Polymer 45 (2004) 7673–7679

www.elsevier.com/locate/polymer

Adverse effects of thermal dissociation of alkyl ammonium ions on

nanoclay exfoliation in epoxy–clay systems
Jonghyun Park, Sadhan C. Jana*
Department of Polymer Engineering, College of Polymer Science and Polymer Engineering, University of Akron, Akron, OH 44325-0301, USA
Received 1 March 2004; received in revised form 19 August 2004; accepted 26 August 2004
Available online 21 September 2004

Abstract
It has been shown recently that storage modulus of intra-gallery epoxy plays a crucial role in producing exfoliated clay structures in epoxy-
nanoclay systems. In this study, the possibility of thermal dissociation of alkyl ammonium ions used as cation exchange agents of layered
silicate clays and its effects on plasticization of epoxy networks and the growth of storage modulus of intra-gallery epoxy were investigated.
It was found that at cure temperatures higher than the dissociation temperature, primary amines were generated from the thermal dissociation
of alkyl ammonium ions and the excess chloride salt, which reacted readily with the epoxy molecules and formed linear chains. In addition,
such reactions resulted in an excess of diamine curing agents, which in turn caused additional plasticization of epoxy networks and lowered
the values of intra-gallery storage modulus. In such cases, only intercalated epoxy composites were produced.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Epoxy–clay nanocomposites; Nanoclay exfoliation; Diamine curing agent

