Polymer Degradation and Stability 91 (2006) 2396e2407

www.elsevier.com/locate/polydegstab

Recyclability of a layered silicateethermoplastic olefin elastomer

nanocomposite
M.R. Thompson*, K.K. Yeung
MMRI/CAPPA-D, Department of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4L7
Received 5 December 2005; received in revised form 27 March 2006; accepted 30 March 2006
Available online 12 May 2006

Abstract

A multiple-pass study was undertaken with a layered silicateethermoplastic olefin elastomer (TPO) nanocomposite to study the impact of
processing history on the properties of the material. A set of 10 passes were completed through a co-rotating intermeshing twin-screw extruder
with samples collected to monitor changes in the composite. The microstructure of the nanocomposite was characterized using TEM, XRD, FT-
IR, steady and complex shear rheology, and mechanical testing. With progressive passes through the extruder, the TPO nanocomposite expe-
rienced both delamination of the organoclay as well as thermo-oxidative degradation. The onset and extent of degradation were found to be
unaffected by the presence of the organoclay species in the polymer, though, inclusion of a maleated compatibilizer led to increased chain scis-
sion. The generated carbonyl groups along the polymer chain as a result of oxidation were speculated to have a significant effect on the devel-
oping percolating network of clay within the material and on the final rheological properties of the composite. Despite the occurrence of
degradation in the nanocomposite during recycling, its rheological and mechanical properties remained significantly higher than those of the
unfilled resin.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Thermo-oxidative degradation; Nanocomposite; Recyclability; Organoclay

1. Introduction part, yet additionally, increases weight which is typically

One polymer family of growing interest to the automotive
industry are thermoplastic olefin elastomers (TPOs) which
are based on polypropylene and an elastomeric resin such as
ethyleneepropyleneediene terpolymer (EPDM), ethylenee
propylene rubber (EPR), or an ethyleneea-olefin metallocene
copolymer. Both compounded and reactor grades exist for
TPO materials. Variation of the rubber content with respect
to the polypropylene as well as the addition of fillers and pro-
cess additives gives end-users the ability to target use of the
TPO to different interior and exterior applications throughout
the vehicle. The use of fillers in a TPO, such as talc, increases
the mechanical properties and scratch resistance of the molded
* Corresponding author. Tel.: þ1 905 525 9140x23213; fax: þ1 905 521
1350.
E-mail address: mthomps@mcmaster.ca (M.R. Thompson).
considered a negative factor in automotive design. Polymer-
layered silicate (PLS) nanocomposites are an emerging class
of polymers requiring considerably less filler content to
achieve similar or improved mechanical properties [1e7].
The layered silicate most commonly chosen for these compos-
ites is montmorillonite, a clay mineral comprised of layered
silicate sheets. The surface chemistry of the montmorillonite
is altered with an organic surfactant, to increase its hydropho-
bicity and allow for improved interactions with polymer
species. The critical issue to the manufacture of nanocompo-
sites is the in situ generation of individual nanometer-scale
silicate sheets (platelets) within the polymer matrix through
a process of intercalation and delamination. Effectively, the
original organoclay particles must be broken down to primary
particles, and polymer chains be allowed to enter and expand
the clay galleries leading to ultimate dissociation of the indi-
vidual silicate sheets [1e3,8,9]. The nanometer-scale dimen-
sion of the exfoliated filler avoids the presence of stress

0141-3910/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2006.03.013
 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
concentrators in the matrix which are regions prone to me-
chanical failure with conventional fillers. Despite the advanta-
geous properties of these new polymers, they remain difficult
to synthesize due to the suspected importance of diffusion-
limited intercalation of polymer chains into the confined
regions within the layered silicate structure [10e12]. It is
the unique nature by which PLS nanocomposites are generated
that also complicates issues of recycling of this material
whether its source comes from post-consumer plastics or pro-
duction scrap. Knowledge of microstructural changes arising
from re-processing of a PLS nanocomposite is important for
evaluating the economical and potential environmental impact
for this relatively new class of material. This paper will limit
its scope of investigation to that of recycling production scrap
by examining the morphological response of a TPO nanocom-
posite subjected to multiple deformation/thermal histories.
