Okada Et Al-2006-Macromolecular Materials and Engineering

Feature Article
1449
DOI: 10.1002/mame.200600260
Summary: More than twenty years have passed since we invented PCN, in which only a few wt.-% of silicate is randomly
and homogeneously dispersed in the polymer matrix. When
molded, these nanocomposites show superior properties compared to those of pristine polymers. The number of papers on
PCN has increased rapidly in recent years, reaching over 500
in 2005 alone. Being pioneers of this new technology, we
review its history relative to the following epochal events:
In 1985 we invented nylon 6-clay hybrid (NCH), the first PCN.
In 1989, cars equipped with a NCH part were launched.
In 1997, Gilman found revolutionary fire retardancy in NCH.

In 1997, a PP-clay nanocomposite was prepared using a
compatibilizer.
In 1998, a compounding method for producing PCN was
completed.
In 2002, Haraguchi invented a revolutionary nanocomposite
hydrogel.
So far, only nylon-clay nanocomposites have been used in
practice, but other PCN will become increasingly useful in the
future.
SEM of etched NCH film.
Twenty Years of Polymer-Clay Nanocomposites

Akane Okada,* Arimitsu Usuki
Toyota Central Research & Development Labs., Inc., Materials Department, Yokomichi, Nagakute, Aichi, 480-1192, Japan
Fax: 81 561 63 5441; E-mail: a_okada@ma.medias.ne.jp; aokada@mosk.tytlabs.co.jp
Received: July 2, 2006; Revised: September 25, 2006; Accepted: September 25, 2006; DOI: 10.1002/mame.200600260
Keywords: clay; hybrids; molecular composites; nanocomposites; NCH
1. Introduction
2. Nylon-Clay Nanocomposites
2.1 Nylon 6-Clay Hybrid (NCH)
2.1.1 Dry Polymerization Method
Dry polymerization method
Characterization of NCH
2.1.2 Wet Polymerization Methods
Wet polymerization method
Wet lactam polymerization method
One-Pot polymerization method
Diamine addition polymerization method
Polymerization/Compounding method
2.1.3 Compounding Methods
Dry compounding method
Wet compounding method
Macromol. Mater. Eng. 2006, 291, 14491476
2.1.4 Structure and Reinforcement Mechanism of

NCH
2.2 Other Aliphatic Nylon-Clay Nanocomposites
2.3 Aromatic Nylon-Clay Nanocomposites
3. Polyimide (PI)-Clay Hybrids
4. Polyolefin-Clay Nanocomposites
4.1 Poly(propylene) (PP)-Clay Nanocomposites
4.2 Polyethylene (PE)-Clay Nanocomposites
4.3 Other Polyolefin-Clay Nanocomposites
4.4 Other Thermoplastic Polymer-Clay
Nanocomposites
5. Rubber and Thermosetting Resin-Clay Nanocomposites
5.1 Rubber-Clay Nanocomposites
5.2 Other Thermoset Polymer-Clay Nanocomposites
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1450
A. Okada, A. Usuki
5.2.1 Epoxy Resin-Clay Nanocomposites

5.2.2 Phenol Resin-Clay Nanocomposites
6. Nanocomposite Hydrogels
8. Introduction of a Layered Microdomain Structure in

Block Co-Polymer by Clay
Conclusion
7. Liquid Crystal-Clay Composites
1. Introduction
In polymer clay nanocomposites (PCN), a few wt.-% of
each silicate layer of clay mineral is randomly and
homogeneously dispersed on a molecular level in the
polymer matrix. When molded, the mechanical, thermal
and barrier properties of these materials are superior to
those of pristine polymers and/or conventional composites. The effects are very striking, and have become well
known since many excellent reviews have been
published.[1]
In 1985 PCN was invented at Toyota Central R&D Labs,
Inc. (Toyota).[2] It bore a new concept of polymer
nanocomposites, expanded the field of polymer science
including preparation, structure and interfaces and led to
new applications for automotive, electric and food
industries. Passenger cars equipped with a PCN part were
launched in 1989, only 4 years after this discovery. Since
then, extensive worldwide research on PCN has been
conducted not only in the industrial sector but also in the
academic sector. Currently, there are international conferences on PCN every year, and papers on PCN in major
journals exceeded 500 in 2005 alone, according to
Thomsons Web of Science (WOS).
As pioneers of PCN, we believe that it is our
responsibility to review the 20-year history of its
development and describe the significance of PCN to as

many polymer and/or organic scientists as possible. In this
article we will focus on the preparation of PCN. Twenty
years ago, the term nanocomposite was not very
popular. We used hybrid or molecular composite.
Actually, according to WOS, the word nanocomposite
appeared in a paper in the polymer field for the first time in
1990 when cars equipped with a polymer-clay hybrid
part were driven through towns and fields. But since many
scientists today use nanocomposite instead of hybrid,
we also use the term nanocomposite in this article.
However, in describing our early work, we will use the term
hybrid, especially for nylon 6 and polyimide.
The major use of polymers is in molded products.
Polymers have been successfully reinforced using glass
fiber, talc, calcium carbonate, carbon black and other
inorganic fillers. The content of the filler is usually
between 20 and 40 wt.-% of a composite, and sometimes
exceeds 50 wt.-% in thermosetting resins. Polymers and
fillers are not homogeneously mixed on a microscopic
level, and are composed of different phases. The
interface is not large, and interaction between the
polymer (matrix) and the filler is limited. Takayanagi
et al. proposed the concept of a molecular composite, on
the basis that if the filler is of molecular size then
mechanical properties could be further improved, and
Akane Okada graduated at Kyoto University in 1969. In 1974 he received a Doctor degree of Science in the
research of Trialkylsilyl Anions Synthesis, Reactions and Application to ESR Spectroscopy from
Tohoku University. In 1974 he joined Mitsubishi Chemical Industry. In 1985 he has joined Toyota Central
R&D Labs., Inc. In 2000 he won jointly the Chemical Engineering Award by the Chemical Society of Japan
for Development of Clay Mineral/Organic Polymer Nano-Hybrid Materials. His major interests are
polymer nanocomposite, organosilicon chemistry, and organic opt-electro materials. He has published 94
papers which cover polymer nanocomposites, organosilicon chemistry, polymer gel actuators, organic
nonlinear optical materials, organic electroluminescence, electroviscoelastic materials, ESR spectroscopy,
organic photochemistry and so on. He has filed 161 patents which cover electrophotographic materials,
vesicular photography, synthesis of phenylacetylens, secondary batteries and gasoline vapor absorbers in
addition to the subjects of papers above. He is now Fellow of Toyota Central R&D Labs., Inc. and belongs
to its Material Department.
Arimitsu Usuki graduated at Nagoya University in 1978. He also received a M.S. degree in Synthetic
Chemistry in 1980 from the same university. The thesis was study of Substitution Reaction of Adamantane
Bridgehead Using Allyl Trimethylsilane Compounds. He joined Toyota Central R&D Labs., Inc. in 1980.
Since then, he has been working in the field of synthesis of polymers, especially p-conjugated polymers,
polymer nanocomposites, functional polymers and biopolymers. In 1996, he received a doctor of
engineering degree from Nagoya university, on the thesis titled Study of Nylon6 Clay Hybrid. He is
especially interested in research and development of polymer materials, extremely useful for weight
reduction of automobiles. He is now research manager of organic materials laboratory of Toyota Central
R&D Labs., Inc.
www.mme-journal.de
1451
showed an example of a nylon matrix containing