1. Introduction absent during curing of epoxy, a majority of the clay

In situ polymerization methods have been successfully
used in the development of polymer-clay nanocomposites
with exfoliated clay structures, e.g. polyamides [1–5],
epoxies [6–18], polyurethanes [19,20], cyanate esters [21–
24], and polymethylmethacrylate [25–28] to name a few. In
a recent study on epoxy–clay nanocomposite systems [11–
13], the role of elastic force—originating inside the clay
galleries from crosslinked epoxy networks—on exfoliation
of organically treated clay particles was highlighted. The
elastic force, measured in terms of storage modulus (G 0 ),
was found to be responsible for exfoliation; stronger elastic
force pushes out the outermost clay layers from the tactoids
against the opposing forces comprised of the electrostatic
attraction between the clay layers and the viscous force
offered by the extra-gallery epoxy [11]. The exfoliation
process continues until all clay galleries are exfoliated or the
cross-linked epoxy turns into gel or glass, whichever occurs
earlier. Since externally applied mechanical shear forces are
* Corresponding author. Tel.: C1 330 972 8293; fax: C1 330 258 2339.
E-mail address: janas@uakron.edu (S.C. Jana).
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.08.075
particles remain parallel even in an exfoliated state. In these
studies [11–13], exfoliated clay structures were produced
when the values of the ratio G 0 /jh*j were high; intercalated
structures resulted for small values of G 0 /jh*j. Here, G 0
refers to storage modulus of intra-gallery epoxy and jh*j
refers to the absolute value of complex viscosity of extra-
gallery epoxy [11,12]. Note that in these studies, the intra-
gallery material was emulated by mixing appropriate
amounts of epoxy, curing agent, and the alkyl amine
hydrochloride. The same alkyl amine hydrochloride was
used to treat the layered silicate clays. It was also found that
the hydrocarbon chains of the alkyl ammonium ions are
capable of plasticizing crosslinked epoxy networks, thereby
reducing the values of G 0 /jh*j and altering the exfoliation
behavior [12]. Fig. 1 presents a case where the value of G 0 /
jh*j ratio depended strongly on the nature of the curing
agents—benzenamine, 4,4 0 -sulfonylbis (DDS) and Jeffa-
mine D230—even though exfoliated clay structures were
produced in both cases. The lower values of G 0 and much
reduced glass transition temperature (Tg) of DDS-cured
intra-gallery epoxy, e.g. 159 and 197 8C, respectively with
and without n-hexadecyl ammonium chloride [12] cannot
7674 J. Park, S.C. Jana / Polymer 45 (2004) 7673–7679
Fig. 1. Evolution of G 0 and jh*j during epoxy curing (a) using
JeffaminewD230 at 125 8C and (b) DDS at 200 8C. The values of G 0 were
obtained by adding n-hexadecyl ammonium chloride in epoxy-diamine
mixture and the values of jh*j were obtained without n-hexadecyl
ammonium chloride when epoxy was cured for the same duration. Solid
lines represent interpolation of data points.
be interpreted solely based on plasticization of crosslinked
epoxy network by the alkyl chains of n-hexadecyl
ammonium chloride. The structure of DDS (Fig. 2) is
much more rigid and therefore, crosslinked epoxy networks
in DDS-cured system should be much less vulnerable to
plasticization effects.
1.1. The nature of organic ammonium ions
The ammonium ions of primary [6–8,11–14,16,18] and
tertiary [10,11,15,17,18] amines have been used in the past
to treat layered silicate clays. In epoxy–clay systems, the
ammonium ions catalyze both epoxy homopolymerization
[6,14,15] and epoxy-diamine reactions [11,12], thereby
creating a disparity in the curing rates of epoxy inside and
outside the clay galleries. The curing rate increases with the
acidity of the ammonium ions, e.g. ammonium ions of
primary alkyl amines are more acidic than quaternary
ammonium ions [7]; nanoclays, treated with primary alkyl
ammonium ions, have been used to produce transparent
clay-epoxy nanocomposites [18]. Despite extensive use of
nanoclays treated with ammonium ions of primary amines, a
Fig. 2. Chemical structures of Epon 828, JeffaminewD230, and DDS.
thorough study on potential detrimental effects of thermal
dissociation of such ammonium ions on clay exfoliation
behavior in clay-epoxy system is still lacking. The
ammonium ions of alkyl amines, e.g. CH3(CH2)15NH2
used by our laboratory [11,12] and their chloride salts, are
capable of undergoing thermal dissociation reactions to
generate primary amines as depicted in Fig. 3. The proton,
thus generated, has been shown to catalyze homopolymer-
ization of epoxies [8]. However, the role of free primary
amines on subsequent steps has not been investigated. The
free amines may react with the epoxide functionalities
present inside the galleries or may diffuse out of clay
particles and react with the epoxide functionalities in the
bulk epoxy (Fig. 4). Such reactions present two unsavory
situations. First, due to the presence of one –NH2 group per
primary amine molecule, the epoxy-primary amine reac-
tions yield only linear cured epoxy chains or chain
segments, which do not contribute much to G 0 /jh*j ratio.
Second, appreciable epoxy-primary amine reactions cause
an imbalance in reaction stoichiometry between epoxy and
diamine curing agent. The excess diamine curing agent may
cause further plasticization of the epoxy networks. There-
fore, the objective this study was to investigate such thermal
dissociation and to evaluate the adverse effects of such
thermal dissociation on clay exfoliation.
2. Experimental
2.1. Materials, preparation, and characterization
The alkyl ammonium ion was derived from a primary
amine, n-hexadecylamine, CH3(CH2)15NH2 (Aldrich, m.p.
43–45 8C, b.p. 330 8C). The alkyl ammonium chloride salt
in solid state was obtained by evaporating an aqueous
solution of n-hexadecyl ammonium chloride, CH3(CH2)15
NHC 3 Cl . Sodium montmorillonite clay, Cloisite NA
K C
(Clay 1), obtained from Southern Clay Products (Gonzales,
 J. Park, S.C. Jana / Polymer 45 (2004) 7673–7679 7675

