Polymer Degradation and Stability 90 (2005) 354e362

www.elsevier.com/locate/polydegstab

Thermal and combustion behaviour of layered

silicateeepoxy nanocomposites
G. Camino a,*, G. Tartaglione a, A. Frache a, C. Manferti a, G. Costa b
a

Politecnico di Torino, Sede di Alessandria, Centro di Cultura per lIngegneria delle Materie Plastiche,
INSTM Research Unit, Viale T. Michel 5, 15100 Alessandria, Italy
b
Istituto per lo Studio delle Macromolecole, CNR, Sezione di Genova, Via De Marini 6, 16149 Genova, Italy
Received 24 December 2004; accepted 5 February 2005
Available online 20 July 2005

Abstract
The present research looks at the thermal properties of epoxyeclay nanocomposites synthesised by in situ polymerisation of
a prepolymer (diglycidyl ether of bisphenol-A) crosslinked with methyl tetrahydrophthalic anhydride. The inorganic phase was
montmorillonite, exchanged with alkylammonium ions in order to give organophilic properties to the phyllosilicate. The
morphology of epoxyemontmorillonite nanocomposites examined by X-ray diraction and transmission electron microscopy
shows that mixed delamination or intercalation or microdispersion can occur depending on type of organoclay. Thermogravimetric
analysis shows that in nanocomposites the epoxy matrix is sheltered from the action of oxygen. Cone calorimeter tests show that the
rate of heat release in the nanocomposite combustion is strongly reduced.
2005 Elsevier Ltd. All rights reserved.
Keywords: Nanocomposites; Thermal stability; Flame retardancy; Cone calorimeter; Epoxy resin; Montmorillonite

1. Introduction
Thermoset polymers are widely used in applications
where insulation must be ensured at high working
temperature because they do not melt. However, being
organic materials they degrade to give volatile combustible products when they are heated above critical
temperatures or involved in res. Fire fatalities due to
the evolved smoke and toxic gases create hazards to
people and the environment. For these reasons it is
fundamental to develop epoxy resins with good thermal
stability and reduced ammability. This can be made by
twofold modication: enhancement of crosslink density
of the polymer and use of re retardant additives.
Halogen-containing-compounds are highly eective

* Corresponding author. Tel.: C39 0131 229361; fax: C39 0131 229331.
E-mail address: giovanni.camino@proplast.it (G. Camino).
0141-3910/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2005.02.022

ame retardants traditionally employed [1e4], unfortunately on combustion they can release corrosive, toxic
and super-toxic chemicals like halogenated dibenzodioxins and dibenzofurans [5e7]. Considering the health
and environmental hazards associated with the production of such compounds, in Europe there are
reservations about their massive use [8,9]. Therefore
there is a trend to replace them with halogen-free ame
retardants.
Polymer/layered silicate (PLS) nanocomposites seem
to be a new class of ame retardant systems. In recent
years they have attracted great interest because they
frequently exhibit remarkable improvements in mechanical and material properties [10e14] when compared
with the matrix polymers alone or with conventional
micro- and macro-composite materials. Improvements
include a higher modulus, optical transparency,
increased strength and keeping biodegradability of
biodegradable polymers, furthermore increased heat

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

resistance and decreased gas permeability and ammability [7,15e22].

