Effect of Zeolite Filler on the Thermal Degradation
Kinetics of Polypropylene
H. Pehlivan, D. Balko ¨se, S. U
¨
lku ¨ , F. Tıhmınlıog ˘lu
Chemical Engineering Department, I
˙
zmir Institute of Technology, Urla, I
˙
zmir, Turkey, 35430
Received 18 November 2004; accepted 15 June 2005
DOI 10.1002/app.23105
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: In this study, the thermal degradation be-
havior of polypropylene (PP) and PP–zeolite composites
was investigated. Clinoptilolite, a natural zeolitic tuff, was
used as the filler material in composites. The effects of both
pure clinoptilolite and silver-ion-exchanged clinoptilolite on
the thermal degradation kinetics of the PP composites was
studied with differential scanning calorimetry (DSC) and
thermogravimetric analysis (TGA). Polymer degradation
was evaluated with DSC at heating rates of 5, 10, and 20°C/
min from room temperature to 500°C. The silver concentra-
tion (4.36, 27.85, and 183.8 mg of Ag/g of zeolite) was the
selected parameter under consideration. From the DSC
curves, we observed that the heat of degradation values of
the composites containing 2– 6% silver-exchanged zeolite
(321–390 kJ/kg) were larger than that of the pure PP (258
kJ/kg). From the DSC results, we confirmed that the PP–
zeolite composites can be used at higher temperatures than
the pure PP polymer because of its higher thermal stability.
The thermal decomposition activation energies of the com-
posites were calculated with both the Kissinger and Ozawa
models. The values predicted from these two equations were
in close agreement. From the TGA curves, we found that
zeolite addition into the PP matrix slowed the decomposi-
tion reaction; however, silver-exchanged zeolite addition
into the matrix accelerated the reaction. The higher the silver
concentration was, the lower were the thermal decomposi-
tion activation energies we obtained. As a result, PP was
much more susceptible to thermal decomposition in the
presence of silver-exchanged zeolite. © 2006 Wiley Periodicals,
Inc. J Appl Polym Sci 101: 143–148, 2006
Key words: composites; degradation; kinetics (polym.);
poly(propylene) (PP); zeolites
INTRODUCTION
Composites with desired properties can be achieved
by the incorporation of fillers into a polymer matrix to
suit various applications. Glass fibers, carbon fibers,
and particulate fillers can be used as reinforcing ma-
terials. The primary advantages of polymeric compos-
ites are increases in stiffness, strength, and dimen-
sional stability; reduced permeability to gases and
liquids; and reduced cost. Polypropylene (PP) is
among the most widely exploited thermoplastic poly-
mers and is of increasing practical importance because
of its good comprehensive use, light weight (0.9 g/cc),
chemical resistance, low cost, ease of processing, and
good recycling properties. It has various applications,
including food packaging, medical delivery systems,
carpets, fibers, protective coatings, and applications in
the automobile, electrical, and furniture industries,
depending on these properties. The properties of the
composite materials are affected by the chemical prop-
erties of the components and the nature of the inter-
action between the phases.
1
Different types of zeolite minerals, either natural
(e.g., clinoptilolite, mordenite, chabazite) or syn-
thetic (e.g., A type, X type, Y type), have been used
as particulate fillers.
2–4
All commercial zeolites owe
their value to one of the following properties: ion
exchange, adsorption, or catalysis. They have un-
usual crystalline structures that give them unique
chemical properties. For instance, in 1 g of natural
zeolite, channels can provide up to several hun-
dreds of square meters of surface area on which
chemical reactions can take place. Natural zeolite
can also absorb up to 30% of its dry weight in gases,
such as nitrogen or ammonia.
Studies have reported on the removal of lead, silver,
and cadmium by clinoptilolite in the presence of com-
peting concentrations of calcium, magnesium, and so-
dium via ion-exchange processes.
5
Silver zeolites are
of great importance because of their potential uses as
germicidal, bactericidal, antifungal, and antiseptic
components in different compositions.
6–8
Silver salts
appear to meet the requirements to as antiseptic
agents. The modification of an inorganic compound
by the addition of silver is attractive because silver
Correspondence to: F. Tıhmınlıog ˘ lu (fundatihminlioglu@iyte.
edu.tr).
Contract grant sponsor: Technical and Scientific Research
Council of Turkey; contract grant number: MI
˙
SAG 129.
Contract grant sponsor: Government Planning Institute;
contract grant number: 120290 K.
Journal of Applied Polymer Science, Vol. 101, 143–148 (2006)
© 2006 Wiley Periodicals, Inc.