Prior studies [3,5,6,13e20] regarding the morphology and
properties of PLS nanocomposites derived from a polyolefin
matrix, namely polyethylene and polypropylene, have high-
lighted the difficulties with non-polar polymers producing
exfoliated structures. The mechanism of intercalation neces-
sary for exfoliation to occur is a diffusion-dependent process
reliant on residence time and the interactions between polymer
and clay to overcome the subsequent entropic penalty resulting
from confinement of the intercalant [10e12,21]. To overcome
the unfavorable approach of non-polar polymers into the gal-
leries of the polar organophilic-coated montmorillonite, a poly-
meric compatibilizer must be introduced in a small quantity
sufficient to improve interactions with the silicate surface
yet remain miscible with the matrix [3,17]. The combination
of an organoclay and polymer compatibilizer has been suffi-
cient to generate partial intercalated/exfoliated structures for
polyolefin-based nanocomposites yet the mechanism of inter-
calation remains hindered. The repercussions of hindered in-
tercalation among non-polar resins such as TPO mean that
under subsequent processing histories, as would be expected
from recycling, there remains the high likelihood of further in-
tercalation/exfoliation. Effectively, repeated recycling of such
materials can be likened to annealing of the nanocomposite in
the presence of shear. Mechanical and rheological properties
would be expected to shift accordingly with changes in the
extent of intercalation/exfoliation. In addition to changes in
the microstructure of the montmorillonite, recycling is
expected to bring about changes in the molecular structure
of the matrix as a result of degradation. The only other known
work examining recyclability of a nanocomposite was con-
ducted by Lew et al. [2], though in their case the chosen matrix
was a polar polyamide-12, which being a polar macromolecule
more readily intercalates the layered silicate than a non-polar
polymer. In their work, delamination continued for seven
passes through a single-screw extruder with simultaneous
crosslinking resulting from thermo-oxidative degradation.
This work attempts to examine the impact of recycling on
intercalation/exfoliation and degradation for a TPO nanocom-
posite. A multiple-pass method, commonly used to study deg-
radation in processing equipment, is uniquely applied in this
paper to follow the relatively slow progression of intercalation
2397
of a non-polar resin into the clay structure. It is the intent of
the study to reveal the interactions of the polymer and organo-
clay during recycling. Use of a TPO in this study was signif-
icant since this resin is one of the earliest examples of
a commercial nanocomposite; however, the fact that it is
a blend of uncertain composition presents some complications
in the present analysis. Particularly, some questions regarding
the participating polymer species in the occurring degradation
of this work will not be fully addressed due to the proprietary
nature of the material.
2. Experimental
2.1. Materials
The chosen matrix was a reactor-grade TPO (Basell Hifax
CA387A). The resin had a melt index of 19 g/10 min (230


C/2.16 kg ASTM D1238). For propriety reasons, no attempt
was made to determine the composition of the material besides
a DSC scan to establish the melting temperature of the mate-
rial. The DSC confirmed that the major component was an
isotactic polypropylene and through our experience with
comparable resins we know that the elastomer phase will
likely make up less than 25 wt% of the alloy. The organoclay
used in the synthesis of our nanocomposite was Cloisite 15A
(Southern Clay Products), a natural montmorillonite modified
with a hydrogenated tallow substituted quaternary ammonium
salt. XRD analysis of the clay filler noted a basal spacing of
d001 ¼ 32.57 Å confirming values provided by the supplier.
The selected compatibilizer (MAdPP) was a functionalized
polypropylene, namely Polybond 3200 supplied from Cromp-
ton Corporation, containing 1 wt% grafted maleic anhydride.
2.2. Sample preparation
Melt intercalation of the polymer nanocomposite was
conducted on a Leistritz 40 L/D ZSE-27 HP co-rotating
twin-screw extruder configured for strand pelletization. The
trials required two different extrusion configurations. The ini-
tial configuration, used only for the first pass, involved
compounding the organoclay into the polymer. A side stuffer
attached to the extruder metered the clay into the molten poly-
mer at a distance of 18 L/D from the feed opening. Two screw
designs were used in this work, a high-work mixing screw and
a moderate-work mixing screw, both shown in Fig. 1. The phi-
losophy behind the design of the high-work screw was to gen-
erate substantial dispersive mixing in order to break-up
agglomerates and to uniformly disperse the clay and compati-
bilizer within the TPO matrix. This screw was only used for
the first pass of our polymer through the extruder. The moder-
ate-work screw design was used for the subsequent nine passes
through the extruder and focused more heavily on distributive
mixing with consideration for both the work needed for melt
intercalation and the need to minimize degradation. Previously
reported studies [1,3,8,14] have indicated that melt intercala-
tion favors distributive mixing with a moderate level of shear.
2398 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
Fig. 1. Schematic diagrams of the (a) moderate work and (b) high-work screw
designs used in the 40 L/D, 27 mm co-rotating intermeshing twin-screw
extruder.
Three resin systems were compounded in this study accord-
ing to the formulations listed in Table 1. The TPO/MAePP
blend and the neat TPO were compounded along with the
nanocomposite to provide a means of analyzing the aspects
of intercalation versus degradation which are otherwise
Table 1
TPO formulations
Sample name TPO resin (wt%) MAePP (wt%) Organoclay (wt%)
VTPO 100 0 0
TPOP 91 9 0
TPOC 88 9 3
Number of passes through the extruder.
coupled phenomena. The extruder was operated with a flat
barrel temperature profile (180
C for the first pass and
200
C for subsequent passes) and a constant screw speed
(200 rpm for the first pass and 75 rpm for subsequent passes).
Colorimetric tracer analysis revealed that the mean residence
time was 32 s for the first pass and 95 s for each subsequent
passes through the extruder for these operating conditions.