aramide fiber whose content was 5 wt.-% and diameter
was 30 nm.[3] We considered that if platelets of nm
dimensions were used instead of fibers, the contact
surface would become much larger. Smectite
clay minerals, especially montmorillonite (MMT), are
potential candidates for a platelet-type filler for
molecular composites, since they are composed of
several layers of silicates. These silicates are 1 nm thick
and have a cross-sectional area of 100 nm2, which is very
small compared to conventional fillers and also aramide
fibers. MMT is the most common and ubiquitous clay
mineral, and it is well known that it undergoes
intercalation and swelling in the presence of water
and organic cations.[4] Syntheses of polymers in the
presence of MMT have previously been reported,[5] but
their major component was clay, and these studies were
not intended to improve polymers but rather to focus
scientific interest. In 1975 Fujiwara et al. of Unitika Ltd.
tried to prepare a polymer composite with nylon 6 and
MMT to make reinforced nylon 6.[6] However, they
obtained composites in which the major component was
ceramic, as in earlier studies. These early materials were
merely ceramic-like powders, incapable of being
injection-molded and therefore practically impossible to
process. An impractical molding might be possible, but even
if barely molded, the test piece had low tensile strength,
brittleness, a very rough surface and a heavy weight;
therefore, they cannot be called polymeric materials.
On the other hand, if the silicates are dispersed randomly
and homogeneously in the polymer matrix, the interface
area is enormous and a large interaction could be expected.
If the silicates are in such a state, interactions between
them must be avoided. The shape of silicates is irregular.
We assumed that they are square to simplify the problem.
Provided that the silicates are 1 100 100 nm3 and all
Figure 1.
edges adjoin, the upper limit of their content vol.-%

(corresponding to 7.5 wt.-%) for nanocomposites. If only
all apexes of the squares touch, the upper limit of the
silicate content is 1.5 vol.-% (3.8 wt.-%). We were
convinced that that the upper limit of clay content is a few
wt.-% for PCN. A small amount of clay has been proven to
be of key importance for nanocomposites.
Actually, it was discovered that when the clay content
was less than 5 wt.-%, such a molecular composite, hybrid
or nanocomposite could be obtained. While some people
classify PCN into the intercalated type, where the
structure of the clay is maintained to some extent, and the
exfoliated type, where silicate is randomly and homogeneously dispersed, we focus on the latter, because the
former may be considered a conventional composite in
many cases. The structure of MMT is shown in Figure 1,
and scanning electron microscopy (SEM) photographs of
glass fiber and clay in the polymer matrix are shown in
Figure 2, where the scales of two photos differ by 100 times.
2. Nylon-Clay Nanocomposites
2.1 Nylon 6-Clay Hybrid (NCH)
2.1.1 Dry Polymerization
Dry polymerization method: We initially discuss nylon
6, since it is a typical engineering polymer in the auto
industry, reinforced by glass fiber.[7] In order to obtain
NCH, we needed to make MMT organophilic.[8] v-Amino
acid (AA) hydrogen chloride with carbon numbers from 2
to 18 was chosen as a swelling agent because the proton of
the carboxyl group ( COOH) of AA initiates polymerization of e-caprolactam (CL), the monomer of nylon 6. From
X-ray diffraction (XRD) studies (see Figure 3), the basal
spacing of AA from C2 to C8 (interlayer distance, ) is the
Structure of montmorillonite.
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1452
A. Okada, A. Usuki
Figure 2.
Comparison of size of glass fiber and montmorillonite in NCH.
same, indicating they are parallel to the silicate. From C8 to

C18, AA cannot be parallel to silicate but is tilted. An
XRD study was done with the mixture of AA and CL
(mp 70 8C) at 25 and 100 8C. At 25 8C all basal spacings
(*) were the sum of the bond length of AA plus 1 nm, the
thickness of silicate. At 100 8C, with molten CL, the basal
spacing (&) of C1 to C8 in AA is the same as the length of
AA plus 1 nm, which means that AA is vertical with
respect to silicate, while that of C11 and higher carbons in
AA is greater than the length of AA, which indicates that
CL molecules occupy the interlayer spacings one after
another.
MMT intercalated with 12-aminododecanoic acid
(ADA) was selected, which is abbreviated to 12-Mt.[9]
We changed the composition to 12-Mt/CL and polymerized CL. Specimens were named NCH2, NCH5, NCH8,
NCH15, NCH30, NCH50, or NCH70 based on the wt.-%

of 12-Mt. To compare, we melt-compounded nylon 6 and
pristine MMT (Na-MMT) to give a conventional composite (nylon 6-clay composite, NCC). Figure 4 shows the
formation of NCH and NCC.
Characterization of NCH: Inorganic content was calculated from ash after burning. End-group analysis of nylon 6
in NCH was done by titration for NH2 and COOH. In
ordinary nylon 6, both values coincide, and the numberaverage molecular weight (M n ) can be calculated. In
Table 1, amounts of MMT and end group values are
summarized. When end-group content is plotted against
the wt.-% value of 12-Mt (Figure 5), COOH increases
linearly with MMT content but NH2 barely changes
(nearly equal to zero). This means that terminal amino
groups in nylon 6 become ammonium ions and are
ion-bonded to silicate. Thus, M n was estimated from
the amount of COOH. Basal spacing is also shown in
Table 1.
M n decreased with increasing MMT content, which
proves that almost all nylon polymerization was initiated
by 12-Mt in the interlayer spaces. Assuming that only
COOH is an initiator and R nylon 6/12-Mt,
M n 1:04 103 R 216
Figure 3.
Basal spacing vs. carbon number of amino acid.
www.mme-journal.de
(1)
The M n calculated from Equation (1) (dotted line) and

