34 Journal of Polymer Engineering and Technology, 2005, 11, 34-37

http://polymer.aut.ac.ir/

Nano Composites
Sajjadi, Seyed Pooyan (s.pooyan@sajjadi.me)
Polymer Engineering Department, Amirkabir university of Technology
P.O.Box: 15875-4413, Tehran, Iran.
Received: February12, 2005; Published: June 8, 2005.

Abstract
Nano composites are an emerging class of mineral-filed plastics that contain relatively small amounts
(<10%) of nanometer-sized clay articles. These mineral significantly enhance the mechanical and
thermal properties of the base resin, as well as improve barrier performance and flame retardancy. All
of these performance benefits are available without increasing the density or reducing light
transmission properties of the base polymer. First developed by Toyota over 10 years ago. Nano
composites are just becoming viable commercial product and nylon 6 was the first polymer to be used
in the development of Nano composites. Although some reports glorify the discovery of nano
composites as revolutionary break thought in science and technology, it should be noted that the basic
synthetic concept has been established for many decades.

Keywords: Nano composites

In fact, pioneering research of Toyota on polyamide
nanocmosites during the 1980, s, the renewed interest
in chemical nanotechnology and the quest for
upgrading of old polymers have stimulated
nanocmosites development. Most R&D is focused on
automotive parts and packaging, although a divers
range of disposable and durable applications are under
development.
Nanocmposites incorporate low loading (typically less
than 5% by weight) of high aspect ratio mineral or
carbon nanotube fillers that have a unique structure.
The resultant high surface area and high aspect ratio
fillers provide similar reinforcing performance of
traditional minerals and fibers used in plastics, and yet
do not increase density since levels are low. Due to the
nanometer size of particles, which is smaller than the
wavelength of visible light, the reinforced polymer
remains transparent. Other characteristics of the
composites include high barrier performance and
improved thermal stability, which make these
compounds suitable for many applications.
Development activities in nancmosites field have
spread to all regions of the world, and active programs
are now focused on creating comounds based on PP,
PET, PVC, acrylics, TPEs, and a range of elastomers,
as well as traditional thermosets. Over the coming 10
years, nanoclay composites of nearly 20 polymers are
expected to be commercialized.
Carbon black used to be the most important reinforcing
agent in the rubber material industry. But its polluting
nature, the monotonous black color of the rubber
material, and its dependence on petroleum caused
researchers to develop other satisfying reinforcing
agents instead. It was well known that the particle size,
structure, and surface characteristics of reinforcing
agents were three main factors that effect or decide its
reinforcing ability, especially the particle size.
Experiments showed that the tensile strength of ultra
fine CaCO3/ Styrenebutadiene rubber (SBR)
composites was improved and 3 times higher than that
of a regular size CaCO3 /SBR blend.
Clay is an inexpensive natural mineral so it has been
used as a filler for rubber and plastic for many years,
but its reinforcing ability is poor because of its big
particle size and low surface activity, and can only be
used for conventional micro composites. A new way to
improve the reinforcing ability of clay was recently
found. Clay has a layer structure; among the layers
there are some ions that can be exchanged with other
organic ions. The layers can not be separated from each
other through general rubber processing means. In
recent years the interest in nanoscale materials was
inspired by the fact that nanoscale materials often
exhibited physical and chemical properties that were
dramatically different from their bulk counterparts. A
novel idea was put forth that polymer could be
intercalated to the clay layer galleries to from
nanocmposites through a special method, and many
kinds of material sprung up that had an ultra fine phase
dimension. Nanocmposites possess unique properties
such as stiffness, strength and gas barrier action for
their dispersion structure.
The structures of polymer-clay nanocmosites are
usually characterized by X-ray diffraction (XRD),
transmission electron microscopy (TEM), atomic force
microscopy (AFM), etc.
Clay minerals, such as montmorillonite and vermiculite
have been widely used to prepare polymer-clay
35 Journal of Polymer Engineering and Technology, 2005, 11, 34-37
http://polymer.aut.ac.ir/
nanocmposites. The layer structure of montmorillonite
(MMT) consists of two silica tetrahedral sheets to an
edge-shared octahedral sheet of either aluminum or
magnesium hydroxide. Stacking of the layers of ca 1-
nm thickness by a weak dipolar force leads to
interlayer or galleries between the layers. The galleries
are normally occupied by actions such as K+, Na+,
Ca2+, Mg2+ and Cg+, by which is easy to form the
organosilicate by an alkylammonium ion-exchange
reaction. The organosilicates can be broken down into
their nanoscale building blocks and uniformly
dispersed in the polymer matrix to from exfoliated
nanocmposites during the compounding process.
Today it is well recognized that silicate modification
and especially interfacial coupling must be tailored
very carefully to achieve property improvements.
Example of organo clay preparation
NA+” type montmoriilonte (NA-MMT) with a cation
exchange capacity of 119 meq (100 g) was gradually