2.3. Characterization
Complex viscosity (h*) and the storage modulus (G0 ) were
determined in the range 0.1e100 s1 for samples from each
pass through the extruder using an ARES (TA Instruments)
parallel plate rheometer. A constant strain of 5% was chosen
for the measurements based on the determined linear visco-
elastic region for our materials from strain sweep testing.
The tests on the parallel plate rheometer were conducted at
210
C. A ROSAND dual-bore capillary rheometer was used
to determine the shear viscosity of the samples for the
shear-thinning region between 100 and 8000 s1 at a tempera-
ture of 210
C. Rabinowitsch and Bagley corrections were
used for all capillary measured data.
Film samples were prepared using a hot press at 180
C
under 350 bar pressure for 2 min. These films were character-
ized at 2 cm1 resolution in a Nicolet 520 FT-IR spectrometer
to observe changes in the different functional group concentra-
tions based on number of passes. To evaluate the extent of
local intercalation that occurred after passing through the
extruder, samples of the TPO nanocomposite were studied
using a transmission electron microscope (TEM) and X-ray
diffraction (XRD). Direct observation of the layered silicate
structure in the polymer matrix was possible using a Philips
CM12 TEM operating at an accelerating voltage of 120 keV
for 45K, 60K and 125K magnification. For TEM micrographs
taken at the 106 magnification, samples were analyzed on
a JEOL 2101F field emissions electron microscope. Speci-
mens were prepared by using a diamond knife to microtome
thin sections (nominally 70-nm thick) perpendicular to the
flow direction from the pelletized samples. Analysis by
XRD was performed on a Bruker D8 diffractometer using
Cu Ka radiation. The scanning rate was 2
/min in wide angle
mode for the 2q range from 0 to 10
.
Mechanical properties were determined for the different
samples on an INSTRON 3366 testing machine. All test spec-
imens were prepared on a 55-ton Arburg injection molding
machine. The flexural modulus was measured by a 3-point
bending test according to ASTM D-740 using a strain rate
of 0.10 mm/min and cross-head speed of 1.43 mm/min. A
 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
17:1 support span ratio was used for the bending tests. The
tensile properties (i.e. Young’s modulus, yield strength, and
elongation at break) were determined according to ASTM
D-638 using a 5 mm/min cross-head speed.
3. Results and discussion
Typically, researchers studying recycling and the subse-
quent degradation that occurs within polymers have relied
heavily on either rheological measures (e.g. zero-shear viscos-
ity, melt index, storage modulus) or gel permeation chroma-
tography (GPC) to determine changes in the molecular
structure. However, this presents a challenge in determining
the level of degradation that occurred in a nanocomposite as
a result of re-processing or normal service life. Molecular
weight determination by GPC becomes infeasible due to the
presence of the nano-scale clay particulate which will either
affect the inlet filters of the instrument or more likely pass
through the filters and proceed to plug the columns and inter-
fere with downstream detectors. Rheological analysis is
normally the more sensitive measure of changes in the molec-
ular structure of a polymer compared to chromatographic tech-
niques [22]; however, no previous studies exist to demonstrate
whether on-going intercalation can be distinguished from
degradation in the case of a PLS nanocomposite. A necessary
aspect of this study was, therefore, to assess the capability of
rheology to study degradation in this new class of polymers.
For clarity of discussion, we will use the terms agglomer-
ate, primary particle, crystallites (tactoids) and platelets
(sheets) in the same manner as previously defined [11].
3.1. TEM and XRD characterization
The high extent of shear and extensional deformation char-
acteristic of the screw design used for the first pass required
the polymer composite to experience the shortest possible
residence time in order to minimize degradation; however, it
was recognized that high shear and short residence time are
not conducive to intercalation of the organoclay. The purpose
of the first pass through the extruder was, therefore, to break-
up the majority of all clay agglomerates prior to subsequent
passes. Observations made by TEM, as exemplified by the mi-
crograph in Fig. 2(a), of samples collected after the first pass
through the extruder suggested that the morphology of the
material could be described as possessing an incomplete exfo-
liated structure (exfoliated platelets with intercalated tactoids
remaining). The micrograph showed dark lines indicative of
tactoids with thicknesses ranging from 9 to 20 nm as well as
grey silhouettes indicative of individual platelets dispersed in
the matrix. The tactoids were often observed to be distorted
rather than rigid flat planar structures in the matrix. High mag-
nification of the tactoids (refer to the micrograph of a sample
from Pass 1 in Fig. 3) showed that expansion of the basal
spacing began at the edges suggesting that the intercalant
(i.e. matrix polymer or compatibilizer) acted as a wedge
disrupting the crystallite structure. Within the interior of the
tactoid structures, the layer order appeared to be undisturbed.
2399
There was no evidence within the TEM micrographs that any
clay agglomerates remained after the first processing pass by
the TPO nanocomposite through the extruder. The high level
of shear of the initial screw design had been sufficient to
break-up the clay into primary particles and further into sepa-
rated tactoids.