obtained from experimental results (*, solid line) are
shown in Figure 6. The gradient of the experimental data is
somewhat low but both are in good agreement.
Dispersion of silicates in NCH was measured by XRD
and transmission electron microscopy (TEM). NCH
powder was used for XRD, and NCH powder, pressmolded and cut with a microtome, was used for TEM. In
NCH70 and NCH50, the basal spacing peak corresponding
to the d(001) plane was observed in XRD, and its basal
1453
Figure 4.
Conceptual picture of preparation of NCH.
spacing was in good agreement with that from the TEM

result. In NCH30 and NCH15, a weak shoulder was
observed. In NCH5 and NCH2 there was no peak.
Figure 7(a) shows a TEM micrograph of NCH5, which
proves that the silicates are exfoliated and randomly and
homogeneously dispersed on the molecular level. A
silicate is seen as a black line. When the surface of
NCH5 film is etched and the surface nylon removed,
silicate can actually be seen as a platelet in SEM
(Figure 7(b)).[10]
NCH with less than 8 wt.-% MMT does not show a clear
d(001) peak, and clay is randomly and homogeneously
dispersed. On the other hand, in NCH with over 10 wt.-%
MMT, clay is molecularly dispersed but maintains a
pristine clay structure, and therefore it is difficult to
designate it as exfoliated PCN. In practice, NCH with over

10 wt.-% MMT becomes very brittle. NCH with less than
5 wt.-% MMT is tough.
According to Unitikas patent,[6] they compounded
6-aminohexanoic acid (AHA) or 11-aminoundecanoic
acid (AUA) and MMT, blended with CL, polymerized CL
and obtained a MMT-nylon 6 composite on ten gram
scale. They reported that basal spacing in the composite
was expanded to 2 nm for AHA and 5 nm for AUA.
However, they used 2333 wt.-% MMT to CL for his
nylon-clay composites. Their products were mainly
ceramic-like composites, as in earlier studies. Actually,
their tensile strength of 0.6 mm f mold was about one
third that of pristine nylon 6, contrary to their purpose of
strengthening nylon 6. However, their technology was
Table 1. Analysis of NCHs.
NCH2
NCH5
NCH8
NCH15
NCH30
NCH50
NCH70
12-Mt
Nylon 6
a)
b)
c)
Clay content
CNH2a)
CCOOHa)
M n b)
Basal spacing
wt.-%
105 eq g1
105 eq g1
kg mol1
nm
1.5
3.9
6.8
13.0
26.2
42.8
59.6
78.7
0
3.85
4.86
6.70
8.04
12.6
12.1
6.64
5.69
5.69
9.49
14.4
22.9
44.3
70.6
86.7
5.41
17.2
10.0
6.34
3.80
1.66
0.810
0.466
(0.216)c)
12.1
6.0
4.4
2.6
1.7
From end group analysis.

From CCOOH.
Molecular weight of 12-aminododecanoic acid.
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1454
A. Okada, A. Usuki
Figure 7.
Figure 5.
Concentration of terminal groups in NCH.
historically on the border between conventional composite and PCN.

Although we also started by using large amounts of
MMT, we discovered that a very small amount of clay gives
improved properties. Exfoliation and loss of the ordered
clay structure is an indicator of success in PCN.
We presented NCH prepared by this method, the
mechanical properties of its injection-molded species,
and its XRD and TEM results for the first time at the 1987
ACS Fall Meetings,[2a] and thereafter, the organic/
inorganic hybrid material began to receive significant
attention, especially in the USA.
2.1.2 Wet Polymerization Methods

Wet polymerization method: The manufacturing
method of nylon 6 is aqueous polymerization of CL at
Figure 6.
M n vs. R (nylon 6/12-Mt).
www.mme-journal.de
NCH images: (a) TEM, and (b) SEM after etching.
high temperatures. The reason we used dried 12-Mt was

that we had a goal to extend base-catalyzed reaction
injection molding. The rate of anionic polymerization,
which should be completely free from water, is 107 times
greater than that of acid-catalyzed polymerization[7] and
allowed molding of some specific parts. However, even if
anionic polymerization was performed above the melting
point of nylon 6, complete exfoliation was not always
attained. In the preparation of NCH by this method, the rate
might be controlled by diffusion of giant silicate
molecules.[11] So, in 1987, we changed to aqueous polymerization. The time and cost consumed in drying 12-Mt
became unnecessary. Thus, filtered but hydrated 12-Mt
cake was obtained and blended with CL, and CL was
polymerized. While more than 60 h was necessary for dry
polymerization, it took 1113 h by this method.[12] The
mechanical properties of the product were the same as
those of the material obtained by the dry polymerization
method. From then on, this procedure became a standard
preparative method. NCH5 can be injection-molded under
the same conditions as nylon 6. NCH10 and NCH15 can be
injection-molded only with difficulty due to their high
viscosity.
Mechanical properties (following ASTM D638M) are
shown in Table 2. Compared with pristine nylon 6, addition
of only several wt.-% of clay improved strength, modulus,
and, in particular, heat distortion temperature (HDT).
These properties are saturated at just 5 wt.-% of clay. If
clay content is increased to 8 wt.-%, few improvements are
observed. The 5 wt.-% clay content reminds us of the 5
wt.-% aramide content of Takayanagis molecular composite,[3] while conventional composites contain around
2040 wt.-% of fillers. The anisotropic coefficient of
thermal expansion indicates anisotropy in the orientation
of molecules.
The appearance of NCH is greatly different from that of
pristine nylon 6. NCH2 and NCH5 are more transparent
than nylon 6. The molded test piece of NCH2 and NCH5 is
much smoother than nylon 6 and resembles brilliant,
shining marble or porcelain. Conversely, NCH15 has a very
rough, bamboo-like surface. Actually, like bamboo, the
skin of NCH15 can be peeled off easily from the surface of
1455
Table 2. Mechanical properties of NCHs.