hexadecyl ammonium chloride at 90 8C for 20 min, and

then mixing the other ingredient for 5 min at 60 8C. It was
noted that the extent of epoxy polymerization during sample
preparation was negligible. The reaction mixtures were
dried in vacuum oven thoroughly and subjected to thermal
scans and isothermal curing in Dupont differential scanning
calorimeter (DSC), model DSC-2910 under nitrogen
environment at a scan rate of 10 8C/min. Thermo-gravi-
metric analysis was carried out using TGA-2950 (TA
Instruments) under nitrogen atmosphere with a scan rate of
Fig. 3. Thermal dissociation of (a) n-hexadecyl ammonium ion and (b) its 20 8C/min. The values of G 0 and jh*j of the reaction mass
chloride salt. In (a), only one negative charge on clay particle is shown for during curing of epoxy with and without n-hexadecyl
illustration purposes. ammonium chloride respectively were measured using
RMS-800 Rheometrics rheometer with 25 mm parallel
TX) was treated in our laboratory with n-hexadecyl plate set up under oscillatory shear flow. A strain of 5%
ammonium chloride to produce Clay 2 containing and a frequency of 5 rad/s were used.
129 mequiv. of ammonium ion per 100 g of clay. This is
in excess of a maximum of 92 mequiv./100 g of clay,
indicating that an excess amount of n-hexadecyl ammonium 3. Results and discussion
chloride was adsorbed onto the clay surfaces. An aromatic
epoxy, diglycidyl ether of bisphenol A (DGEBA),
3.1. Thermal dissociation of n-hexadecyl ammonium
Eponw828 of Shell Chemical (Houston, TX), with epoxide
chloride
equivalent weight of 178–190, viscosity of 11–15 Pa s, and
specific gravity of 1.15 at 25 8C was used to produce clay-
The ammonium chloride, n-C16H33NHC 3 Cl , was sub-
K
epoxy composite. Curing agents were benzenamine, 4,4 0 -
jected to thermal scans in DSC and TGA to investigate its
sulfonylbis (DDS, HT976) obtained from Ciba (Tarrytown,
thermal dissociation patterns. The thermal scan in DSC
NY) and JeffaminewD230 of Huntsman Corporation
showed four endothermic peaks as in Fig. 5. The
(Houston, TX), which offered significant differences in
endothermic peak at 71 8C appeared due to melting of an
curing temperatures. DDS is a solid (m.p. 180 8C) and
impurity or free amines. The peak at 103 8C is assigned to
JeffaminewD230 is a liquid at room temperature. The
melting of the chloride salt. The peak at 156 8C corresponds
structures of the ingredients are shown in Fig. 2.
to thermal dissociation of the ammonium chloride, which
Clay 2, thoroughly dried in vacuum oven at 80 8C for
leads to formation of n-C16H33NH2 and HCl, as in Fig. 3(b).
48 h, was intercalated by epoxy at 90 8C for 6 h. The
It appears from Fig. 5 that thermal dissociation started at
resulting mixture was dried in a vacuum oven at 80 8C for
w130 8C and continued until w162 8C, with some loss in
30 min, mixed with stoichiometric amount of curing agent
weight of the specimen, purportedly due to volatile
for 5 min at 60 8C, degassed in a vacuum oven for 5 min at
hydrogen chloride. The endothermic peak at 227 8C is due
60 8C, and cured in an aluminum mold. The reaction
to degradation of the hydrocarbon chain as the n-hexadecyl
mixtures containing JeffaminewD230 were cured at 75, 100,
ammonium chloride and its dissociated products were
and 125 8C for 3 h and those containing DDS were cured at
thermally stable up to 205 8C (Fig. 6). Since n-C16H33NH2
180 and 200 8C for 3 h. Binary mixtures of epoxy-curing
agent, epoxy-n-hexadecylamine, and epoxy-dry n-hexade-
cyl ammonium chloride were prepared at 60 8C by mixing
the ingredients for 5 min. Ternary mixtures of epoxy, curing
agent, and dry n-hexadecyl ammonium chloride and epoxy,
n-hexadecyl amine, and dry n-hexadecyl ammonium
chloride were prepared first by mixing epoxy and n-