Previous studies about nanocomposites synthesis
show that it is a very complex process because the
inorganic llers dispersion in the polymeric matrix is
prevented by their hydrophilic nature.
Even if in their pristine form the inorganic llers are
hydrophilic, they can be organically modied to enhance
their compatibility with polymers. In literature amino
acids and quarternized ammonium or phosphonium
cations, preferably with long alkyl chains, are organic
modiers widely used to achieve a good dispersion of
llers in polymeric matrices.
Depending on the functionality, packing density,
and length of these modiers, the organically modied
layered silicate (OLS) may be engineered to optimise
compatibility with a given polymer. In general, polymer/
layered ller nanocomposites obtained are of three
dierent types, namely (1) intercalated nanocomposites,
for which insertion of polymer chains into a layered
silicate structure occurs in a crystallographically regular
fashion, with a repeat distance of few nanometers, (2)
occulated nanocomposites, for which intercalated and
stacked silicate layers occulated as a consequence of
the hydroxylated edgeeedge interactions of the silicate
layers, and (3) exfoliated nanocomposites, in which the
single silicate layers are dispersed in the polymer matrix
and separated by average distances that depend only on
the clay loading [12]. Real samples are often in between
these idealised morphologies that have to be considered
as extreme situations.
It has been shown that depending on the alkyl chains
length of the alkylammonium ion in modied montmorillonite, an intercalated and partially exfoliated or
a totally exfoliated epoxy nanocomposite can be
obtained [14,23e27]. The studies of Pinnavaia and Lan
[28,29] show that using diglycidyl ether of bisphenol-A
prepolymer as a matrix, alkyl chains shorter than eight
carbon atoms tend to give intercalated nanocomposites
and no exfoliation occurs.
Also other parameters such as the chemical structure
of alkylammonium cations present in the interlayer
gallery of the phyllosilicate, conditions of swelling of the
organoclay by epoxy prepolymer and curing temperature are critical in preparation of epoxy nanocomposites.
Montmorillonite (MMT) is the most commonly used
layered silicate for the preparation of polymer nanocomposites. The single layers thickness is around 1 nm
and the lateral dimension can vary up to several
microns. Its very high aspect ratio (O1000) in a delaminated structure gives a very extensive llerematrix
contact surface which improves thermal, physical and
mechanical properties with low loading of organoclay
[10e14]. Indeed, while classic halogen-free ame retardants like aluminium hydroxide and magnesium hydroxide

355

require a lling level of more than 60 wt.% to achieve

suitable ame retardancy, only 5e10 wt.% montmorillonite content is necessary to reduce maximum rate of
heat release by 70% [7,18,30e32]. Even if so far, in most
cases, polymer layered nanocomposites often do not
pass some commercial combustion tests, such as UL-94
and LOI, their combination with conventional re
retardant additives is attracting research attention.
Indeed, preliminary results show that nanocomposites,
owing to their low combustion rate, can reduce the
amount of classical re retardants required to satisfy
industrial demands.
The eects of swelling conditions, mechanical stirring, sonication and curing temperature were studied for
the synthesis of the composites.

2. Experimental
2.1. Materials
Diglycidyl ether of bisphenol-A [DGEBA, LY 575
supplied by Ciba] was cured by methyl tetrahydrophthalic anhydride [MTHA, HY 917 supplied by Vantico].
Sodium montmorillonite (NANOFIL 757, Sud Chemie,
NaC) and organoclay octadecyl ammonium montmorillonite (NANOFIL 848, Sud Chemie, ODA), dimethyl
ditallow ammonium montmorillonite (NANOFIL 15,
Sud Chemie, 2M2T), benzyl dimethyl tallow ammonium
montmorillonite (NANOFIL 32, Sud Chemie, B2MT),
methyl tallow (z65% C18, z30% C16, z5% C14)
bis(2-hydroxyethyl) ammonium montmorillonite (CLOISITE 30B, Southern Clay Products, MT2EH) and
dimethyl hydrogenated-tallow (2-ethylhexyl) ammonium
montmorillonite (CLOISITE 25A, Southern Clay Products,
2MHTEX) were used as received after manual grinding in
an agate mortar.
2.2. Methods
Homogeneous mixtures DGEBA/montmorillonite
were obtained by dispersing montmorillonite powders
1.05 g (21 wt.%) in DGEBA 5.00 g. The mixtures were
treated at 80  C either by sonication for 1 h using an
ultrasonic-bath AC14 (EMME GI) or by electromechanical stirrer EURO-ST P CV (IKA) to favour
epoxy intercalation in the montmorillonite interlayer
galleries. The anhydride curing agent (90 phr) was added
to the DGEBA/clay mixtures at 80  C with manual
stirring. The samples (ca. 10.55 g) were centrifuged,
recovered and poured in an aluminium mould. Curing
was performed in 15 h at 120  C in a vented oven to
produce the nanocomposites containing 10 wt.% organoclay.
Unlled resin was prepared as reference. The crosslinking reaction of the pure epoxy resin was catalysed by