Property
Tensile strength
Elongation
Tensile modulus
Flexural Strength
Flexural modulus
Charpy impact strength (without notch)
Heat distortion temperature
Coefficient of thermal expansion
Comment
Unit
NCH2
NCH5
NCH8
Nylon 6
23 8C
120 8C
23 8C
120 8C
23 8C
120 8C
23 8C
120 8C
23 8C
120 8C
MPa
76.4
29.7
>100
>100
1.43
0.32
107
23.8
2.99
0.75
102
118
97.2
32.3
7.30
>100
1.87
0.61
143
32.7
4.34
1.16
52.5
152
6.3 105
13.1 105
93.6
31.4
2.5
51.6
2.11
0.72
122
37.4
5.32
1.87
16.8
153
68.6
26.6
>100
>100
1.11
0.19
89.3
12.5
1.94
0.29
>150
65
11.7 105
11.8 105
Flow direction
Perpendicular direction
the test piece just by using a nail repeatedly, although the

test piece is flat and not cylindrical like bamboo. If the clay
content is more than 10 wt.-% (4 vol.-%), characteristics of
clay (ceramics) appear strongly, and NCH with more than
10 wt.-% clay is useless as a polymeric material. Also, it is
completely opaque. From NCH70 to NCH2, the XRD and
TEM results show a change, continuous but gradual, from
the intercalated to the exfoliated state, and the dispersion of
silicates also seems to change continuously and gradually
from a very ordered state to a random, homogeneous state.
However, just a glance at an injection-molded specimen
would destroy any illusion that the intercalated type is a
nanocomposite the same as the exfoliated type. Both types
are completely different chemical species. Anyone would
acknowledge that the intercalated type of nanocomposite is
not PCN. In fact standard commercial (optimum) NCH
appears to contain 2 wt.-% (0.8 vol.-%) of clay. The value
corresponds to half of the value with which only all apexes
of silicates touch one another (3.8 wt.-%, as described in
the introduction). That means that all the silicates neither
touch nor are stacked with other silicates, but that they are
separated and dispersed on a molecular level in PCN.
A decrease in gas permeability is observed in PCNs,
which is independent of the type of gas (H2, O2,
H2O, gasoline).[13b] Gas barrier properties are common
among PCNs. Its recycling character is similar to that of
pristine nylon 6 and it can be re-used at least 6 times without
any deterioration.[13c] The fatigue lifetime was about
10 times as long as glass-fiber-reinforced nylon 6.[13d]
Wet lactam polymerization method: 12-Mt was replaced
with MMT organized with CL hydrogen chloride (L-MMT)
in the above wet method. In this study AHA was added to
catalyze polymerization. A large amount of CL was added
to the mixture, and this underwent polymerization to give
NCH (L-NCH) (1988).[14] L-NCH5 was further improved
with respect to strength, modulus and HDT compared to the
product of standard wet polymerization method. The reason
this method showed better results is that the standard
www.mme-journal.de
%
GPa
MPa
GPa
kJ m2
8C
cm 8C1
method gave a co-polymer of nylon 6 and rubber-like nylon

12, although the nylon 12 unit was about 1 mol-%, but the
lactam method gave a nylon 6 homopolymer.
One-Pot polymerization method: Although 12-Mt produced by the standard method is hydrophobic and can be
filtered easily, L-MMT is hydrophilic and was filtered with
much difficulty. Thus, filtration of L-MMT was avoided.
Acid was added to an aqueous suspension of CL and heated
at 250 8C, giving NCH. This process can be carried out in
one vessel, and we named it the one-pot method (1988).[15]
The mechanical properties of one-pot NCH coincided with
those of wet-lactam-method NCH. In this procedure, an
acid with pKa < 3 was needed to complete exfoliation and
obtain good mechanical properties. Mainly phosphoric
acid, which is not a strong acid, was used. However, since
many polymerization vessels are made of stainless steel,
even phosphoric acid might cause corrosion of the vessel.
Thus, this method is not practical in some cases.
In 1992, Yasue et al. of Unitika Ltd. applied for a patent
which claimed that NCH could be made without any acid if
synthetic mica was used instead of MMT.[16] It received
much attention, since this method would not cause
corrosion of the reactor. This seemed superior to Toyotas
one-pot method, which needs an acid of pKa < 3. However,
Yasue et al. later published a paper that stated that
exfoliation did not occur, and good mechanical properties
could not be obtained without using acid of pKa < 3. They
also used phosphoric acid. They reached the same
conclusion as Toyota had reached 4 years before, and
reported that a pKa of less than 3 was critical if the kind of
clay was different.[17]
Diamine addition polymerization method: Modulus
and impact strength (toughness) sometimes have a tradeoff relationship. It was tried to depress exfoliation and
sacrifice modulus in order to improve impact strength.
Divalent cations are likely to cause combination and
aggregation of silicates. One terminal group of NCH is
COOH. We added 1/4-molar, 1/2-molar and equimolar
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A. Okada, A. Usuki
Table 3. Mechanical properties of diamine-modified NCH5s.

Property
Tensile strength
Elongation
Tensile modulus
Flexural strength
Flexural modulus
Charpy impact strength (without notch)
Comment
Unit
NCH-1/4h
NCH-1/2h
NCH-1h
NCH5
23 8C
120 8C
23 8C
23 8C
120 8C
23 8C
120 8C
23 8C
120 8C
MPa
104
33.0
9.10
1.90
0.57
147
30.9
4.20
1.37
77.7
149
93.6
31.4
78.8
1.80
0.46
134
30.3
3.96
1.09
87.1
143
89.9
31.4
>100
1.65
0.56
125
27.9
3.55
0.95
100
142
97.2
32.3
7.30
1.87
0.61
143
32.7
4.34
1.16
52.5
152
%
GPa
MPa
GPa
kJ m2
8C
hexamethylenediamine (HMDA) to the COOH group and

performed standard wet polymerization. The properties of
the products are shown in Table 3 where NCH-1/4h denotes
1/4 molar addition of diamine to COOH. The brittleness
of NCH by this method was improved compared to
standard NCH5. Thus, modification of the terminal group
allows control of properties (1987).[18]
The numbers of stacked silicates of NCH-1h were
counted by TEM (Figure 8). Although both terminals of
nylon 6 were ammonium and any nylon 6 was present as a
bivalent cation, most of the silicate was in monolayer form.
The NCH-1h was fundamentally the exfoliated type, with a
very small amount of the intercalated type.
Polymerization/compounding method: In 1989 Toyota
and Ube Ind. jointly developed a new polymerization and
compounding method (describing in the next section). In
this method, 12-Mt, CL, nylon 6, and water were blended
in a twin-screw extruder, the solvents were removed, and
the product was pelletized.[19] This NCH showed the same
mechanical properties as the standard wet polymerized
NCH.
As mentioned before, we presented NCH for the first