The subsequent micrographs presented in Fig. 2(b)e(d)
show the progression of intercalation and delamination within
the composite over time under lower shear conditions than
experienced by the material during the first pass through the
extruder. The moderate-work screw was designed to maximize
residence time and distributive mixing in order to provide
optimal conditions for intercalation [1,2,8]. The micrographs
show that an increasing number of platelets were present
with each successive analyzed pass and that conversely, the re-
maining tactoids displayed less silicate sheets in their stack
structure as well as an increasing frequency of basal expansion
localized at their edges (more fraying similar to that shown in
Fig. 3). The change in thickness of the tactoids shown by TEM
was quantified by image analysis software (SigmaScan) using
the value of the minor axis for the determined area of each tac-
toid. The variation in thickness for the clay particulate within
each nanocomposite sample over the different passes through
the extruder is shown in Fig. 4 as a set of histograms. During
earlier recycling passes the tactoids showed progressive reduc-
tion in their thickness through continuous delamination. How-
ever, the similarity of the distributions between the seventh
and tenth passes indicated that further delamination beyond
the seventh pass was not achieved.
Further analysis of the structure of the tactoids shown in
Fig. 2 made note of the constant gallery spacing regardless
of the number of passes through the extruder. While XRD
measurements of the basal spacing can be less accurate at
determining the actual gallery size due to defects in the stack-
ing structure [10,11], the data confirmed the TEM observa-
tions that the d-spacing of the organoclay filler was
effectively constant over all 10 passes regardless of the extent
of residence time and deformation experienced. A constant
d-spacing for the organoclay during delamination was simi-
larly noted by Lele et al. [18] with polypropylene as the matrix
resin. It appeared to the authors that the tactoids were being
split into thinner crystallites generally near the mid-plane.
The tactoid dimensions did not appear to change significantly
between the seventh and tenth passes, suggesting that any
further delamination of the clay would be minor.
Shear-induced splitting of the tactoids (observed within the
TEM micrographs) appeared to be the significant mechanism
for dispersion of the filler within our non-polar matrix since
this phenomenon would maintain the interlayer spacing while
diminishing the thickness of the individual tactoid. It is un-
clear why the interior layer order of the clay was not notably
changed by intercalation; however, based on clay colloid
chemistry it is reasonable to speculate that the negative dipole
at the anhydride oxygen precluded its adsorption into the neg-
ative interlayer surfaces of the clay and so the anhydride group
would remain located at the clay edges which are the more fa-
vorable location for associations with polyanions [23,24]. It
2400 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
Fig. 2. TEM micrographs at 60K magnification of the TPO nanocomposite for (a) Pass 1, (b) Pass 4, (c) Pass 7, and (d) Pass 10.
appears, however, that the intercalating compatibilizer or ma-
trix resin may only need to expand the edge of a tactoid to ini-
tiate shear-induced splitting. Certainly, among the tactoids
seen under TEM that were being sheared, fraying of the edges
was always observed. Dennis et al. [1] proposed that for
Fig. 3. TEM micrographs at 106 magnification of the TPO nanocomposite after
the first pass through the twin-screw extruder.
exfoliation to occur within systems like ours where marginal
compatibility existed between the clay and polymer, both
shear and chemical compatibilization are necessary. In the
case of our TPO nanocomposite, the compatibilization strat-
egy appeared to be inadequate, despite the high weight frac-
tion of additive already employed, and the morphology
seemed incapable of progressing to a fully exfoliated structure.
3.2. Steady and complex viscosity
The complex and steady shear viscosity of both unfilled
TPOs (i.e. neat and PPeMA blend) and the TPO nanocom-
posite are plotted in Fig. 5 with a notable discontinuity
between the two sets of measurements. The discontinuity
highlights the failure of these materials to satisfy the Coxe
Merz rule. Failure of the rule implies that the microstructure
of these materials is sensitive to the mode of deformation
applied; a phenomenon correspondingly noted by other
researchers for reinforced and elastomer-modified polymers
[12,18,19,25,26]. At the lowest shear rate in the figure, we
find that the nanocomposite exhibited a substantially larger
viscosity (for the first pass, 120% over the TPO blend and
 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
Fig. 4. Histograms of particle thickness for the organoclay obtained by image analysis of TEM micrographs of the TPO nanocomposite for (a) Pass 1, (b) Pass 4, (c)
Pass 7, and (d) Pass 10. Number-average (tn ) and weight-average (tw ) thickness values for the distributions are included.
144% over the neat TPO) owing to restrictions in long chain
segmental motion within the newly developed percolating
network structure of tactoids [19]. As seen in the figure,
this shear rate lies in the Newtonian region for the neat
TPO and TPO/PPeMA blend; however, with the inclusion
of the clay the Newtonian plateau was shifted below the
measurement range of our rheometer. In the shear-thinning
region (particularly for shear rates larger than 103 s1),
Fig. 5. Flow curves of the three polymer systems determined from parallel
plate and capillary rheometers.