356

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

adding 1% imidazole with respect to the total weight of

the DGEBA/MTHA mixture since in previous research
we conrmed the need of a catalyst to promote
polymerisation [33]. Complete cure was performed in
2 h at 120  C in a vented oven. Imidazole was not
necessary for crosslinking in the case of the composites
because of the catalysing eect of the phyllosilicate on
the epoxy ring opening reaction [29,33]. Epoxy composites cured without imidazole showed better thermal
stability, if compared with those prepared with imidazole. This eect was attributed by Torre et al. [33] to the
action of the catalyst that promotes crosslinking reaction outside the borders of the organoclay. The blank
epoxy resin is named ER while the composites are
named ER/X where X corresponds to the number
appearing in the above clays trade-names used for the
preparation, e.g.: 15, 32, 30 B, 25A for NANOFIL 15,
NANOFIL 32, CLOISITE 30B e CLOISITE 25A,
respectively.
2.3. Characterization
Nanocomposite morphology was investigated by
means of X-ray diractometry (Philips Instrument
PW1830 with CoKa radiation (l Z 0.179 nm) and
transmission electron microscopy (Zeiss EM 900 apparatus at 80 KeV).
Thermal analysis (TGA) was performed using a TA
Instrument thermobalance, TGA 2050, under nitrogen
and air ow, at a heating rate of 10  C/min.
Combustion studies were performed using an oxygen
consumption calorimeter (Fire Testing Technology
Limited FFT Cone Calorimeter model). Heat ux:
50 kW/m2, sample: 75 mm diameter, 5 mm thick. Heat
release rate measurements were carried out in duplicate
or triplicate. Experimental error was evaluated to be
G5e10%.

3. Results and discussion

3.1. Morphological characterization
3.1.1. DGEBA/clay mixture
The degree of swelling of the layered silicates by
DGEBA and interlamellar distance of the nanocomposites were investigated by WAXD and TEM.
The procedure for the synthesis of nanocomposites
was an in situ polymerisation achieved in two stages:
the rst involved the intercalation by sonication of the
DGEBA epoxy prepolymer into the organically modied silicate, the second concerned the curing of the
intercalated prepolymer. The morphology of the material was determined at the two stages of the nanocomposite synthesis by the X-ray diraction peaks of
montmorillonite powders before and after curing.

Organically modied montmorillonites show a strong

X-ray diraction peak with a characteristic interlayer
spacing. Upon sonication with DGEBA the diraction
peak of montmorillonites is usually shifted to smaller
angles corresponding to a larger distance. Dierent
types of structures were obtained depending on the
organic modier.
Table 1 presents in the second and third column
interlayer distances corresponding to the clay and
DGEBA/clay mixtures, respectively, while the dierence
between mixtures and clay interlayer distance is reported
in the fourth column. The same results were obtained in
both sonication or mechanical stirring (e.g.: Fig. 1).
In the case of the sodium clay (NANOFIL 757)
mixing with the epoxy prepolymer slightly increases the
interlayer distance of the clay from 1.13 to 1.30 nm.
Taking into account that the van der Waals dimensions
of epoxy monomer are 1.46 ! 0.44 ! 0.35 nm [28] no
intercalation occurs with the sodium clay. Whereas
organoclays NANOFIL 848, CLOISITE 25A and
CLOISITE 30B show a clear increase in interlayer
distance upon mixing with DGEBA reaching 2.70e
2.90 nm (Table 1, Fig. 2) indicating that intercalation of
the epoxy between the layers of the clay has occurred. In
the case of the organoclay NANOFIL 15, NANOFIL 32,
respectively a negligible increase or decrease in the
interlayer distances is found upon mixing with DGEBA.
However, in both cases the nal interlayer distance is
large enough to host DGEBA monomers.
Upon DGEBA intercalation into the clay galleries,
the organic modiers reorient from their initial structure
to an orientation more perpendicular to the clay layers.
The interlayer distance of the intercalated DGEBA/
clays mixtures is therefore determined by the modier
alkyl chain length [28,34e36]. Since all the commercial
clays used here contain organic modiers with similar
tail maximum length, all the mixtures show similar clay
interlayer distances (in Table 1) after DGEBA/clay
mixing whatever the initial clay modier structures and
hence, interlayer spacing.
3.1.2. Curing
Curing conditions are of paramount importance to
the nal morphology of the composite. Indeed, it is
Table 1
Interlayer spacing of clay and mixtures
Interlayer ion
(commercial clay)

NaC (NANOFIL 757)

ODA (NANOFIL 848)
MT2EH (CLOISITE 30B)
2MHTEX (CLOISITE 25A)
2M2ODA (NANOFIL 15)
B2MODA (NANOFIL 32)

d-Spacing (nm)

Dd-Spacing (nm)

Clay Mixture
Mixture clay
DGEBA/clay
1.13
1.78
1.85
1.86
2.87
3.12

1.30
2.90
2.89
2.70
2.90
2.52

C0.17
C1.12
C1.05
C0.71
C0.03
0.60

357

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

Intensity [a.u.]