time at the 1987 ACS Fall Meetings, and NCH began to be
known from that time. We also reported NCH at the 1989
MRS Fall Meetings (November 1989) with new knowledge
from 1987.[20] As the session symposium name was
Polymer-Based Molecular Composites, which fit
exactly with NCH for its audience, our presentation drew
much attention, and after that time research on PCN began
to expand surprisingly rapidly worldwide. Although filler
content is conventionally around 2040 wt.-%, that fact
that just a few wt.-% of filler can improve polymer
properties while more than 10 wt.-% filler can cause them
to deteriorate seemed astonishing to polymer scientists and
engineers.
Interestingly, Ube Ind. had begun to manufacture NCH
at that time, and we launched a passenger car named
Starlet with an NCH timing belt cover in the very next
month, December 1989.[21]
During the early period, when interest in hybrid
materials was not high (the term nanocomposite was
not generally used, and appeared in a major journal in the
polymer field for the first time in 1990, as mentioned
before), we made up, jointly with Ube Ind., a wide and
exclusive PCN patent network including almost all
polymeric materials, preparations, polymer blends and
applications by 1990. We had licensed nylon-based
nanocomposite patents to several American, European
and Japanese leading nylon-manufacturers by 2002.[22]
The major application of NCH is automotive parts and
household electrical appliances. In these products, high
strength, high heat resistance, high gas barrier properties,
Table 4. Mechanical properties of NCH by AlliedSignal.
Property
Figure 8.
Clay content
Organic modifier
Tensile strength
Elongation
Tensile modulus
Heat distortion
temperature
Numbers of laminated layers.
Comment Unit
www.mme-journal.de
RT
RT
RT
NCH
2.95
Dibenzylamine
MPa
80
%
44
GPa
3.37
8C
72
Nylon 6
66
26
2.41
55
1457
Table 5. Mechanical properties of NCH by compounding methods.

Property
Comment
Clay content
Organic modifier
Preparative method
Tensile strength
Tensile modulus
23 8C
23 8C
Unit
NCH
NCH
Nylon 6
MPa
GPa
8C
1.8
C18-amine
Dry compound
82
1.41
135
1.6
Wet compound
82
1.38
102
Polymer
69
1.1
75
good recycling characteristics, a long lifetime, high

smoothness, paint ability and weight savings are advantageous. The other main application is food-packaging film,
which makes use in particular of the high gas barrier
properties and tensile strength of NCH. Applications in the
future are expected to utilize fire retardancy (FR).
2.1.3 Compounding Methods

Dry compounding method: Production of NCH by
polymerization methods is limited to large nylon manufacturers. It was natural for most users to make NCH by
compounding nylon 6 and clay, as for conventional
composites. In 1991, Maxfield et al. of Allied Signal (now
Honeywell) obtained a composite by blending organized
clay and nylon 6 with shear stress over 10 s1.[23] The
properties in their EP patent are shown in Table 4. In
comparison to polymerization, the improvement compared
to nylon 6 was small, and it is thought that the reason for
this was the absence of exfoliation, although there was no
TEM micrograph available.
In 1999 Liu et al. obtained an exfoliated composite by
compounding organic clay and nylon 6 using a twin-screw
extruder at 30 rpm and by increasing the temperature from
180 8C at the hopper to 220 8C at the die.[24] Improvement
was seen compared to those of AlliedSignal, but tensile
strength and HDT are inferior to those of wet polymerization.
In 1998 completely exfoliated NCH was at last obtained
by a compounding method using a twin screw extruder,
under optimum conditions of pressure and shear energy as
Table 6. Mechanical properties of NCH by Singh.

Property
Comment
Unit
NCH
Nylon 6
MPa
GPa
MPa
GPa
J m1
4.0
Tetraphenylphosphonium
107
2.1
150
0.2
26.0
60
1.1
93.5
2.4
28.0
8C
112
62
Clay content
Organic modifier
Tensile strength
Tensile modulus
Flexural strength
Flexural modulus
Notched Izod
impact strength
Heat distortion
temperature
RT
RT
RT
RT
RT
www.mme-journal.de
well as NCH produced by polymerization methods.[25] The

properties are shown in Table 5.
Producing NCH by a compounding method was
successful 13 years after the polymerization method.
Three months later, Singh et al. of Triton Systems, Inc.,
obtained NCH by dry compounding using MMT modified
with tetraphenylphosphonium salt, which is a rather
expensive reagent (Table 6).[26]
With the dry compounding method, it has become
possible to produce many nanocomposites from homopolymers and co-polymers of nylon.
Wet compounding method: In order to lower the cost of
NCH, compounding pristine MMT, nylon 6 and water in a
twin screw extruder to give an exfoliated composite was
tried.[27] However, the HDT of the sample was 30 8C lower
than that of the dry compounding method, while the
strength and modulus were similar (Table 6). This method
was unsuccessful in producing NCH.
2.1.4 Structure and Reinforcement

Mechanism of NCH
So far we have dealt with NCH using MMT as clay. Here
we describe NCH made from other clays such as synthetic
fluoromica, saponite, and hectorite with clay contents of
28 wt.-% by standard wet polymerization.[28] For any
clay, the effect of reinforcement was saturated at 5 wt.-%.
The properties of NCH with 5 wt.-% of different clays are
shown in Table 7. Among various clays, the effect of
reinforcement is as follows: MMT > mica > saponite >
hectorite.
Based on titration results, we consider that the terminal
ammonium NH
3 of nylon 6 is bound to silicate and that
the other terminal COOH is free. About 20 000 nylon
molecules are bonded to silicate, and silicate works as a
crosslinker, as shown in Figure 9. The assembled
molecular weight is 200 million (Figure 9).
We deduced from this that the ionic bond strength
between silicate and the terminal ammonium ion is
important. To evaluate the bond strength, we prepared
15
N-labeled glycine intercalated between silicates as
model compounds of NCH and studied 15N CP-MAS
NMR spectra of them. The spectra are shown in Figure 10.
The chemical shifts of glycine-clay composites with
glycine hydrogen chloride (completely ionized ammo 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1458
A. Okada, A. Usuki
Table 7. Mechanical properties of NCHs with a variety of clays (5 wt.-%).