2401
differentiation based on viscosity of the nanocomposite
from the other two polymers was much more difficult owing
to shear-induced disruption of the clay network and the sub-
sequent alignment of tactoids and platelets in the direction of
flow [18,26]. Between the first and tenth passes (representing
a cumulative residence time of 15 min in the extruder), the
TPO/PPeMA blend experienced the greatest decrease in
viscosity followed by the neat TPO and finally the nanocom-
posite. In the case of the unfilled TPOs, the reduction in
viscosity was readily attributed to thermo-oxidative degrada-
tion. With polypropylene making up the bulk of our material,
the decrease in viscosity was explained by the occurrence of
b-scission reactions. The ethylene comonomer present in the
elastomer phase may have led to some extent of crosslinking,
though its effects (if present) were not observable in compar-
ison to the influence of scission on viscosity. For the nano-
composite, the effects of degradation on viscosity were less
prominent, either compensated to some degree due to
progressive tactoid shearing and exfoliation or delayed due
to the clay inhibiting oxidization. In order to determine the
role of the organoclay in degradation of the nanocomposite,
it is necessary to attempt to distinguish the effects of the two
correlated phenomena, namely delamination and degradation,
within the rheological data. A key question for this recycla-
bility study lies with whether the clay influences thermo-
oxidative degradation; it has been suggested in the literature
that degradation appears to a higher extent in PLS
2402 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
nanocomposites compared to a neat resin, due to interference
by the clay on the performance of antioxidants [7,13,27].
3.3. Extent of degradation
First, the two unfilled TPO systems were examined to de-
termine the extent of degradation in the absence of the clay.
The pass-by-pass changes in the molecular structure of these
two materials were approximated by their zero-shear viscosity
(h0) (refer to Table 2). The zero-shear viscosity for the TPO
nanocomposite was not included in Table 2 since a Newtonian
plateau was not reached within the shear range of our rheom-
eter. The neat TPO and TPO/MAePP blend both showed a de-
crease in their zero-shear viscosity over the 10 passes through
the extruder; the apparent onset of degradation being noted for
the TPO blend during the third pass through the extruder. The
extent of degradation (u) was estimated from this data accord-
ing to:
 3:71
DM M 0  M h
u¼ 0 ¼ 0
¼ 1  00
M M h0
where M0 and h00 is the molecular weight and zero shear vis-
cosity of the polymer, respectively at t ¼ 0 and M corresponds
to the molecular weight at some time during processing. This
measure of degradation uses the approximate power-law rela-
tionship between weight-average molecular weight and zero-
shear viscosity [28], but it is considered to be only a basic
indicator since it neglects the polydisperse nature of the poly-
mer in the calculations. Using Eq. (1), we estimate that the
overall extent of degradation after 10 passes for the TPO blend
was more than twice than that for the neat TPO, i.e. u ¼ 0.26
versus u ¼ 0.12, respectively. It has been noted [29] that com-
posites containing the maleated compatibilizer consumed anti-
oxidants more readily and demonstrated degradation sooner in
oxidative studies compared to non-compatibilized systems. In
addition, it is known from studies examining the free radical
grafting of maleic anhydride onto polypropylene [30] that
grafted maleic anhydride may act as a chain transfer agent,
further promoting degradation reactions. We surmise that the
increased susceptibility of samples containing the maleated
compatibilizer arises from the labile hydrogen on the attached
Table 2
Zero-shear viscositya
Extrusion pass Neat TPO (Pa s) TPO/MAePP blend (Pa s)
1 3136  218 3476  379
2 e 3670  321
3 e 2132  48
4 e 2285  254
5 1925  58
e
6 e 1956  70
7 e 1553  399
8 e 1478  32
9 e 1396  193
10 2001  48 1204  58
a
Estimated by cross model using complex viscosity data.
succinyl anhydride groups along the polymer backbone.
Likely, the same susceptibility is experienced by the TPO
nanocomposite which also includes the compatibilizer but its
influence cannot be readily observed due to the coupled inter-
actions between degradation and clay delamination.
To investigate the evolving microstructure caused by the
coupled interactions of degradation and clay delamination in
the nanocomposite, the storage modulus was analyzed to study
changes in chain mobility which may be elucidated from var-
iation in shear rate.
3.4. Change in storage modulus with recycling
Fig. 6 compares the storage modulus (G0 ) for the three
polymer systems over a frequency range between u ¼ 0.1
and u ¼ 100 rad s1. The plot in Fig. 6(a) shows the modulus
decreasing with each of the successive pass through the ex-
truder for both neat TPO and the TPO blend. The general re-
duction in G0 indicated greater chain mobility, which has
already been attributed to chain degradation, predominantly
ð1Þ via b-scission. No observable evidence in the curves was pres-
ent to suggest that the elastomeric phase was affected by recy-
cling; close examination of the low frequency region did not
show the increase in G0 noted by other authors [31] which
they attributed to crosslinking and aggregation of the elasto-
mer phase in their impact-modified polypropylene. Similarly,
the tensile and flexural moduli discussed in a later section of
this paper did not show evidence of significant crosslinking
within these materials.
