Use of Pyrolysed Oil Shale as Filler in Poly(ethylene-co-
vinyl Alcohol)
Ronilson Vasconcelos Barbosa, Ricardo Baumhardt-Neto, Raquel Santos Mauler, Carlos José,
Perez Gorga, Cla ´udia Gazzana Schneider
Instituto de Quı ´mica, Universidade Federal do Rio Grande do Sul, Departamento de Quı ´mica Orga ˆnica, Avenida Bento
Gonc ¸alves, 9500, Porto Alegre, Rio Grande do Sul, Caixa Postal 15003, CEP 91501–970, Brazil
Received 23 June 2003; accepted 27 October 2003
ABSTRACT: The pyrolysed oil shale (POS) obtained from
the pyrolysis of bituminous rock was used as filler in poly-
(ethylene-co-vinyl alcohol) (EVAL). The effects of vinyl al-
cohol content in the EVAL and the particle size of pyrolysed
oil shale in the mechanical properties were investigated. The
EVAL was prepared by hydrolysis of poly(ethylene-co-vinyl
acetate) (EVA) with 8 and 18 wt % of vinyl alcohol content.
The composites were prepared in a rotor mixer at 180°C
with concentration of pyrolysed oil shale up to 5 wt %.
Stress–strain plots of compression-molded composites
showed a synergic behavior in the mechanical properties for
low concentrations (1–5 wt %) of POS in all particle sizes and
EVAL used. Such behavior indicates a close packing and
strong interactions between the inorganic filler and the poly-
mer. Increasing of the vinyl alcohol content of EVAL im-
proved the compatibility between the polymer and filler, but
decreasing the POS particle size had no effect on the
properties. The modulus and the ultimate tensile strength
also increased in all concentrations of POS for both EVAL.
Mechanical properties and dynamic mechanical analysis
also demonstrated the compatibility between EVAL and
POS. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1658 –1665,
2004
Key words: composites; fillers; mechanical properties
INTRODUCTION
Pyrolysed oil shale (POS) is an inorganic material that
originates from the oil extraction of bituminous rock,
through pyrolysis at approximately 400°C. POS, with
low oil concentration (between 12% wt), goes back to
the mines after extraction, increasing production costs
and requiring appropriate environmental control.
During the pyrolysis process the organic material con-
tained in the rock is transformed into oil and gas, and
another part produces a coke that is retained in the
mineral matrix. POS is a black mineral consisting of a
consolidated organic–inorganic mixture with most of
the inorganic part constituted of silicates. Many of the
mineral fillers currently being used in plastics, such as
clay, mica, and talc, also consist of silicate.
1
The use of
mineral as fillers in polymeric materials is an eco-
nomic practice in the polymer industry today. Most
mineral fillers are used in industry to reduce produc-
tion costs; among them the most important are alu-
mina, calcium carbonate, talc, clay, and others. The
use of POS as filler in polymer materials is new and
few works referring to the subject are found in the
specialized literature.
1
According to the literature, the
objective of blending oil shale with polymer is to
promote the decomposition of the oil shale in the
pyrolysis process.
2,3
In previous work we showed the role of surface
organic compounds on pyrolysed oil shale in promot-
ing a better dispersion between high-density polyeth-
ylene (HDPE) andPOS.
4
These interactions are also
responsible for better phase dispersion and the lost of
ultimate tensile strength and elongation at break with
the decrease of particle size of pyrolysed oil shale.
4,5
The results of mechanical properties of poly(ethylene-
co-vinyl acetate) (EVA)-8/POS and EVA-18/POS
showed that three factors were related to the mechan-
ical properties of the mixtures of polymer/POS: (a)
POS particle size: the smaller the particle size, the
better the mechanical properties of the composites
compared to the pure polymer. This behavior may be
explained by the best dispersion of the particle in the
polymer matrix; (b) concentration of POS: the amount
of POS or any other filler is very important for the
mechanical properties. The increase of filler content
tends to determine losses in the mechanical properties,
mainly when the interface polymer/filler shows poor
dispersion; (c) the polarity of the polymer: when the
polymer polarity (vinyl alcohol (VA) content) was
increased, the mechanical properties remained almost
the same at higher filler content compared with the
pure polymer.
Correspondence to: R. V. Barbosa (Ronilson@iq.ufrgs.br).
Contract grant sponsor: CNPq, FAPERGS, ANP/CTPE-
TRO, and TECPOL-Tecnologia em Polı ´meros.
Journal of Applied Polymer Science, Vol. 92, 1658 –1665 (2004)
© 2004 Wiley Periodicals, Inc.