2.90 nm

A
2.94 nm

2 [deg]
Fig. 1. X-ray diraction patterns of DGEBA/848 mixture after: (A)
1 h mechanical stirring at 80  C and (B) 1 h sonication at 80  C.

important to select curing conditions that balance

intragallery and extragallery polymerisation rates to
allow ller exfoliation. If the curing temperature is too
low and the rates of epoxy and crosslinker intercalation
are slow, then extragallery polymerisation is faster than
intragallery polymerisation and intercalated composites
are formed. Intercalated composites also are formed if
curing temperature is high and the extragallery polymerisation is favoured by high temperature [28,34].
The morphology obtained in the composite upon
crosslinking of the intercalated DGEBA/clays systems
depends on competition between intragallery and
extragallery polymerisation. In the case of organoclay

2.89 nm

1
C
C

2.90 nm

Intensity [a.u.]

Intensity [a.u.]

2.70 nm

1.85 nm

1.86 nm

A
2

10

12

A
14

10

12

14

3
C

Intensity [a.u.]

2.90 nm

B
1.78 nm

A
2

10

12

14

2
Fig. 2. XRD of organoclay (A), mixtures with epoxy (B), cured composites (C) for: (1) CLOISITE 25A; (2) CLOISITE 30B; (3) NANOFIL 848.

358

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

CLOISITE 25A crosslinking leads to a further shift of

the clay diraction peak as compared to the DGEBA/
25A mixture, corresponding to an increase in the
interlayer distance from 2.70 to 2.89 nm (Fig. 2(1)).
Thus an intercalated nanocomposite is obtained. An
intercalated structure similar to ER/25A is found on
crosslinking of DGEBA/15 or DGEBA/32 mixtures.
Since ER/15 and ER/32 show a thermal and combustion
behaviour very close to that of ER/25A only this last
will be considered in the following.
With organoclay CLOISITE 30B crosslinking leads
to broadening and shifting of the composite diraction
peak which extends below the lowest accessible 2q angle
by the instrument used here (2  ) which corresponds to
an interlayer distance around 4e5 nm (Fig. 2(2)). Since
exfoliated nanocomposites imply an interlayer distance
twoethreefold than that of the original organoclay
[13] the ER/30B composite can be dened as a mixed
intercalated exfoliated nanocomposite. This behaviour
can be attributed to initiation of crosslinking interlayer
polymerisation by the modier hydroxyl groups which
can open the epoxy ring of intercalated DGEBA
[12,23,37,38]. The resulting acceleration of intragallery
polymerisation leads to favourable conditions for interlayer expansion and clay delamination which is,
however, incomplete. The intragallery polymerisation
is also favoured by the polar nature of the organic
modier which favours the diusion of DGEBA within
the interlayer space to take part in the crosslinking
process.
In the case of organoclay NANOFIL 848 behaviour
similar to that of CLOISITE 30B is found (Fig. 2(3))
with, however, a large reduction in the diraction signal
in the low angle range.
WAXD data were conrmed by a morphological
investigation performed by transmission electron microscopy. To achieve meaningful results a large number
of ultrathin cryo-sections, obtained from dierent zones
of each compound, were investigated. In a rst approach
the samples were observed at dierent magnications, to
verify the homogeneity of the ller dispersion; afterwards, to provide an accurate morphological characterization, higher magnications were used. Fig. 3 presents
TEM micrographs of the composites containing NaC
clay [ER/757], and organoclays [ER/25A], [ER/30B] and
[ER/848].
ER/757 presents a very heterogeneous morphology
along the sample thickness. There are two clearly
separated phases: the upper surface is poor in clay while
the bottom is rich. On the surface the ller content is
negligible, only thin aggregates oat on the surface while
under them no ller particles are present. From the bulk
of the composite to the bottom, ller particles increase
their dimension from 1 mm to large aggregates around
10 mm in diameter typical of a microcomposite formation (Fig. 3A).