Property
Unit
NCH/MMT
NCHM/mica
NCHP/saponite
NCHH/hectorite
Nylon 6
MPa
97.2
32.3
7.3
1.87
0.61
152
61.1
63.6
93.1
30.2
7.2
2.02
0.52
145
57.2
59.6
84.7
29.0
>100
1.59
0.29
107
51.5
53.4
89.5
26.4
>100
1.65
0.29
93
48.4
50.4
68.6
26.6
>100
1.11
0.19
65
70.9
70.9
Clay
Tensile strength
Elongation
Tensile modulus
23 8C
120 8C
23 8C
23 8C
120 8C

Heat of fusion
Heat of fusion
%
GPa
8C
J g1
J g1nylon
nium) and HMDA (neutral nitrogen) are summarized in

Table 8.
These results show that the nitrogen peaks of glycine
between clay layers are shifted towards low field compared
to neutral nitrogen, and that they have a partial positive
charge (d) and are partially ionized. Among the clays, the
magnitude of the partial positive charge is as follows:
MMT > mica > saponite > hectorite. This order agrees
with the mechanical properties. The moduli at 120 8C
vs. chemical shifts are plotted in Figure 11.
The results strongly indicate that chemical bond strength
directly affects macroscopic mechanical properties.[29]
The results also explain why the composites which
Yasue et al. prepared without acid,[16,17] and the composite
which we prepared by the wet compounding method using
pristine MMT,[27] did not show good properties. The
chemical bond between polymer and silicate is indispensable in PCN, in addition to exfoliation and random and
homogeneous dispersion.
Then, the GC-MS spectrum of NCH was measured. It
was considered that ADA was bound to silicate and the CL
molecules would attach one after another by ring opening
polymerization; we expected the spectrum to resemble that
of the nylon 6 homopolymer, except for the terminal nylon
12 unit. A detailed fragmentation study of the spectrum
indicated that the nylon 12 unit was not at the terminal but
inside the nylon 6, so that the spectrum was that of
co-polymer of nylon 6 and nylon 12.[29] This means that
the NH
3 group of the nylon 12 unit originally bound to
silicate can freely exchange with other NH

3 and/or NH2
groups at the polymerization temperature (around
250260 8C) and that silicate is a weak crosslinker which
undergoes bond scission with organic moieties.
Figure 12 shows the melt viscosity vs. shear rate of
NCH2 and nylon 6. At lower shear rates, the melt viscosity
of NCH is higher than nylon 6 and NCH is more restricted,
but at higher shear rates (conditions of injection molding)
both viscosities are very similar, which means that the bond
between clay and nylon 6 undergoes scission under the
molding conditions. We said that the apparent M n of NCH
is 200 million at room temperature, but it lowers to about
13 00015 000, the same as nylon 6, both at 250 8C and at a
shear rate of 104 s1. Thus, NCH2 and NCH5 can be
injection molded under the same conditions as pristine
nylon 6.
Figure 9.
Figure 10.
Crosslinking of nylon molecules by a silicate.
www.mme-journal.de
15
N-chemical shift of intercalated glycine.

1459
Table 8.
15
N NMR chemical shift of model compounds.

da)
Compound
ppm
ClNH
3 CH2COOH
Montmorillonite NH
3 CH2COOH
CH
COOH
Mica NH
2
3
Saponite NH
3 CH2COOH
Hectorite NH
3 CH2COOH
HMDA
a)
ppm relative to
15.6
11.2
9.4
8.4
8.3
7.0
15
NH4NO3.
NCH is very anisotropic, as seen from thermal expansion coefficient in Table 2. These results excited our
interest in the orientation of both clay and nylon 6 in NCH.
We studied a 3 mm thick injection-molded bar, which is a
standard shape for tensile testing,[30] conducting XRD
measurements while cutting from the surface (0 mm) into
the center (1.5 mm) in detail. Figure 13 shows six
diffraction patterns for two specimens of the surface area
(00.5 mm in depth) and inner area (0.51.5 mm in
depth). The diffraction photographs are terminated through
(thru)-, edge-, and end-view patterns with the x-ray beam
incident on the NCH bar along the x-, y-, and z-axes. In the
edge- and end-view patterns of the surface and inner layers,
a pair of strong streaks can be seen in the horizontal (x)
direction from the center, which suggests a planar
orientation of silicates to the bar surface. The streaks in
the end-view of the inner layers become slightly broader in
the azimuthal direction, suggesting the degree of planar
orientation is somewhat broader than the surface area.
In NCH, nylon 6 is a g-form crystal, whose orthorhombic lattice is shown in Figure 14.
Figure 11.
Tensile modulus at 120 8C vs. chemical shift.
www.mme-journal.de
Figure 13 shows that nylon 6 crystallites have a preferred

orientation in both the surface and inner layers of the NCH
bar, since the edge- and end- view patterns show arc-like
reflections. g-form nylon 6 crystals have three XRD
peaks, 2u 12.5, 23.1, and 24.98, assigned to the (002),
(110), and (020) reflections. They correspond to the chain
axis plane, the zigzag plane of the carbon backbone plane,
and the hydrogen-bonded sheet plane. Ordinarily, the (110)
and (020) peaks are observed as one peak.
We measured the XRD peaks of the (002) and (020)/
(110) reflections from the surface to the center (1.5 mm),
gradually cutting the bar sample. The intensities of the
(002) reflection profile and the (020)/(110) reflection
profile are shown in Figure 15(a) and (b), respectively.
These results show that the nylon 6 axis is parallel to the
surface, although it is randomly oriented within the bar
plane near the surface. The axis is perpendicular to the bar
surface from 0.51.2 mm from the surface, and becomes
random in the center, from 1.21.5 mm. The orientation
of silicates and nylon axes in each direction is illustrated in
Figure 16.
Figure 12. Melt viscosity of NCH (clay content: 2 wt.-%) vs.

shear rate.
1460
A. Okada, A. Usuki
Figure 13.
X-ray diffraction photograph of injection molded NCH test piece.
While the pristine nylon 6 bar showed no axis orientation in any area, NCH shows very peculiar orientations of
both silicate and polymer axes. The fact that the orientation
of silicates, which are more rigid than in nylon 6, is parallel
to the flow direction explains the decrease in the thermal
expansion coefficient for that direction (Table 2). The
orientation of the silicate and nylon 6 molecular axes
parallel to the surface on the skin surface may explain the
smooth surface of the bar, which is similar to brilliant,
shining marble or porcelain.
Gilman et al. found that NCH5 had revolutionary fire
retardant (FR) properties,[31a] and showed that the peak
heat release rate is decreased by 63% compared to nylon 6.
They explained that silicate works as an insulator and as a
mass transport barrier for volatile products from the
decomposition of nylon 6. Another advantage is that clay
does not cause deterioration of polymer properties, instead
improving them, while other FR additives have a negative
effect. In addition, clay does not produce hazardous
Figure 14.
products such as carbon monoxide. Gilman et al. published

many reports on FR properties of various PCNs.[31bd]
2.2 Other Aliphatic Nylon-Clay Nanocomposites