Fig. 4. Schematic of intra-gallery reaction with epoxy and diffusion to

extra-gallery by n-hexadecylamine. Fig. 5. DSC thermal scans of n-hexadecyl ammonium chloride.
7676 J. Park, S.C. Jana / Polymer 45 (2004) 7673–7679
Fig. 6. Thermogravimetric analysis of n-hexadecyl ammonium chloride.
has a boiling point of 330 8C, the weight loss apparent in
Fig. 6 between 162 and 210 8C was due to volatile hydrogen
chloride molecules as the HCl content in n-hexadecyl
ammonium chloride—13.2 wt%—is the same as the loss of
materials seen in Fig. 6 between 103 and 210 8C.
3.2. Catalyzed and uncatalyzed epoxy-amine reactions
Let us now evaluate if n-hexadecyl ammonium ion
influenced epoxy-amine reaction rates as well as the peak
reaction temperatures. The thermal scans of epoxy-diamine
curing agent reactions with and without n-hexadecyl
ammonium chloride are presented in Fig. 7. Fig. 8 presents
data on epoxy-n-hexadecylamine reactions. Except in the
case of DDS, epoxy-amine reactions were accelerated due
to the presence of n-hexadecyl ammonium chloride, e.g. in
epoxy-JeffaminewD230 system, the exothermic peak
appeared at 102 8C when cured in the presence of
Fig. 7. DSC scans of curing of epoxy; (a) with JeffaminewD230, (b) with JeffaminewD230 and n-hexdecyl ammonium chloride, (c) with DDS, and (d) with
DDS and n-hexdecyl ammonium chloride. The weight ratio of epoxy to n-hexdecyl ammonium chloride was 10:1. (I) and (II) represent area under the peak.
ammonium chloride (Fig. 7(b)) compared to 124 8C in
uncatalyzed system (Fig. 7(a)). Such catalytic effect was not
observed in DDS-cured system (Fig. 7(c) and (d))—the
main peak at 223 8C did not change much when cured in the
presence of n-hexadecyl ammonium chloride. Instead, a
new exothermic peak appeared at 127 8C in addition to the
usual peak seen at 221 8C, Fig. 7(d). We attribute the peak at
127 8C in Fig. 7(d) to reactions between epoxy and n-
hexadecylamine derived from the dissociation of n-
hexadecyl ammonium chloride as depicted in Figs. 4 and
5. The rationale behind such assignment comes from the fact
that the area ratio between the curves (I) and (II) in Fig. 7 (d)
is 14:86, the same as the ratio of molar amounts of n-
hexadecyl ammonium chloride and DDS in the initial
mixture. Fig. 8 shows that uncatalyzed n-hexadecyl amine-
epoxy reactions had an exothermic peak at 130 8C, while the
same reactions, catalyzed by ammonium ion showed a peak
at 102 8C. A comparison of Fig. 7(d) with Fig. 8(a) reveals
that the exothermic peak at 127 8C is indeed due to epoxy-n-
C16H33NH2 reactions.
This is further confirmed from the inspection of DSC
scans of the mixture of n-hexadecyl ammonium chloride
and Eponw828 in the absence of DDS, as in Fig. 9. The two
endothermic peaks at 77 and 104 8C, were also observed in
the thermal scan of n-hexadecyl ammonium chloride, in Fig.
5 and attributed to melting of impurities (77 8C) and n-
hexadecyl ammonium chloride (104 8C). The area of the
exothermic peak at 130 8C, labeled III, in Fig. 9 is the same
as the area of peak I in Fig. 7(d). In view of this, in DDS-
cured system, the reactions between the primary amine
derived from n-hexadecylamine hydrochloride and epoxide
groups of Eponw828 occurred earlier and at much lower
temperature than that between DDS and Eponw828.
Consequently, the faster intra-gallery epoxy curing
 J. Park, S.C. Jana / Polymer 45 (2004) 7673–7679
Fig. 8. DSC scans of curing of epoxy. (a) with n-hexadecylamine and (b) n-hexadecylamine and n-hexadecyl ammonium chloride. The weight ratio of epoxy to
n-hexadecyl ammonium chloride was 10:1.
expected due to catalytic effect of the alkyl ammonium ion
was absent in DDS-cured system. In this case, DDS-epoxy
reactions started much after n-hexadecyl ammonium
chloride dissociated and epoxy-n-hexadecylamine reactions
were completed. In view of these observations, we can now
study why the Tg was so much reduced in DDS-cured
Eponw 828 system in the presence of n-hexadecyl
ammonium chloride and why only intercalated clay
composites were produced in DDS-cured system when the
curing temperature was in the range of 170–190 8C.
3.3. Elasticity of crosslinked epoxy networks
Fig. 10 shows how the values of G 0 and jh*j changed
during epoxy curing using two curing agents, DDS and
JeffaminewD230. Recall that the intra-gallery composition
was emulated by mixing epoxy, curing agent, and 3.4 wt%
n-hexadecyl ammonium chloride and G 0 represents elas-
ticity of intra-gallery epoxy networks [11,12]. The viscosity
of extra-gallery epoxy jh*j was obtained by curing epoxy
with the diamine curing agent in absence of n-hexadecyl
ammonium chloride. In each case, epoxy was cured to the
same extent as monitored by DSC. The thermal dissociation
of alkyl ammonium chloride affected the results only in the
case of DDS-cured system at 180 8C. Tests using wide angle
Fig. 9. DSC scan of a mixture of n-hexadecyl ammonium chloride and
epoxy. The weight ratio of epoxy to n-hexadecylamine hydrochloride was
10:1.
7677