TEM micrographs conrmed the formation of

an intercalated structure for the ER/25A composite
(Fig. 3B). ER/30B, ER/848 show a partially delaminated
morphology in which a mixture of intercalated as well as
exfoliated layers exist (Fig. 3C,D). From image analysis,
performed on at least 10 representative micrographs, the
d-spacing of the nanocomposites obtained were calculated. Interlamellar distance varying from 4 to 18 nm
was found for ER/848 nanocomposites, while ER/30B
presents a more uniform and ordered morphology with
4.5 nm average interlamellar spacing. Larger interlamellar spacing in ER/848 composite is likely to be
due to higher catalytic crosslinking activity of the
organic modier ODA (NANOFIL 848) as compared
to MT2EH (CLOISITE 30B) because of its higher
acidity. Indeed it was found that increasing Bronsted
acidity of the clay cation, that means passing from
tetraalkyl to monoalkyl onium ions, intragallery catalysis increases favouring clay exfoliation [28,34].
Comparison between nanocomposite morphology obtained with organoclays NANOFIL 848 and CLOISITE
30B suggests that a strong clay interlayer catalytic
eect is of paramount importance to reach exfoliation
as compared to diusion rate of DGEBA. This results
from the fact that a larger exfoliation is obtained in the
case of ODA modier (NANOFIL 848) which has no
polar group in the organic tail to favour DGEBA
diusion, whereas MT2EH (CLOISITE 30B) is much
more polar.
3.2. Thermal characterization
3.2.1. Thermogravimetry (TGA, DTG)
Thermal properties of the nanocomposites have been
investigated by thermogravimetric analysis. In nitrogen,
pure epoxy resin thermally degrades through a double
step process with maximum rate at 301 and 414  C
leaving a 4.1% residue [39]. The rst step of degradation
involves water elimination which results in formation of
CeC unsaturations [1,39e44]. Carboneoxygen bonds
in beta position to these unsaturations (allylic bonds)
become the thermally weakest bonds in the epoxy
network. They break down giving fragmentation of
the crosslinked structure that eventually produces fragments small enough to evaporate at these temperatures.
Volatilisation is, however, limited up to 350  C because
it is contrasted by rearrangements such as cyclisation
that produce a relatively stable structure which breaks
down in the second step of degradation. In this step
extensive break down of chemical bonds of the epoxy
network takes place including C-phenyl bonds of
bisphenol-A, leading to almost complete volatilisation.
A minor amount of charred residue is formed (ca. 4%)
due to limited recombination to a thermally stable
charred material of reactive degrading species during
decomposition.

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

359

Fig. 3. TEM images of cured epoxy resin composites: (A) ER/757 microcomposite (aggregates); (B) ER/25A intercalated nanocomposite; (C) ER/30B
ordered intercalated/exfoliated nanocomposite; (D) ER/848 intercalated/exfoliated nanocomposite.

The epoxy network shows a good resistance to

thermal oxidation (Fig. 4) since the weight loss curves
of neat ER in nitrogen and air up to 400  C are
coincident. However, charring of the epoxy network in
the second degradation step takes place in air at a higher
yield (ca. 20% at 400  C) than in nitrogen, due to
catalysis by oxygen. Complete oxidationecombustion
of the char takes place in air with maximum rate at
535  C (Fig. 4).
The composites undergo a degradation mechanism
very similar to that described above.
In air the rst degradation step is strongly reduced
in all the composites. While the unlled resin starts
to degrade at 200  C, composites are stable up to

250e300  C (Fig. 4). The thermogravimetric curves of

the nanocomposites show a maximum rate of weight
loss at a lower temperature (385e395  C) than the neat
resin (Table 2).
This is probably due to the catalytic activity of the
clay on polymer decomposition process due to Bronsted
and Lewis acid sites constituted by the clay lattice
hydroxyl groups, which contact with the polymer matrix
is large in nanocomposites. This could explain why
nanocomposites ER/30B, ER/848 and ER/25A show
lower thermal stability in the main degradation process
than the epoxy resin (Table 2). Furthermore the
Homan decomposition of the onium modier of
clays gives protonated montmorillonite that can act as

360

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

Weight [%]

80
60
40
20

Derivative weight [%/C]

0
1,6

A
B
C
D
E
F

1,4
1,2
1,0
0,8
0,6
0,4
0,2
0,0
-0,2
0

100

200

300

400

500

600

700

800

Temperature [C]
Fig. 4. Thermogravimetric curves under air ow of epoxy resin
composites: (A) ER/757; (B) ER/25A; (C) ER/30B; (D) ER/848 and
blank ER in air (E) and nitrogen ow (F).