Nylon 66 is prepared from HMDA and adipic acid. It had
been difficult to prepare completely exfoliated nylon
66-clay nanocomposites by polymerization methods, since
diamine is likely to cause aggregation of silicates.[18] In
1998 a nylon 66-clay nanocomposite was obtained by the
compounding method, along with NCH.[25] TEM observations proved that it was exfoliated, and tensile strength
increased from 75 (pristine nylon 66) to 81 MPa with
loading of 1.6 wt.-% clay. In 2002, Liu et al. also prepared
nylon 66-clay nanocomposites by the compounding
method using clay co-intercalated with quaternary
ammonium salt and epoxy resin.[32] They confirmed
exfoliation using XRD and TEM and demonstrated
improvement of properties. Their nylon 66-clay nano-
g-Nylon 6 crystal and its orthorhombic lattice.
www.mme-journal.de
1461
Figure 15.
surface.
Peak intensity of reflection of g-nylon 6 in NCH from depth of the molded
composite containing 5 wt.-% clay showed improvements

in tensile strength from 78 (pristine nylon 66) to 98 MPa,
notched Izod strength from 96 to 146 J m1, and HDT
from 75 to 164 8C. Wu et al. obtained exfoliated nylon
1012 by condensation polymerization and reported
increases in strength and gas barrier properties.[33] Liu
reported the preparation of an exfoliated nylon 11-clay
nanocomposite with excellent mechanical and thermal
properties.[34]
composite is suitable for drink bottles. As a bottle for beer,

a multi-layer PET/MXD6-clay nanocomposite bottle has a
shelf life seven times as long as a PET bottle and three
times as long as a multi-layer PET/MXD6 bottle. He
reported that the multi-layer PET/MXD6-clay nanocomposite bottle is not hazardous, and therefore its market can
be expected to expand rapidly.
3. Polyimide (PI)-Clay Hybrids

2.3 Aromatic Nylon-Clay Nanocomposites
Nylon MXD6, made from m-xylylenediamine and adipic
acid, has a high gas barrier property compared with nylon 6
or nylon 66, and has a special market position. Nylon
MXD6-clay nanocomposites was prepared. Maruo of
Mitsubishi Gas Chemical demonstrated exfoliation by
TEM, and the high gas barrier properties are shown in
Table 9, although clay content was not disclosed.[35]
In particular, the gas barrier properties are higher than
those of poly[ethylene-co-(vinyl alcohol)] (EVOH) at
greater relative humidity so that the MXD6-clay nano-
Figure 16.
test piece.
Polyimide-clay hybrid films were prepared by: 1) blending N,N-dimethylacetamide (DMAC) solutions of 4,4dimethylaminodiphenyl ether and pyromellitic anhydride;
2) addition of DMAC suspension of MMT intercalated with
dodecylammonium salt (C12-MMT) to the above solution;
3) casting of the mixture to a glass plate; and, 4) heating at
300 8C for 2 h, as shown in Figure 17.[36]
To prepare PI hybrid, no shear is needed, but the clay is
perfectly exfoliated and the transparency of the hybrid film
is almost the same as that of pristine PI. Silicates in the film
are oriented completely parallel to the surface. While we
tested nine kinds of long-chain ammonium salt, only
Orientation of montmorillonite and nylon 6 crystallite in the molded NCH
www.mme-journal.de
1462
A. Okada, A. Usuki
Table 9. Properties of MXD6 nanocomposite films.

Property
Tensile strength
Elongation
Tensile modulus
Haze
O2 permeabilitya)
CO2 permeabilitya)
Water vapor permeabilitya)
a)
Comment
Unit
MXD6 nanocomposite
MXD6
RT
RT
RT
RT
23 8C, 60% RH
23 8C, 60% RH
40 8C, 60%RH
MPa
%
GPa
%
cm3 mm m2 d1 atm
cm3 mm m2 d1 atm
g mm m2 d1
83
2.9
3.5
1.5
0.02
0.10
0.28
85
3.3
3.1
1.3
0.08
0.20
0.62
Thickness 0.03 mm Maruo, 1994.
C12-MMT gave an exfoliated product. The choice of

organic modifier is always critical. A decrease in gas
transparency and decrease in thermal expansion coefficient
were observed. The gas barrier property can be explained
by a model where a gas molecule detours around the clay
layers, as shown Figure 18, using Equation (2).[37]
Pc =Pp 1=1 L=2WVf
(2)
Here, Pc and Pp are the permeability constants of the

PI-clay hybrid and the pristine PI, and L, W and Vf represent
the plate length, width and volume fraction of clay,
respectively.
We then prepared PI-clay hybrids using various clays

and found that gas permeability preeminently depends on
the kind of clay (Figure 19). For example, addition of 2
wt.-% mica gave a gas permeability of one-tenth that of
pristine PI.[38]
When L for each silicate was measured and substituted
into Equation (2), the calculated values agreed very well.
Pinnavaia et al. prepared PI-clay nanocomposites in a
similar fashion to ours. They reported that aggregation was
extensive, but confirmed the effect on the gas barrier
property of CO2.[39] Morgan et al. reported preparation of a
poly(ether imide)-clay nanocomposite, but it was just an
intercalated composite due to the difficulty of synthesis.[40]
Figure 17. Preparation of polyimide clay hybrid film.

