Introduction
Acrylonitrile–butadiene–styrene (ABS) is an impor-
tant engineering terpolymer. Due to its superior me-
chanical properties, chemical resistance, ease of pro-
cessing and recycling ability is widely used in the
industry. Those properties are directly related to the
polar nature of the acrylonitrile component. Typi-
cally, ABS consists of a styrene/acrylonitrile continu-
ous phase (SAN matrix) partially grafted to a dis-
persed butadiene phase, which acts as impact
modifier, giving excellent mechanical properties to
the polymer. ABS has various application, e.g. in ar-
chitecture and construction, personal care products,
toys, computer and business equipments, medical de-
vices and in automotive interior components. ABS is
also used with fiber-reinforcement to enhance the me-
chanical properties such as tensile strength, flexural
modulus and hardness [1, 2]. Another reason to use
ABS is its price that is between the lower priced
commodity thermoplastics and the more expensive
high performance engineering plastics [2].
Thermogravimetric analysis (TG) and differen-
tial thermal analysis (DTA) are commonly used meth-
ods to investigate the thermal stability of polymers
and composites [3]. With proper experimental proce-
dures, information on the degradation kinetics of de-
composition can be obtained. There are several re-
ports on the thermal analysis (TG, DTA, FTIR, DSC)
of ABS as well its individual components under vari-
ous conditions (purging gases, heating rates, etc.)
[3–15]. Degradation of ABS is a radical process
where end-chain and random scission occurs. Based
on different characterizing conditions the degradation
of ABS took place either in one step or two steps with
different kinetic parameters (degradation starting
temperature, ending temperature, peak temperature,
reaction order, pre-exponential factor and activation
energy) by assuming different kinetic models [14].
M. Yang [3] reported that the activation energy for
ABS is 175.8 kJ mol
–1
(using Flynn–Wall approach, dy-
namic method, 5, 10, 20 and 40°C min
–1
heating rates and
N
2
atmosphere) by using Freeman and Carroll isothermal
approach from 350 to 450°C in N
2
atmosphere, the acti-
vation energy is 134.0 kJ mol
–1
. A similar value was
found by S. Yang et al. [14], the activation energy
was 134.4 kJ mol
–1
, using also Freeman and Carroll ap-
proach, in an isothermal method at 370 to 560°C, while in
another work [15] at 10% conversion, N
2
atmosphere and
at 0.5, 1, 2, 5 and 10°C min
–1
heating rates, an activation
energy of 190.0 kJ mol
–1
was reported by Day [15]. Un-
der dynamic circumstances (nitrogen atmosphere and
heating rates between 5–30°C min
–1
) by assuming an
autocatalytic model [16] the activation energy is varied
between 140–160 kJ mol
–1
as determinate by Balart [16].
Experimental
The degradation process of three different commer-
cial ABS: GP, an ABS for general-purpose use; HI, an
ABS high impact; and HH, an ABS high heat resis-
tance was studied. The ABS samples were produced
by addition of styrene and acrylonitrile to poly-
butadiene latex; the resultant is a material with
polybutadiene grafted with acrylonitrile and styrene
(a SAN matrix) that is essential to obtain the required
properties of the desired polymer.
1388–6150/$20.00 Akadémiai Kiadó, Budapest, Hungary
© 2009 Akadémiai Kiadó, Budapest Springer, Dordrecht, The Netherlands
Journal of Thermal Analysis and Calorimetry, Vol. 95 (2009) 1, 131–134
DEGRADATION BEHAVIOR AND KINETIC STUDY OF ABS POLYMER
H. Polli
1*
, L. A. M. Pontes
1
, A. S. Araujo
2
, Joana M. F. Barros
2
and V. J. Fernandes Jr.
2
1
UNIFACS – Department of Chemical Engineering, Av. Cardeal da Silva, 132, 40.220-141 Salvador, BA, Brazil
2
Federal University of Rio Grande do Norte, Department of Chemistry, CP 1662, 59078-970 Natal, RN, Brazil
The degradation kinetics of the ABS terpolymer (acrylonitrile–butadiene–styrene) was investigated by means of thermogravimetric
analysis. The samples were heated from 30 to 900°C in nitrogen atmosphere applying three different heating rates: 5, 10
and 20°C min
–1
. The Vyazovkin model-free kinetic method was used to calculate the activation energy (E) of the degradation
process as a function of conversion and temperature. Between 20 and 80% of conversion, E was calculated and the figures were : for
ABS GP, E is 204.5±11.5 kJ mol
–1
(medium value); for ABS HI, E is 239.0±9.8 kJ mol
–1
; for ABS HH, E is 242.4±5.4 kJ mol
–1
.
Keywords: acrylonitrile–butadiene–styrene (ABS), model-free kinetics, thermal degradation, thermogravimetry
* Author for correspondence: polli@unifacs.br