a protonic acid catalyst. The lower thermal stability

of the ER/848 composite at the onset at 5 wt.% loss
(Table 2), if compared to the other lled composites,
could come from a larger catalytic activity related to the
monoalkyl structure of its organic modier as compared
to the di to tetraalkyl substitution of the other clays.
The yield of charred epoxy can be calculated from
data of overall char yield in Table 2, subtracting the
amount of clay added to the polymer matrix, that is
10% weight in the microcomposite ER/757 and 5e10%
in the nanocomposites, to allow for the thermal
degradation of the organic modier. From this evaluation it can be seen that the presence of the clay does not
signicantly aect the oxidative charring process of the
epoxy matrix.
Whereas, we have previously reported that above
500  C thermal oxidation of the char produced in
Table 2
Thermal oxidation of epoxy resin and composites
Sample

ER
ER/757
ER/848
ER/30B
ER/25A

Tmax ( C)
1st
Step

2nd
Step

Char
oxidation

300
e
e
e
e

409
415
395
386
387

535
538
608
570
542

T5 wt.%
(  C)

loss

Char yield %
(500  C)

polymer thermal oxidation is delayed in lamellar nanocomposites because of the oxygen barrier eect of the
inorganic layers reassembling on the surface of the
ablating material [14,22,33,45e47].
Data of Table 2 show that the largest shielding
eect from oxygen is obtained in the char formed from
the nanocomposite ER/848 which shows by XRD
(Fig. 2(3)) and TEM (Fig. 3D) the most exfoliated
structure. A lower oxidation protection is found for
ER/30B which shows a lower degree of exfoliation as
compared with ER/848, whereas the intercalated nanocomposite ER/25A and the microcomposite ER/757 do
not give oxygen shielding in these conditions (Table 2,
Fig. 4) in agreement with our previous results [39].
3.2.2. Cone calorimeter test
Flame retardant properties of the neat resin and the
composites have been investigated by cone calorimetry.
In a typical experiment the heat release rate (HRR) is
recorded as a function of time. In Fig. 5 and Table 3 it is
seen that for all the nanocomposites the peak of heat
release rate (PHRR) is reduced, which is a major
parameter in controlling ame propagation in res [48].
The best re retardant performance is shown by the
nanocomposite ER/30B with 68% HRR maximum
decrease and time to reach it increase from 90 to
150 s. The nanocomposite ER/848 which showed the
best exfoliated morphology (Fig. 2(3)) and oxygen
sheltering action in thermal oxidation (Fig. 4), gives
a good performance which is, however, much reduced as
compared to ER/30B. The re retardant mechanism
proposed for lamellar nanocomposites burning in the
cone calorimeter is associated to the creation of a protective ceramic skin on the surface of the polymer
material by ablative reassembling of the inorganic
lamellae [14,22,33,45e47]. The above results show that
besides these physical eects which should be maximized
in the most exfoliated nanocomposite ER/848, also
a chemical eect plays a role which is larger in the
2000

A
B
C
D

1800
1600

HRR[kW/m2]

100

1400
1200
1000
800
600
400
200

267
340
288
329
342

18
24
27
25
24

0
0

50

100

150

200

250

Time[s]
Fig. 5. Cone calorimeter analysis of epoxy resin composites: (A)
ER/25A; (B) ER/30B; (C) ER/848 and (D) blank ER.

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

Table 3
Comparison of time to ignition (tig) and HRR of ER-composites
Sample

ER/pure
ER/848
ER/30B
ER/25A

tig (s)
34.5
34.5
34.5
44.0

HRR (max)
Time (s)

kW/m2

Percentage (%)

90
115
150
90

2030
1250
650
1570

100
62
32
77

nanocomposite ER/30B. An increased charring catalysis

during combustion would indeed supply additional re
retardancy.
The intercalated nanocomposite ER/25A shows
the lowest HRR reduction as compared to exfoliated/
intercalated nanocomposites ER/848 and ER/30B
(Table 3), whereas no reproducible results were obtained
in the case of ER/757 microcomposite because of its
heterogeneous structure. Samples burned exposing to the
heater, the upper face which is poor in clay because of
sedimentation, give the same results as the pure ER resin.
Turning the sample over with the upper face down,
a material rich in clay is heated which provides a protection comparable to that of ER/848 because polymer
ablation leads to an inorganic surface protection although
made of a large concentration of micro particles. Both
exfoliated/intercalated nanocomposites ER/848 and ER/
30B do not increase time to ignition (tig) which is increased
in the intercalated nanocomposite ER/25A. Exfoliated/
intercalated nanocomposites do not increase tig probably
because of their lower thermal stability as shown by TGA
measurements of the onset at 5 wt.% loss.