added to a solution of dimethyl distearyl ammounium
bromide and vigorously stirred at 70 c for 24 h. The
treated clay was washed repeatedly with deionized
water until no further AgBr formation was observed
through titration with 0.1N AgNO3. The product was
filtered and dried in a vacuum oven at 50 c for 24h and
was termed Org-MMT.
To prepare NBR/clay nanocomposites, the Org-MMT
was mixed as 15 parts per hundred rubber (phr) with
NBR in a Banbury type internal mixer at 60 rev min-1
and at 50 C for 10 min. A small amount (1 phr) of
dicumyl peroxide as a curative was then mixed in a
towrol mill. For comparison, Na-MMT and
conventional carbon black (N-220 type, Lucky Carbon
Black, Korea) was also mixed with NBR using the
same procedure. The mixed composites were cured at
170 C for 15 min in a heated press under a pressure of
29.4 Mpa. Table 1. Shows the tensile and tear
properties of the NBR composites. Figure 1. Shows the
organo-clay structure and intercalated and exfoliated
nanocomposites.
Methods for Nanocomposites preparation:
The methods for nanocomposites included in situ
ploymerization, solution intercalation, and melting
intercalation. In situ polymerization needs special
monomers and clay treatment; this limits its application
in other polymers. The solution method needs a
compatible polymer-solution system and organically
modified clay; its disadvantage is that the solvent must
be deabsorbed. Melting intercalation can be applied to
most polymers, especially plastic, but it needs polymer
that has good properties in the melting state.
Clay can be modified with organic quaternary
ammonium salts; thus, some modified clay can be
swollen in nonpolar solvents such as toluene. The clay
layer can be steadily dispersed in water for the
hydration of the ion among the layers; the layers are
separated from each other. Some polar compounds can
intercalate to the clay layer galleries. These
characteristics provided a way to prepare the rubber-
clay nanocomposites. The molecular weight of the
rubber was higher than plastic; it had very high
viscosity in the process state, and most of the rubbers
gad latex forms and could blend with a clay-water
dispersion without coagulation. A new method has
developed to prepare rubber-clay nanocomposites
through mixing and coagulation of rubber latex, which
has named the latex method. Figure 2. Shows a
schematic of the formation of the nanocomposites use
latex method.
Example of nanocomposites preparation
use in situ polymerization
The surface of silica was modified by aminobutyric
acid first, then the modified silica was dried in an oven
for the preparation of nylon 6 silica nanocomposites.
The preparation of nylon 6 silica nanocomposites
included two processes; the modified silica particles
were dispersed in E-caproamide at 90 C, and
naminocapric acid as the initiator was introduced at the
same time; then this mixture was polymerized at a high
temperature under a nitrogen atmosphere.
Example of nanocomposites preparation
use solution method:
A suspension of an industrial sodium montmorillonite
modified by means of sodium cation exchange with 38
wt% diemethyl distearyl ammoinium salt in toluene
was mixed with a toluene solution containing the same
amount of rubber-butadiene rubber (BR) or styrene-
butadiene rubber (SBR)- followed by stirring for 24h
and subsequent solvent evaporation in vacuum for 5d
at 40 C. in a second filler preparation process, 10phr
bid (triethoxylilylproyl)- tetrausuflfan TESPT was
added to the toluene solution of the elastomer. The
increase of interlayer distance increased from 1.26nm
for montmorillonite to 2.59nm for the organo clay and
ranged from 3.59 to approximately 6nm for the rubber
swollen organocaly. Then samples were treated on a
improving filler dispersion. The compounds were
vulcanized for 30 min at 165 C in a hot stage press
under vacuum containing sulfur, vulcanization initiator
N-cyclohexylbenzothiazole-2-sulfenamide (CBS) and
accelerator zinc distearate.
36 Journal of Polymer Engineering and Technology, 2005, 11, 34-37
http://polymer.aut.ac.ir/
Example of nanocomposites preparation
use melt intercalation:
The melt compounding of PP/clay composites was
carried out with a Brabender single-screw extruder.
The clay (organoclay) and polymer samples were dried
in an air circulatory oven at 65 C for 8h prior to
compounding.
The temperature zones ranged from 160 to 200 C, and
the revolutions-per-minute rate was 45. One
composition containing polymer (84%) compatibilizer
(12%), and clay (4%) was prepared for each clay.
Example of nanocomposites preparation
use latex method:
Clay was dispersed in water with strong stirring (2%
disperesed in water); then the latex was added and
Fig 1. a schmatic of the formation of the nanocomposites.
Fig 2. Organo clay
mixed for a period of time. It was coagulated in dilute
hydrochloric acid solution, washed with water until its
pH was about 7, and dried at 50 C.
For SBR Wang et la. Showed that the mechanical
properties of the nanocomposites produced by the latex
method were better than those produced by the solution
method.
The improved properties of the former could be
interpreted to be its better dispersion of silicate layers.
Table II summarize the mechanical properties of
nanocomposites and other reinforced SBR. Material
had different proporties with different reinforcing
methods. The data exhibited that clay was a good
reinforcing agent like the carbon black in the studied
range.
37 Journal of Polymer Engineering and Technology, 2005, 11, 34-37
http://polymer.aut.ac.ir/

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