Structure and Properties of Strain-Induced Crystallization
Rubber–Clay Nanocomposites by Co-coagulating the
Rubber Latex and Clay Aqueous Suspension
Yiqing Wang,
1
Huifeng Zhang,
1
Youping Wu,
1
Jun Yang,
2
Liqun Zhang
1,2
1
Key Laboratory for Nano-materials, Ministry of Educational, Beijing 100029, China
2
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of
Chemical Technology, Beijing 100029, China
Received 20 May 2003; accepted 13 August 2004
DOI 10.1002/app.21408
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Natural rubber (NR)– clay (clay is montmo-
rillonite) and chloroprene rubber (CR)– clay nanocomposites
were prepared by co-coagulating the rubber latex and clay
aqueous suspension. Transmission electron microscopy
showed that the layers of clay were dispersed in the NR
matrix at a nano level, and the aspect ratio (width/thick-
ness) of the platelet inclusions was reduced and clay layers
aligned more orderly during the compounding operation on
an open mill. However, X-ray diffraction indicated that there
were some nonexfoliated clay layers in the NR matrix.
Stress–strain curves showed that the moduli of NR were
significantly improved with the increase of the amount of
clay. At the same time, the clay layers inhibited the crystal-
lization of NR on stretch, especially clay content of more
than 10 phr. Compared with the carbon-black-filled NR
composites, NR– clay nanocomposites exhibited high hard-
ness, high modulus, high tear strength, and excellent anti-
aging and gas barrier properties. Similar to NR– clay nano-
composites, CR– clay nanocomposites also exhibited high
hardness, high modulus, and high tear strength. © 2005 Wiley
Periodicals, Inc. J Appl Polym Sci 96: 318 –323, 2005
Key words: clay; strain-induced crystallization rubber;
nanocomposites; structure; mechanical properties; gas per-
meability
INTRODUCTION
Polymer– clay nanocomposites, especially plastic ma-
trices, have attracted much attention recently, and
these nanocomposites exhibit outstanding mechanical
properties, low gas permeability, and excellent fire
retardant properties
1–6
. But there are only a few stud-
ies on rubber– clay nanocomposites. Synthesis of rub-
ber– clay nanocomposites has typically involved rub-
ber melt or solution intercalation of organclay, which
has organic ammonium salts, or protonated amino-
terminated polybutadiene/poly(butadiene-co-aryloni-
trile) in the interlayer space
7–10
. A new approach for
rubber matrices introduced in a patent
11
by the au-
thors of this article involves mixing the rubber latex
and the clay aqueous suspension and cocoagulating
by adding electrolyte, which is simpler and cheaper
than the methods using organic clay. In our previous
work, morphology and mechanical properties of non-
crystallizing rubber such as styrene butadiene rub-
ber–, carboxylated acrylonitrile butadiene–, and nitrile
rubber– clay nanocomposites are investigated
12–15
.
Since natural rubber (NR) and chloroprene rubber
(CR) are strain-induced crystallization rubbers and
possess high strength without reinforcement, it is in-
teresting to investigate the properties of NR– clay and
CR– clay nanocomposites. In this paper, the effects of
the amounts of clay on mechanical properties, gas
permeability, and air-oven aging properties of NR–
clay or CR– clay nanocomposites are studied in detail.
EXPERIMENTAL PROCEDURES
Materials
The clay (Na-montmorillonite), with a cationic ex-
change capacity of 93 meq/100 g, is from Liufangzi
Clay Factory (Jilin, China). NR latex is from Beijing
Latex Products Factory (China). CR latex is from
Shanxi Latex Factory (China).
Preparation of rubber-clay nanocomposites
The clay aqueous suspension, the rubber latex, and the
interfacial agent (C
4
H
9
N
+
(CH
2
CH
2
OH)
3
Br
-
, 0.1 mol/
Correspondence to: L-Q. Zhang (zhangliqunghp@yahoo.
com).
Contract grant sponsor: National Natural Science Foun-
dation of China; contract grant number: 05173003; contract
grant sponsor: Beijing New Star Plan Project; contract grant
number: H010410010112; contract grant sponsor: Key Project
of Beijing Natural Science Foundation; contract grant num-
ber: 2031001; contract grant sponsor: National Tenth-five
Program; contract grant number: 2001BA310A12.
Journal of Applied Polymer Science, Vol. 96, 318 –323 (2005)
© 2005 Wiley Periodicals, Inc.