Youngs modulus

of recycled PET reinforced glass fibre composites.

The fibre length, as supplied, was around 4.5 mm, giving a L/D ratio around 400, whereas after the extrusion and
granulation processes, the fibre size found had no more than
1 mm length (L/D 90). The experimental condition 3 for
the extrusion process (200 rpm and 40% torque) presented the
higher amount (12%) of small fibres, below 0.1 mm length.
As shown in Fig. 2, the experimental values of Youngs
modulus for recycled PET reinforced glass fibre composites
didnt match very well to the values given by Halpin model,
who does not consider the full parallel alignment of the fibres
through the axial direction of the specimen.
As expected, the tensile strength for recycled PET glass
fibre reinforced composites increased with the fibre addition
(Table 3). An estimation of the fibrematrix interfacial shear
strength () could be done by fitting the measured c values
according to the theoretical equation for the tensile strength
of unidirectional fibre composites with fibre length shorter
than the critical length, through Eq. (6):
 
1
c =
(6)
+ m (1 )
d
In the above equation ( c ) and ( m ) are the tensile strength
of the composite and matrix, respectively, l the fibre length
and d is the fibre diameter. As shown in Table 3, an average value close to 96 MPa was obtained, indicating a good
level of adhesion between both matrix and fibres. This result
suggests that the aminosilane-coupling agent used to modify the glass fibres surface probably reacted with the acid
groups of poly(ethylene terephthalate) matrix, improving the
properties of the composites. It was noted that conditions 3
and 4 (Table 3) presented a significant increase compared to
the conditions 1, 2 and 5. An explanation of this could be a
higher fibre volumetric fraction found for this composite in
the calcinations tests.

Fig. 3. Storage modulus, loss modulus and tan for recycled PET.

3.2. Inluence of processing variables in the thermal

dynamic-mechanical properties
DMTA results, in Fig. 3, show the storage and loss modulus, and tan for recycled PET. It can be seen that around
70 C there is peak relative to transition. Foreman and
Blaine [26] showed a beta transition at around 75 C in
their studies with PET film. Illers and Breuer [27] suggested
that the peak around 70 C was assigned to the motions of
carbonyl groups in trans conformation.
More recently, NMR results obtained by English [28]
showed that the molecular motions in PET below the relaxation should be attributed to the motions of phenyl rings.
These works were followed by the studies of Maxwell et
al., carried out by NMR, dynamic mechanical and dielectric
investigations [29]. These authors concluded that the relaxation peak consists on two different relaxation processes:
one the high temperature side of the mechanical peak and
one on the low temperature side of the peak. A detailed examination of the peak suggests that the high temperature
side of the peak is probably due to motion of the phenyl rings,
whereas the low temperature side of the peak appears to be
due to carbonyl relaxations.
Kubat [21] showed that the effect of the interphase region
on the dynamic properties can be quantified in a direct way. As
a first approximation, it can be assumed that the mechanical
loss factor tan c of the composite can be writen as show Eq.

Table 3
Samples composition, average fiber length and tensile strength of the studied composites
Sample
Composites of recycled PET + 30% FG

Recycled PET
Recycled and processed PET

1
2
3
4
5

Fiber volume fraction (%)

Average fiber length (mm)

a (MPa)

17.5
18.1
19.1
18.3
17.7

0.23
0.25
0.28
0.26
0.21

86
97
112
102
82

94

A.L.F. de Moura Giraldi et al. / Journal of Materials Processing Technology 162163 (2005) 9095

(7):

4. Conclusions

tan c = vi tan f + vi tan i + vm tan m

(7)

where the subscripts f, i, and m denote fibre, interphase, and

matrix, respectively, and v is the corresponding volume fraction. It is quite obvious that Eq. (7) does not provide a detailed prediction of the mechanical loss factor of the composite since it involves a combination of series and parallel
coupling of the phases. Nevertheless, it will be used as a starting point, as outlined below, when aiming at comparing the
effect of different surface treatments on the state of adhesion
between the phases. Assuming that tan i
= 0 and that the volume fraction of the interphase is rather small, Eq. (7) can be
rearranged to give
tan c
= (1 vi )(1 + A)
tan m

(8)

with
A=

vi tan i
1 vi tan m

(9)

Strong interactions between the fibre and the matrix at

the interface tend to reduce the macromolecular mobility in
the vicinity of the fibre surface compared to that in the bulk
matrix. This reduces tan i and thus A. A low value of A thus
indicates a high degree of interaction or adhesion between
the phases.
Fig. 4 shows how the factor A varies with the temperature
for each processing condition for the recycled PET composite. The A values for conditions 35 stay almost similar between temperatures 70 at 110 C. This indicate that adhesion
between the two phases is better for this range of temperature. This is in contrast with the behaviour observed when
no covalent bonding exists between the recycled PET matrix
and the fibre. It is observed that the factor A increases above
the temperature of 115 C, which indicates a deterioration in
the adhesion degree.

Fig. 4. The parameter A from Eq. (9) relative to the processing conditions
of recycled PET composites as a function of temperature.

Glass fibre reinforced poly(ethylene terephthalate) with

30% by weight were prepared and characterized both thermally, mechanically and by thermal dynamic-mechanical. A
factorial experimental design was used to study the effect of
processing variables of a twin-screw extruder (screw speed
and torque) in the compounding of a recycled PET fibre glass
reinforced on the mechanical and thermal properties. The following conclusions can be made:
The Youngs modulus and the tensile strength of the composites were determined and analyzed by comparison with
theoretical values. These two parameters increased with addition of glass fibre. Screw speed at a level of 200 rpm and
torque at a level of 60% were significant to increase Youngs
modulus and Impact strength. Youngs modulus values for
the composites didnt match quite well a with theoretical
prediction, which assumes full fibre alignment in the tensile
direction.
The processing conditions 3 and 4 of recycled PET composites indicated a good level of adhesion between matrix
and fibres, evaluated by the tensile strength (). Measurements of the effect of temperature and adhesion factor A
through DMTA analysis showed that: (i) above the temperature of 115 C, the factors A increased for all conditions,
which indicates a deterioration of the adhesion degree between fibre and matrix; (ii) between the temperature range
of 70110 C, the A values of conditions 35 were almost
similar.

Acknowledgment
Authors thank to Ministerio de Ciencia e Tecnologa,
CNPq (Government of Brazil) for financial support.

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