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Recycled poly(ethylene terephthalate) reinforced with basalt fibres: Rheology,

structure, and utility properties

Article in Polymer Composites · April 2008

DOI: 10.1002/pc.20425

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Recycled Poly(ethylene terephthalate) Reinforced With
Basalt Fibres: Rheology, Structure, and Utility Properties

Milan Kráčalı́k,1 Ladislav Pospı́šil,2 Miroslav Šlouf,3 Jana Mikešová,3 Antonı́n Sikora,3,4
Josef Šimonı́k,4 Ivan Fortelný3,4
1
Institute of Plastics Processing, University of Leoben, 8700 Leoben, Austria

2
Polymer Institute Brno Ltd., Tkalcovská 2, 656 49 Brno, Czech Republic

3
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic,
162 06 Prague, Czech Republic

4
Faculty of Technology, Tomas Bata University in Zlı́n, 762 72 Zlı́n, Czech Republic

Utilization of recycled poly(ethylene terephthalate) (PET) 20% in the United States only [1, 2]. Problems with PET
as a matrix for composite materials prepared by contin- recycling arise also from limited applications of recyclate
uous compounding is challenging from the environmen- (mostly staple fibers, packaging, films, and strapping bands)
tal as well as industrial point of view. In our work, cut ba-
salt fibers and talc powder of various compositions [3]. Up to now, glass fibers as a reinforcement of recycled
were used and their reinforcing effect on recycled PET PET have been studied [4–10]. However, some disadvan-
was tested by rheology (Advanced Rheometric Expan- tages associated with glass fibers limit their applications.
sion System), differential scanning calorimetry, and ten- For example, skin irritation avoids applications, in which
sile experiments. The quality of filler dispersion in released fibers might have contact with the human skin
recycled PET matrix was investigated by scanning elec-
tron microscopy (SEM) and melt rheology. Processing [11]. Moreover, basalt fibers form a better surface as com-
and utility properties of composites were enhanced as pared to glass fibers [12]. Concerning technological and ec-
compared with those of unfilled matrix. Higher melt elas- onomical evaluation, filling of basalt fibers affords rein-
ticity, interfacial adhesion, and better mechanical per- forcement within the range of glass and carbon filaments.
formance of the composites were in a good agreement High heat resistance, high stability in aggressive media,
with the structure observed from SEM micrographs.
POLYM. COMPOS., 29:437–442, 2008. ª 2008 Society of Plastics substantial sound absorption, and enormous physical dura-
Engineers bility of basalt fibers results in glass fiber replacement in
various industrial applications and hereby opens new fields
of application [13, 14]. Basalt fibers spun from melted ba-
salt stone possess a higher tensile modulus (at least 16%),
INTRODUCTION equivalent strength, and higher alkaline resistance [15]
The use of polymer materials has been increasing world- compared with glass fibers [16], enhanced interfacial adhe-
wide every year. Replacement of classical (metals, glass, sion [15] and are available commercially [17]. It is also use-
ceramics) materials by plastics requires a good recycling ful to mention, that basalt is the most current igneous rock
strategy. Poly(ethylene terephthalate) (PET) as the leading on the Earth. According to Czigány [18] the cheap basalt
synthetic polymer for beverage bottles production is fibers can be efficiently applied in hybrid composite sys-
recycled of 30% on average in the European Union and tems. He found out that basalt fiber hybridization of poly-
propylene-hemp fiber composites increased mechanical
properties only moderately while significant enhancement
Correspondence to: Milan Kráčalı́k; e-mail: [Link]@[Link] of PP-carbon fiber and PP-glass fiber systems with basalt
Contract grant sponsor: Ministry of Industry and Trade of the Czech fibers loading was reached. So far, no mention about
Republic; contract grant number: 1H-PK2/67; contract grant sponsor:
recycled PET-basalt fibres systems appeared in available
Polymer Institute Brno, Ltd., Brno, Czech Republic.
DOI 10.1002/pc.20425
literature. In this work, also relationship between melt rhe-
Published online in Wiley InterScience ([Link]). ology, structure, thermal, and mechanical characteristics of
C 2008 Society of Plastics Engineers
V composites containing recycled PET matrix is discussed.

POLYMER COMPOSITES—-2008
 TABLE 1. Specification of composites. diameter 15 mm) were supplied by the Polymer Institute Brno,
Ltd. To improve processing and utility properties (higher inter-
Composition (%) WPL 6938 WPL 6939 WPL 6941 WPL 6940
facial adhesion, dispersion, stability), Naintsch A-3 talc, Lico-
PET-R 78.8 68.8 68.8 58.8 wax OP flow modifier (1%), and Ultranox 626 antioxidant
Basalt fibers 20 30 20 30 (0.2%) were added before compounding (Table 1).
Talc 0 0 10 10