4. Conclusions
Thermoset epoxy nanocomposites were prepared
by in situ polymerisation of diglycidyl ether of
bisphenol-A cured by methyl tetrahydrophthalic
anhydride. A wide variety of organically modied
montmorillonite and a natural sodium montmorillonite
were used in this study. The epoxy prepolymer
intercalates between the layers of organophilic clays
whereas the sodium clay is dispersed in micron size in
the epoxy prepolymer. Further crosslinking polymerisation leads to intercalated or exfoliated structures
depending on competition between extragallery and
intragallery polymerisation, respectively. The competition seems to be driven by the catalytic polymerisation
activity of the organic modier more than by diusion
of the reactants within the interlayer space.
Thermal oxidation of exfoliated materials is slowed
down by the formation of a protective skin created by
ablative reassembling of the clay layers, whereas in the
combustion scenario of the cone calorimeter, besides
the physical surface protection eectively provided by

361

exfoliated nanocomposites, also a chemical role of the

clay contributes to the re retardance mechanism. This
could be for example the charring action that we have
recently pointed out to be promoted by the clay in epoxy
nanocomposites heated in absence of air [39] that is an
environment similar to the oxygen deprived atmosphere
above the surface of a specimen burning in the cone
calorimeter.

Acknowledgments
This project was carried out in the frame of an Italian
interuniversity research program (Con 2000) funded by
the Ministry of Education, University and Research
(MIUR).

References
[1] Levchik SV, Camino G, Luda MP, Costa L, Muller G, Costes B,
et al. Polym Adv Technol 1996;7:823.
[2] Ho SM, Lee YJ. MRL Bull Res Dev 1998;2:27.
[3] Shaw SJ. In: Chemistry and technology of epoxy resins. Glasgow,
NZ: Chapman and Hall; 1993. p. 117.
[4] Tanaka Y. In: Epoxy resins chemistry and technology. New York:
Dekker; 1988. p. 719.
[5] Camino G, Lomakin S. In: Fire retardant materials. Cambridge
CB1 6AH, England: Woodhead Publishing Limited; 2001. p. 318.
[6] Halpern Y, Mott DM, Niswander RH. Ind Eng Chem Prod Res
Dev 1984;23:233.
[7] Lomakin S, Zaikov GE. Ecological aspects of ame retardancy. Zeis,
Netherlands: V S P International Science Publishers; 1999. p. 170.
[8] Bergendhl CG. In: Bergendhl CG, editor. International conference on halogen free materials for electronic and electric products;
27e29 November 1999. [Gothemburg, Sweden.]
[9] Dumler R, Thoma H. Chemosphere 1989;19:305.
[10] Alexandre M, Dubois P. Mat Sci Eng R 2000;28:1.
[11] Giannelis EP. Adv Mater 1996;8:29.
[12] Ray SS, Okamoto M. Prog Polym Sci 2003;28:1539.
[13] Vaia RA. In: Pinnavaia TJ, Beall GW, editors. Polymer-clay
nanocomposited. New York; 2000. p. 244.
[14] Zanetti M, Lomakin LS, Camino G. Macromol Mater Eng
2000;279:1.
[15] Alexandre M, Beyer G, Henrist C, Cloots R, Rulmont A,
Jerome R, et al. Macromol Rapid Commun 2001;22:643e6.
[16] Bartholmai M, Schartel B. Polym Adv Technol 2004;15:355e64.
[17] Beyer G. Polym News 2001;26:334e42.
[18] Gilman JW, Kashiwagi T, Giannelis EP, Manias E, Lomakin S,
Lichtenhan JD, et al. Fire retardancy of polymers: the use
of intumescence. In: Camino G, Le Bras M, Bourbigot S,
DeLobel R, editors. Cambridge: The Royal Society of Chemistry;
1998. p. 203.
[19] Gilman JW, Jackson CL, Morgan AB, Harris R, Manias E,
Giannelis EP. Chem Mater 2000;12:1866.
[20] Kojima Y, Usuki A, Kawasumi M, Okada A, Fukushima Y,
Kamigaito O. J Mater Res 1993;8:1185.
[21] Wang Z, Pinnavaia T. J Chem Mater 1998;10:1820.
[22] Zanetti M, Camino G, Mulhaupt R. Polym Degrad Stab
2002;74:413.
[23] Brown JM, Curliss D, Vaia RA. Chem Mater 2000;12:3376e84.
[24] Lagaly T. Appl Clay Sci 1999;15:30.
[25] Le Baron PC, Wang Z, Pinnavaia TJ. Appl Clay Sci 1999;15:11.