X-ray diffraction and transmission electron microscopy
revealed that, of the three cases presented in Fig. 10,
exfoliated nanocomposite was obtained only in the case of
epoxy cured at 100 8C with Jeffamine D230. This is not
surprising considering that the value of G 0 of intra-gallery
epoxy was approximately two orders of magnitude greater
than the value of jh*j of extra-gallery epoxy, e.g. for
jh*jw100 Pa-s, G 0 w104 Pa. In the other cases considered in
Fig. 10, the values of G 0 were of the same order as jh*j.
Consequently, clay remained as intercalated tactoids [11].
In DDS-cured system at 180 8C, the thermal dissociation of
n-hexadecyl ammonium chloride took place readily at the
beginning of curing step. As a result, intra-gallery curing
reactions between epoxy and DDS were not catalyzed by the
alkyl ammonium ion; the values of G 0 of intra-gallery epoxy
and the values of jh*j of extra-gallery epoxy grew at
comparable rates. In addition, faster epoxy-n-hexadecyl-
amine reactions yielded linear epoxy molecules and an
Fig. 10. Evolution of G 0 and jh*j during epoxy curing. The values of G 0
were obtained by adding n-hexadecyl ammonium chloride in epoxy-curing
agent mixture. The values of jh*j were obtained without n-hexadecyl
ammonium chloride in epoxy-curing agent mixture. Epoxy was cured for
the same duration while measuring G 0 and jh*j in each case.
7678 J. Park, S.C. Jana / Polymer 45 (2004) 7673–7679
excess of DDS, which in turn reduced the values of storage
modulus.
3.4. Epoxy–clay nanocomposites
Epoxy-diamine mixtures were separately cured in the
presence of 4 wt% clay and the results of thermal scan are
presented in Figs. 11 and 12. In each case, single exothermic
peaks were obtained, even in DDS-cured system (Fig. 12). It
was anticipated that such thermal scans would not reveal the
features seen in Figs. 7–10, as the clay content was small
and the amount of alkyl ammonium ions with treated clay
was even smaller, e.g. approximately 1 wt%. Consequently,
the absence of exothermic peak at w127 8C does not
indicate that the ammonium ions and excess salt—
129 mequiv./100 g vs. 92 mequiv./100 g maximum—did
not undergo dissociation as seen in Fig. 7(d).
These observations pose an interesting possibility for
epoxy-nanoclay systems. For clays treated with alkyl
ammonium ions of primary amines, there is a maximum
curing temperature beyond which the ammonium ions and
the excess ammonium chloride dissociate to yield primary
amines. Note that this dissociation temperature is much
lower than the thermal decomposition temperature of
hydrocarbon chains, as seen in Fig. 5. The primary amines
consume epoxies to produce linear polymers and cause
stoichiometric imbalance between epoxy and diamine
curing agents. The excess diamine curing agents then
exert plasticization effects in addition to the hydrocarbon
chains of the primary amine. This scenario was true in the
case of DDS and n-hexadecyl ammonium chloride at a
curing temperature of 180–200 8C. In view of this, a test of
compatibility between the alkyl ammonium ions and epoxy
curing conditions should be developed. In such a test, the
DSC thermal scans of the alkyl ammonium salt, as presented
in Fig. 5 for n-hexadecyl ammonium chloride, must be
carried out. The epoxy-diamine curing temperature should
Fig. 11. DSC scans of epoxy-JeffaminewD230 mixtures (a) No clay, (b)
4 wt% Clay 2, (c) 4 wt% Clay 1.
Fig. 12. DSC scans of epoxy-DDS mixtures (a) No clay, (b) 4 wt% Clay 1,
(c) 4 wt% Clay 2.
be lower than the dissociation temperature of the alkyl
ammonium salt.
4. Conclusions
This study established that proper consideration should
be given to the possibility of thermal dissociation of alkyl
ammonium ions in organically treated nanoclay while
developing clay-epoxy nanocomposites. The epoxy curing
temperature must be chosen lower than the thermal
dissociation temperature of the alkyl ammonium ions to
avoid poor nanoclay exfoliation behavior due to reduced
intra-gallery storage modulus and possible plasticization
effects.
Acknowledgements
This research was supported by National Science
Foundation in the form of CAREER grant (DMI-0134106)
to SCJ.
References
[1] Usuki A, Kawasumi M, Kojima Y, Okada A, Kurauchi T,
Kamigaito O. J Mater Res 1993;8(5):1174–8.
[2] Usuki A, Kojima Y, Kawasumi M, Okada A, Fukushima Y,
Kurauchi T, Kamigaito O. J Mater Res 1993;8(5):1179–84.
[3] Kojima Y, Usuki A, Kawasumi M, Okada A, Fukushima Y,
Kurauchi T, Kamigaito O. J Mater Res 1993;8(5):1185–9.
[4] Yano K, Usuki A, Okada A, Kurauchi T, Kamigaito O. J Polym Sci
Part A: Polym Chem 1993;31(10):2493–8.
[5] Okada A, Usuki A. Mater Sci Eng C 1995;3(2):109.
[6] Lan T, Pinnavaia TJ. Chem Mater 1994;6:2216.
[7] Lan T, Kaviratna PD, Pinnavaia TJ. Chem Mater 1995;7:2144.
[8] Lan T, Kaviratna PD, Pinnavaia TJ. J Phys Chem Solids 1996;57:
1005.
[9] Shi H, Lan T, Pinnavaia TJ. Chem Mater 1996;8:1584.
[10] Messersmith P, Giannelis EP. Chem Mater 1994;6:1719.
 J. Park, S.C. Jana / Polymer 45 (2004) 7673–7679 7679