Preparation of Composites
The effect of talc admixture on basalt fibers-PET interfacial The recycled PET flakes were dried at 1208C in oven for
adhesion is investigated. From the industrial point of view, 6 h. The polymer was compounded with basalt fibers, talc,
the recycling of PET by continuous melt compounding flow modifier, and antioxidant in a corotating twin-screw
using good performance and low cost basalt fibers can be extruder (Werner & Pfleiderer ZSK 25, d ¼ 25 mm). The
interesting. compounding process proceeded at 260–2758C and the
screw speed about 200 rpm. Recycled PET composites
were injection-molded (injection moulding machine Batten-
EXPERIMENTAL PROCEDURES feld BA750/200) to specimens at 260–2758C, the mould
temperature ranged from 40 to 1208C.
Materials
Structure of Composites
Color-sorted recycled poly(ethylene terephthalate) (PET-
R), with the intrinsic viscosity 0.95 dl/g (phenol/tetrachloro- The scanning electron microscopy (SEM) measurements
ethane 1:3) as well as cut basalt fibers (average length 4 mm, were performed with a JEOL JSM 6400 scanning electron

FIG. 1. SEM micrographs of composites (dispersion).

438 POLYMER COMPOSITES—-2008 DOI 10.1002/pc

 FIG. 2. SEM micrographs of composites (interfacial adhesion).

microscope. The samples were fractured in liquid nitrogen Thermal Properties

and SEM microphotographs of surface area were obtained.
Thermal characterization of the polymer matrix and
Before experiments, the samples were sputtered with plati-
composites was carried out by differential scanning calo-
num using a vacuum sputter coater (SCD, Balzers). All
rimetry (Perkin Elmer, Pyris 1 DSC) using a standard
SEM pictures were secondary electron images taken at an
mode: 308C for 3 min, heating from 308C to 2808C at 108C/
acceleration voltage of 30 kV.
min, 2808C for 2 min. The thermal parameters, glass transi-
tion temperature (Tg), cold crystallization temperature (Tc),
Melt Rheology melting temperature (Tm), enthalpy of cold crystallization
(DHc), and enthalpy of melting (DHm) were calculated. The
Rheological properties were studied using an ARES 3 crystalline content (Xc) in composites was evaluated by
Rheometer (Advanced Rheometric Expanded System, Rheo- assuming the DHm for hypothetical 100% crystalline PET
metric Scientific, USA) with parallel-plate geometry of 25- to be 117.6 J/g [19].
mm diameter plates. All measurements were performed with
two automatically switched force transducers with a torque
range of 0.02 (2,000 gcm). The samples thickness ranged
Mechanical Testing
from 0.9 to 1.1 mm. Experiments were performed at 2708C
under nitrogen to prevent degradation of samples. The fol- Tensile properties were tested using an Instron 5800 R
lowing types of rheological measurements were carried out: instrument. Experiments were performed according to ISO
(1) dynamic strain sweep test (at 6.28 rad/s) to confirm the 527-2 standard. The crosshead speeds were for tensile mod-
linearity of viscoelastic region, (2) dynamic frequency sweep ulus measurements 1 mm/min and for all other characteris-
test over a frequency range of 0.1 (100 rad/s, at the strain 2% tics 50 mm/min. The toughness was measured according to
for the composites and 30% for the matrix. ČSN EN ISO 179-1 standard.

DOI 10.1002/pc POLYMER COMPOSITES—-2008 439

 FIG. 3. Dynamic flow curves of the matrix and composites. FIG. 4. Storage modulus of the matrix and composites.