362

G. Camino et al. / Polymer Degradation and Stability 90 (2005) 354e362

[26] Zilg C, Reichert P, Dietsche F, Engelhard T, Mulhaupt R.

Kunstst-Plast Eur 1998;88:1812.
[27] Zilg C, Thomann R, Finter J, Mulhaupt R. Macromol Mater Eng
2000;280/281:41.
[28] Lan T, Kaviratna PD, Pinnavaia TJ. Chem Mater 1995;7:2144e50.
[29] Kaviratna L, Pinnavaia PD. J Phys Chem Solids 1996;57.
[30] Gilman JW, Kashiwagi T, Lichtenhan JD. SAMPE J 1997;33:40.
[31] Lee J, Giannelis E. Polym Prepr 1997;38:688.
[32] Gilman JW, Kashiwagi T, Nyden M, Brown JET, Jackson CL,
Lomakin S, et al. Chemistry and technology of polymer additives.
In: Ak-Malaika S, Golovoy A, Wilkie CA, editors. Oxford:
Blackwell Science Ltd; 1999. p. 249.
[33] Torre L, Frulloni E, Kenny JM, Manferti C, Camino G. J Appl
Polym Sci 2003;90:2532.
[34] Pinnavaia TJ, Lan T, Wang Z, Shi H, Kaviratna PD. In:
Chow G-M, Gonsalves KE, editors. ACS Symposium Series 622.
Washington, DC: American Chemical Society; 1996. p. 250.
[35] Lan T, Kaviratna PD, Pinnavaia TJ. Proc ACS Div Polym Mater
Sci Eng (PMSE) 1994;71:528.
[36] Usuki A, Kojima Y, Kawasumi M, Okada A, Fukushima Y,
Kurauchi T, et al. J Mater Res 1993;8:1185.
[37] Chen JS, Poliks MD, Ober CK, Zhang Y, Wiesner U,
Giannelis EP. Polymer 2002;43:4895.
[38] Zilg C, Mulhaupt R, Finter J. Macromol Chem Phys
1999;200:661e70.

[39] Camino G, Tartaglione G, Frache A, Manferti C, Finocchiaro P,

Falqui L. Fire and Polymers IV: Materials and concepts for
Hazard prevention. In: Wilkie CA, Nelson GL, editors. ACS
Symposium Series, Oxford University Press, in press.
[40] Camino G. Chemistry and technology of polymer additives.
In: Ak-Malaika S, Golovoy A, Wilkie CA, editors. Oxford:
Blackwell Science Ltd; 1999. p. 108.
[41] Levchik SV, Camino G, Luda MP, Costa L, Costes B, Henry Y,
et al. Polym Adv Technol 1995;6:53.
[42] Levchik SV, Camino G, Costa L, Luda MP. Polym Degrad Stab
1996;54:317.
[43] Levchik SV, Camino G, Luda MP, Costa L, Muller G, Costes B.
Polym Degrad Stab 1998;60:169.
[44] Kandola BK, Horrocks AR, Myler P, Blair D. Fire polymers.
In: Nelson GL, Wilkie CA, editors. ACS Symposium series 797.
Washington, DC: American Chemical Society; 2001. p. 344.
[45] Zanetti M, Camino G, Reichert P, Mulhaupt R. Macromol Rapid
Comm 2001;22:176.
[46] Zanetti M, Camino G, Canavese D, Morgan AB, Lamelas FJ,
Wilkie CA. Chem Mater 2002;14:189.
[47] Zanetti M, Kashiwagi T, Falqui L, Camino G. Chem Mater
2002;14:885.
[48] Babrauskas V. Ignition handbook. Issaquah, WA 98027: Fire
Science Publishers. A division of re science and technology Inc;
2003.