Fig. 6(b) compares the storage modulus of the polymer ma-
terial with and without clay in the matrix. At low frequencies
(u < 1 rad s1), the storage modulus of the nanocomposite
was significantly larger in value compared to the TPO/MAe
PP blend for all samples and exhibited a slope close to 0.5
in the terminal region by the fourth pass. The change in the
slope of the curve within the terminal region of the graph
and the corresponding increase in modulus have been identi-
fied by others [12,16,18,19,26] as corresponding to short-
range fillerefiller interactions. It is our belief that crosslinking
similarly had no significant contribution to the storage modu-
lus of the nanocomposite as found with the TPO/PPeMA
blend. The only possible case by which the extent of crosslink-
ing could be conceivably greater for the nanocomposite than
the TPO blend would arise if the filler participated in degrada-
tion as a radical transfer agent or initiator but research results
in the literature indicate that organoclays do not participate in
radical reactions with the polymer [32]. Analysis in the subse-
quent sections of this paper would appear to corroborate that
the organoclay does not participate in thermo-oxidation
reactions.
At high u, the storage modulus decreased as the number of
passes through the extruder increased, though the change was
minor for the nanocomposite in comparison to the TPO blend.
The low frequency and high frequency behaviors of these ma-
terials in the plots of Fig. 6 showed distinct differences which
can be related to different aspects of chain motion within the
microstructure during oscillatory testing. It is postulated that
 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
Fig. 6. Storage modulus of the (a) TPO/MAePP blend compared to the neat
TPO resin; and (b) TPO nanocomposite compared to the TPO/MAePP blend.
the effects of the clay network and degradation on the rheol-
ogy of the polymer may be partially separated through their
frequency-dominated behavior. At this point we are simply
looking for a tool to address our need to determine whether
the nanoclay additive is actively participating in thermo-oxida-
tion reaction.
3.5. Degradation and clay delamination in the
nanocomposite
It is generally stated that under oscillatory shear, large-scale
motion of polymer chains predominates at low frequencies,
yet become largely restricted at higher frequencies with only
local segmental motion being possible. Following this line
of thought, the restrictive nature of the percolating clay net-
work on the movement of the polymer matrix can be expected
to significantly influence the storage modulus at low frequen-
cies, producing a highly elastic response in the material. How-
ever, the influence of this network structure will become
increasingly difficult to detect due to shorter relaxation times
as the frequency increases. These viscoelastic features of
2403
a filled polymer exhibiting a percolating network under oscil-
latory deformation have been similarly noted by other authors
[33,34], albeit for larger scale particles. In view of the rheolog-
ical work of Wu and Zheng [33] which examined the sensitiv-
ity of the storage modulus in detecting variations in the
percolating network of a carbon black filled polyethylene at
different frequencies, a frequency u ¼ 100 rad s1 should rea-
sonably minimize the effects of clay in our measurements. The
effects of b-scission on G0 , as already shown in Fig. 6, are ob-
servable across the full frequency range of the rheometer re-
sulting in a downward shift of the curve. However, its
effects will only be observable within the measurements
when the effects of the clay network are effectively diminished
because of the small magnitude of change brought about by
scission. Using the highest and lowest frequencies capable
of our parallel plate rheometer, we can attempt to separately
discuss apparent changes to the clay network structure (i.e. de-
lamination) and the polymer microstructure (i.e. degradation)
for the nanocomposite based on the frequency specific storage
modulus.
Fig. 7 shows G0 at u ¼ 0.1 rad s1 (to represent the low fre-
quency region) and u ¼ 100 rad s1 (to represent the high fre-
quency region) plotted versus the number of passes through
the twin-screw extruder for the TPO/PPeMA blend and
TPO nanocomposite. The standard error of G0 for the blend
was 4.4%, while for nanocomposite the error was slightly
less at 3.6%. Looking at the high frequency (u ¼ 100 rad s
1
) G0 data in Fig. 7, it was apparent that the trends were sim-
ilar between the two different polymer systems. For the first
two passes through the extruder, the G0 did not change and
then for each subsequent passes, the storage modulus de-
creased. The difference in magnitude between the two poly-
mers indicated that the influence of the percolating network
was never fully negated at this frequency else they should
match, though the fact that the trend for the nanocomposite
does not bear any resemblance to its curve at low frequency
suggests that the clay had very little affect. Linear regression
applied through the data between Passes 2 and 10 indicated
that the rate of decrease for the storage modulus at this
Fig. 7. Variation of the storage modulus at u ¼ 0.1 and 100 rad s1 with re-
spect to number of extrusion passes by the TPO blend (TPOP) and TPO nano-
composite (TPOC) (lines included for clarity).
2404 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407

frequency was 1607 Pa/pass and 1609 Pa/pass for the TPO/ the polymer and filler phases is improved. The interference
PPeMA blend and nanocomposite, respectively. The similar- of the degraded polymer species on the network structure is
ity in the change of modulus at high frequency suggests that speculated to follow the conceptual associations shown in
degradation progressed at nearly equal rates for both the ma- Fig. 8. Once the polymerefiller interactions increased to a com-
terials. This would mean that the clay did not have any signif- parable level to those experienced between the adjacent tactoid
icant effect on the stability of the polymer. It is most likely that and platelet particles, the network structure was not further af-
any perceived susceptibility of a nanocomposite to thermo-ox- fected and a plateau in the modulus of the material resulted.
idative degradation is attributed to the compatibilizer rather
than the clay.