RESULTS AND DISCUSSION further growth of melt viscosity, where the 30% addition
Two different concentrations of cut basalt fibers (20 and was concomitant with a high viscosity increase. The nearly
30%) and variations with and without talc as a coupling Newtonian behavior of all the composites and the matrix
agent have been chosen for this study. As the importance of would suggest that fillers particles are well incorporated in
processing parameters has been increasing in plastics indus- polymer structure. Usually, addition of a filler to polymer
try, rheological properties of composite melts were dis- melt shows the ‘‘yielding’’ phenomenon, described as vis-
cussed with the structure (analyzed from high magnification cosity increase in the range of low shear rates with subse-
SEM micrographs) and utility (thermal and mechanical) quent viscosity decline during a shear rate increase. The ab-
characteristics. sence of this behavior can be associated with high filler-ma-
Morphological analysis examined the level of dispersion trix interactions and high level of dispergation. This
and interfacial adhesion of basalt fibers in recycled PET conclusion is supported by Fig. 4, where the storage modu-
(Figs. 1 and 2). According to Fig. 1, all the composite sys- lus (elastic part of the complex viscosity) is plotted as a
tems exhibited a high level of dispersion and homogeneity function of the shear rate. The G0 secondary plateau,
of fiber distribution in polymer matrix. The difference in fil- observable for composites at low shear rates, is the indica-
ler concentration is also remarkable. Addition of talc into tion of strong filler-matrix interactions. Formation of this
the composites did not result in lower separation and clus- plateau is also associated with physical network between
tering of fibers. Furthermore, the presence of talc particles filler particles and polymer chains in a composite system
in composite system substantially facilitates fiber-matrix [20]. However, the composites described in this article did
adhesion, as shown in Fig. 2. The growth of filler content in not show the ‘‘yielding’’ effect; therefore, the mentioned G0
composite did not cause clustering of fibers and highly dis- plateau is reflecting rather high interfacial fiber-matrix ad-
persed structure was maintained. hesion.
In Fig. 2, interfacial adhesion of the filler to the matrix Concerning thermal properties (Table 2), the results of
can be observed. The composites containing only basalt differential scanning calorimetry revealed interesting ther-
fibers and PET matrix revealed poor fiber-matrix adhesion.
Addition of talc to the mixtures resulted in remarkable TABLE 2. Thermal properties of matrix and composites.
higher interfacial interactions, as indicated by cover of Tga Tmfb DHmfc Tmd DHme Xcf
fibers with the polymer. This structural change is reflected Composite (8C) (8C) (J/g) (8C) (J/g) (%)
in rheological, thermal, and mechanical properties
described later. The gap between the matrix and fiber in WPL 6938 74.3 171.7 2.9 252.0 35.0 29.8
WPL 6938 composite can be caused by displacement of WPL 6939 76.6 174.5 2.3 256.0 34.5 29.3
WPL 6941 75.9 168.7 2.2 252.9 32.6 27.7
some fibers applying impact forces during fracturing. How- WPL 6940 76.2 – – 252.5 25.3 21.5
ever, Fig. 1 shows most of the fibers tightly held by the ma- PET-R 75.6 – – 252.2 43.2 36.7
trix.
a
Dynamic rheological characteristics of the composites Glass transition temperature.
b
are in a good accordance with the observed structures. First melting point.
c
Enthalpy of first melting (first crystalline fraction).
From the flow curves (Fig. 3), the 20 and 30% additions of d
Melting point.
reinforcing fibers led to a considerable increase in complex e
Enthalpy of melting.
f
viscosity. Filling the systems with talc particles resulted in Relative crystalline content.

440 POLYMER COMPOSITES—-2008 DOI 10.1002/pc

 TABLE 3. Mechanical properties of composites.

Properties WPL 6938 WPL 6939 WPL 6941 WPL 6940

Tensile 95 112.9 100.7 122.8

strength (MPa)
Elongation at 2.9 2.9 2.1 2.2
break (%)
Tensile modulus 6,418 8,655 9,693 12,770
(MPa)
Flexural modulus 5,639 7,739 8,817 11,750
(MPa)
Impact strength 32.2 43.5 40.9 41.7
(kJ/m2)
Notch impact 5.7 8.1 5.4 5.7
strength (kJ/m2)

ity, while a remarkable difference in talc-enriched mixtures

FIG. 5. DSC characterization of composites filled with basalt fibers. was observed.
Mechanical properties of the composites are listed in
Table 3. The results of tensile, flexural, and impact tests are
modynamical behavior unusual for recycled PET-glass fiber
in good agreement with structural changes, as well as rheo-
composites or recycled PET-organoclay nanocomposites
logical and thermal behavior. Addition of talc and higher
[6, 20]. Composites WPL 6938, WPL 6939, and WPL 6941
concentration of basalt fibers in composites resulted in bet-
showed the first endothermic melting peak Tmf at about
ter mechanical performance, manifesting itself mostly by
1708C related to crystalline fraction on the surface of fibers
tensile strength, stiffness, flexural modulus, and toughness.
(Figs. 5 and 6). The composites without talc addition show
The values of extensibility were independent of talc and
a decrease in the first crystalline fraction (DHmf) with
fiber loading. The system filled with talc and 30% of fibers
higher fiber content. This behavior can be associated with
showed the highest reinforcement.
steric hindrance of fiber excess to the growth of crystalline
nuclei during heterogeneous crystallization. Can be also
observed in talc-containing systems, where the higher CONCLUSIONS
amount of fibers resulted in disappearance of the first melt- Highly dispersed uniform structures of short basalt fibers
ing peak (Fig. 6). Addition of talc to the 20% composite led in recycled PET were achieved by continuous compounding
to a remarkable decrease in the first crystalline fraction. The in a co-rotating twin-screw extruder. In the systems contain-
values of glass transition temperature and melt temperature ing talc, the recycled PET matrix adhered significantly more
were similar compared with the neat matrix. The level of to the surface of the reinforcing fibers. Their linear visco-
total crystallinity of composites was lower than that of the elastic properties reflected structural changes (variations of
unfilled matrix. Similarly to the first crystalline fraction, a basalt concentration and talc addition) in composites. Higher
higher content of fibers resulted in a lower total crystallin- values of the complex viscosity and storage modulus con-
firmed an increase in interfacial filler-matrix adhesion. Util-
ity properties of recycled PET were significantly enhanced
by the 20% and 30% filling with basalt fibers.

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