[11] Park J, Jana SC. Macromolecules 2003;36:2758. [20] Pattanayak A, Jana SC. Macromolecules. In review.
[12] Park J, Jana SC. Macromolecules 2003;36:8391. [21] Morgan AB, Gilman JW. J Appl Polym Sci 2003;87:1329.
[13] Park J, Jana SC. Polymer 2003;44:2091. [22] Gilman JW, Harris Jr R, Hunter D. SAMPE Symp 1999;44:1408.
[14] Wang MS, Pinnavaia TJ. Chem Mater 1994;6:468. [23] Varghese S, Karger-Kocsis J, Gatos KG. Polymer 2003;44:3977.
[15] Becker O, Simon GP, Russell JV, Halley PJ. Polym Eng Sci 2003;43: [24] Varghese S, Karger-Kocsis J. Polymer 2003;44:4921.
850. [25] Wang D, Zhu J, Yao Q, Wilkie CA. Chem Mater 2002;14:3837.
[16] Kong D, Park CE. Chem Mater 2003;15:419. [26] Choi YS, Choi MH, Wang KH, Kim SO, Kim YK, Chung IJ.
[17] Brown JM, Curliss D, Vaia RA. Chem Mater 2000;12:3376. Macromolecules 2001;34:8978.
[18] Chen C, Curliss D. SAMPE J 2001;37:11. [27] Zeng C, Lee LJ. Macromolecules 2001;34:4098.
[19] Tien YI, Wei KH. Macromolecules 2001;34:9045. [28] Huang X, Brittain WJ. Macromolecules 2001;34:3255.