3.6. Mechanical properties
The low frequency (u ¼ 0.1 rad s1) G0 data in Fig. 7 for the
TPO/PPeMA blend only displayed a steady decrease in value
Mechanical testing was performed under both flexure and
with increasing number of passes, mirroring the results at high
tension for the TPO nanocomposite and TPO/MAePP blend
frequency with regards to the influence of chain scission on the
to further differentiate the stability of these two materials in
polymer structure. For the nanocomposite, the effect of the
regards to degradation, and due to the importance of this
clay was seen as having a dominant effect on the G0 at this fre-
data to the automotive industry. The results are summarized
quency, and the influence of chain scission was considered to
in Fig. 9 showing the tensile and flexural moduli, yield
be indiscernible based on arguments given later in the discus-
strength and elongation at break data for samples of both the
sion. The G0 (u ¼ 0.1) trend for the nanocomposite displayed
materials corresponding to the first, fourth, seventh and tenth
a steady increase in the stiffness of the material up to the third
passes through the extruder. With the addition of 3 wt% orga-
pass, followed by an abrupt drop till the sixth pass, and then
noclay to the TPO, it can be seen in the figure that after the
finally exhibited a plateau. The initial increase in G0 for the first
first pass, the yield strength increased by 11% while the tensile
three passes through the extruder was attributed to increased
and flexural moduli increased by 30% and 31%, respectively.
fillerefiller interactions as a result of continued delamination
This significant increase in stiffness at low loadings of filler
during recycling. The XRD and TEM results confirmed that
highlights the importance of this new class of material to the
the sizes of tactoids were continually decreased by delamina-
polymer industry, being particularly beneficial to the automo-
tion after the first and fourth passes through the extruder.
tive sector where the continued need for material weight re-
The increase in the modulus per pass corresponded to decreas-
duction must always be balanced with consideration of
ing ‘n’ with respect to G0 wun (shown in Fig. 6) as the elastic-
structural requirements. The most dramatic change in
ity of the material became increasingly independent of
frequency (below 10 rad s1). The subsequent drop in G0 after
the third pass was less apparent as to its cause. The drop in G0
was not likely due to agglomeration of the tactoids since this
was not observed by TEM and XRD. Degradation would
seem to be the most likely cause for this phenomenon, though
perhaps not due to chain scission as might be initially believed.
As already argued the modulus contribution derived from the
percolating network will be reasonably insensitive to the differ-
ent relaxation behavior of cleaved chains. This argument is fur-
ther reinforced by the presence of a plateau in Fig. 7 for the low
frequency G0 after the sixth pass. We know from TEM analysis
that delamination did not significantly proceed between the
seventh and tenth passes, and therefore, in the absence of de-
lamination as a counter-effect to degradation, the decrease in
G0 if caused by scission between the third and sixth passes
should have continued (or decreased even faster) for the subse-
quent passes through the extruder. The most plausible explana-
tion for the decrease of the low frequency G0 in Fig. 7 is that
fillerefiller interactions of the nanocomposite were reduced
due to the increasingly polar nature of the matrix as the nano-
composite was recycled. As thermo-oxidative degradation pro-
ceeded with each subsequent passes through the extruder, there
would have been an increase in the concentration of oxidation
functionalities grafted onto the polymer [35,36] and these car-
Fig. 8. Conceptual representation of the percolating network of tactoids (a)
bonyl species could be reasonably expected to interfere with
edge-to-edge and edge-to-face associations between the tactoids due to the
the hydrogen-bonding associations formed within the percolat- hydrophilic edges of organophilic clay swollen with a polycation and (b) in
ing network. It has been shown in other work [37] that the elas- the presence of carbonyl functionalized polymer, a competition for association
ticity of a composite decreases as the compatibility between with the clay surface develops.
 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
Fig. 9. Change in mechanical properties with progressive passes through the extruder.
mechanical behavior that resulted from the inclusion of the
clay was at failure, with the percent elongation at break having
decreased by 180% after the first pass. All these reported
changes in mechanical properties due to the inclusion of orga-
noclay are consistent in magnitude with the data presented by
Lee et al. [38] regarding a similar grade TPO.
For subsequent passes through the extruder, the TPO ma-
terials exhibited changes in mechanical properties (Fig. 9)
that are consistent with degradation. For the TPO blend,
the flexural modulus indicated a steady decrease in stiffness
with continued recycling through the extruder, which ulti-
mately resulted in a reduction by 20% after the tenth pass.
The tensile modulus for this material also decreased but to
a lesser extent, dropping by only 13% after the tenth pass.
The yield strength for the blend dropped slightly (4%) while
the percent elongation at break declined by 68%. For the
TPO nanocomposite, the moduli (both flexural and tensile)
remained relatively constant over the first four passes and
then decreased. The fourth pass corresponds to the observ-
able onset of polymerefiller interactions as noted by the rhe-
ological testing. Losses in stiffness were considerably less for
the nanocomposite in comparison to the TPO blend, decreas-
ing by less than 10% after all 10 passes had been completed.
The yield strength of the nanocomposite showed a slight in-
crease with progressive recycling; the small increase could be
attributed to on-going delamination of the clay and possibly
by a reduction of the elastomeric domain size which has
been noted by other researchers [38]. The elongation
2405
behavior of the nanocomposite followed the trend demon-
strated by the modulus, dropping in value beyond the fourth
pass through the extruder.
The mechanical data found for the nanocomposite showed
that the value-added benefits of the organoclay addition were
retained despite the occurrence of degradation. Interestingly,
the mechanical behavior of the reinforced material did not
show any increase in stiffness though delamination continued
after the first pass; losses in properties were only observed af-
ter the fourth pass when greater allowances for chain mobility
was observed within the percolating network (similar to our
observations in the rheological analysis).
3.7. Infra-red spectroscopic analysis
The mid-range infra-red spectra of samples for the TPO
blend and TPO nanocomposite are shown in Fig. 10. Spectra
corresponding to the first and tenth passes for each polymer
system are highlighted in the figure to demonstrate the major
changes, if any, to the molecular structure of the matrix as a re-
sult of recycling. We surveyed the bending mode vibrational
bands between 800 and 900 cm1 (in Fig. 10(a)) for indications
of vinylidene generation caused by b-scission while the stretch-
ing mode vibrational bands between 1700 and 1850 cm1 (in
Fig. 10(b)) were examined for the presence of carbonyl species
attributed to oxidation products (i.e. aldehydes, ketones, and
carboxylic acid). Despite rheological evidence of thermo-oxi-
dative degradation, it appears that no evidence was found
2406 M.R. Thompson, K.K. Yeung / Polymer Degradation and Stability 91 (2006) 2396e2407
Fig. 10. Mid-range transmission FT-IR spectra of the TPO nanocomposite and
TPO/MAePP blend, examining two regions (a) 400e1000 cm1 and (b)
1500e2000 cm1.
indicating the presence of oxidation functionalities from these
plots. It has been well established in the literature that car-
bonyl-based functional groups (i.e. aldehydes, ketones, and
carboxylic acid) are always generated through the thermo-
oxidative reaction pathway within the range of processing
temperature used in this work [35,36]. The most reasonable
explanation for the absence of visible functional groups in
the infra-red spectra was that their concentration was too low
for detection. Either the intensity of vibrations pertaining to
other functional groups (particularly the clay and compatibil-
izer) obscured the peaks being sought or the extent of degrada-
tion was low and thus the concentrations of the functionalities
were simply below the sensitivity of the instrument. As a point
of note, the authors attempted FT-IR analysis of the samples
using both film transmission and attenuated total reflectance
(ATR) approaches with no differences noted in the findings.
4. Conclusions
The recyclability of a current state-of-the-art TPO nano-
composite has been studied in this work and shown to
represent a complex problem with coupled interactions be-
tween morphological development of the clay network struc-
ture and degradation. The benefit of recycling a non-polar
PLS nanocomposite comes from its inability to completely ex-
foliate the organoclay under normal (single-pass) production.
Subsequent processing steps further promote development of
a percolating network of tactoids in the matrix thereby mini-
mizing the inevitable impact of thermo-oxidative degradation
on rheological and mechanical properties. Inevitably, delami-
nation will eventually cease to alter the tactoid structure of
the material; though, a recommended recycling strategy for
this class of material might be to introduce both additional an-
tioxidant and compatibilizer for subsequent passes through
processing machinery. The onset of degradation appeared to
occur following the second pass through the twin-screw ex-
truder and the presence of the organoclay was concluded to
have no effect on either the onset or the extent of degradation
experienced by the TPO matrix. Rather, it was felt that the
maleated compatibilizer increased the extent of degradation
within the matrix, likely due to the participation of its grafted
functional group as a chain transfer agent. Oxidative modifica-
tion of the matrix as a result of degradation was felt to have
a negative effect on the stiffness of the material derived
from the percolating network structure consisting of exfoliated
platelets and dispersed tactoids. A decrease and subsequent
plateau in the storage modulus between the third and sixth re-
cycling passes through the extruder suggested reorganization
of the microstructure of the nanocomposite as the increasingly
polar polymer matrix participated in bond associations with
the network structure.
Ultimately, the study demonstrated that rheological and
mechanical properties of the recycled PLS nanocomposite
far surpassed the performance of neat material even with
only a small addition of organoclay.
Acknowledgements
The authors wish to thank the AUTO21 Network Centres of
Excellences and the Natural Sciences and Engineering Re-
search Council (NSERC) of Canada for their funding for
this work. The authors wish to go onto thank Decoma Interna-
tional for the donation of the resin, Drs. Rempel and McManus
from the University of Waterloo for their assistance with the
FT-IR analysis, and Drs. Botton and Britten at McMaster for
their help and technical advice regarding the TEM and XRD
analyses.
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