www.mme-journal.de
1463
Figure 18.
film.
Detour model of gas diffusion in polyimide clay hybrid
4. Polyolefin-Clay Nanocomposites
4.1 Poly(propylene) (PP)-Clay Nanocomposites
Poly(propylene) is the most widely used polymer in the
automotive industry and in commodity products. While it
is less expensive, its mechanical and thermal properties are
inferior to engineering plastics such as nylons. However,
there is a strong need to improve the mechanical properties
of poly(propylene), owing to its low price. After nylon 6
was successfully developed, various research efforts were
made worldwide to reinforce PP using clay, but to the best
of our knowledge no successful examples of reinforced
PP-clay nanocomposites (PPCN) have yet been reported.
Since clay is hydrophilic and PP is hydrophobic, there is
enormous difficulty in making PPCN. In order to do this, a
different method was applied from that of nylon and PI
synthesis, using a third component, a compatibilizer with a
functional group and polyolefin unit. Specifically, we
chose maleic anhydride (MA)-grafted PP oligomers
(PP-MA). The PP-MAs we used, from Sanyo Chemical
Ind., Ltd. are shown in Table 10.
First of all we prepared MMT organized with octadecylammonium salt (C18-MMT), and compounded
PP-MA using an extruder, successfully giving MMTintercalated PP-MA. This was then compounded with
pristine PP, also using an extruder. All final products
contained 5 wt.-% of clay. Among the products, PPCN
(U1010 C18-MMT) had a peak of 6.0 nm in XRD,
and PPCN (U1001 C18-MMT) had a shoulder around
45 nm but no clear peak, while C18-MMT had a peak at
2.2 nm. TEM micrographs of PPCN (U1001 C18-MMT)
are shown in Figure 20; these indicate that exfoliation was
just attained. Compounding of C18-MMT, PP-MA and PP
at the same time also proved to give an exfoliated product.[42]
Observation of photographs from a polarized microscope shows that there was macro-phase separation in
PPCN (U1010 C18-MMT) but PPCN (U1001
C18-MMT) had no such separation and was homogeneous.
The TEM and microscope studies indicated that while the
MA unit is necessary for exfoliation, its presence in excess
amounts seems to decrease compatibility with the pristine
PP. The relative storage moduli of two PPCN samples to
pristine PP are plotted in Figure 21.
The moduli of both samples were 1.51.8 times as
high as that of the pristine PP from 5080 8C, but at
other temperatures they were lower than that of the
pristine PP. This may be caused by the fact that PPCN
Table 10. Properties of poly(propylene) modified with maleic
anhydride.
PP-MA
U1010
U1001
U1004
Figure 19.
a)
b)
Relative permeability on clay mineral.
www.mme-journal.de
Maleic Anhydridea)
Melting Pointa)
wt.-%
8C
4.5
2.3
2.3
145
154
155

M w M w b)
30 000
40 000
80 000
Catalog data.
Catalog data determined by GPC measurements.
1464
A. Okada, A. Usuki
Figure 20.
TEM of PP-clay nanocomposite.
contains oligomers. The tensile strength of PPCN was

almost the same as that of PP. A study using PP oligomers
with terminal OH groups was also carried out.[43,44]
In conclusion, the preparation was accomplished of an
exfoliated nanocomposite even with a hydrophobic PP.
Sun et al. prepared PPCN using organized clay and
methylaluminoxane (MAO) and a transition metal catalyst
by a polymerization method, and demonstrated exfoliation
by XRD and TEM. However, the mechanical properties
were not described.[45]
4.2 Polyethylene (PE)-Clay Nanocomposite

In the preparation of a polyethylene-clay nanocomposite
(PECN), in contrast with PP, the polymerization method
preceded the compounding method. Muelhaupt et al.
polymerized ethylene with organized clay using transition
metal catalysts such as Zr, Ni, or Pd activated with
MAO.[46] Shin et al. reacted silicate with vinyl alcohol and
tried to obtain PECN using the vinyl group as an initiation
terminal of polymerization.[47] Jin et al. also tried to obtain
PECN by polymerizing ethylene with organized clay using
a Ziegler-Natta catalyst.[48] However, in these cases the
dispersion of clay was insufficient, and they were

unsuccessful in obtaining homogeneously dispersed
PECN.
While the synthetic method was not successful, PECN
was prepared by compounding C18-MMT, PE and PE-MA
as a compatibilizer using an extruder as PPCN.[49] PE-MA,
Fusabond MB-226D (DuPont, 0.9 wt.-% MA) and pristine
PE, KF380 (Japan Polyethylene Corp.) were used. The
samples prepared are shown in Table 11.
The XRD and TEM results (Figure 22) indicate that
PECN was homogeneously exfoliated.
The properties of PECN are summarized in Table 12. In
contrast to PPCN, because the strength and modulus of
PE-MA are higher than those of PE, the reinforcement
effect of PECN was better than PPCN.
We consider that compounding using a compatibilizer is
a key technology for preparation of polyolefin-clay
nanocomposites.
4.3 Other Polyolefin-Clay Nanocomposites

Giannelis et al. prepared intercalated PCN by direct
compounding of organized clay and polystyrene (PS), but
exfoliation was not observed.[50] In contrast, Sogah et al.
succeeded in the preparation of exfoliated PSCN using
living radical polymerization in the interlayer space of
organized clay.[51] GM and Basell announced that their
thermoplastic polyolefin (TPO) with 23 wt.-% clay had
stiffness equal to TPO with 2535 wt.-% talc, and they
commercialized a step assist for van-type cars in 2002.
Although they claimed that the product was a nanocomposite (TPOCN), there was agglomeration of clay and
exfoliation was not completed.[52a] Mehta et al. also tried to
prepare TPOCN, but they reported that their product
contained stacks about 1050 nm thick, corresponding to a
stack of 525 clay platelets.[52b]
A nanocomposite of ethylene-propylene-elastomer
modified MA (EPRCN) was obtained and confirmed
exfoliation was achieved. The storage modulus at room
temperature of the product containing 8 wt.-% clay was
five times as high as that containing the same wt.-% of
Table 11. Polyethylene-clay nanocomposites.
Sample
Figure 21.
Relative storage modulus of PP-clay nanocomposite.
www.mme-journal.de
PE
PE-MA
PE1
PECH1
PECH2
PECH3
PECC
Clay
C18-MMT
C18-MMT
C18-MMT
MMT
Composition
PE
PE-MA
wt.-%
wt.-%
100
0
70
70
70
0
70
0
100
30
30
30
100
30
Clay
wt.-%
0
0
0
5.4
3.5
5.2
5.7
1465
strength or other properties. Large-scale preparations of

cyclic oligomers are expected.
Nanocomposites of poly(L-lactic acid) (PLA), a biodegradable polymer, were reported by Ray et al.[56] However,
PLA has a serious problem a lower HDT in comparison
with PP, a typical commodity polymer. So far, PLACN has
been focused on L-PLA. It is known that a stereo-complex
of L-PLA and D-PLA results in increasing melting points
from 170 to 220 8C for each enantiomer, but blending
both stereoisomers results in the presence of a 170 8C
component. L-PLA in the presence of organized clay was
synthesized and compounded with D-PLA, resulting in a
stereo-complex of melting point 220 8C, without the
170 8C component.[57]
Figure 22.
5. Rubber and Thermosetting

Resin-Clay Nanocomposites
TEM of PE-clay nanocomposite.
5.1 Rubber-Clay Nanocomposites

carbon black or talc, and swelling in hexadecane was
one-fourth that of its counterparts.[53]
4.4 Other Thermoplastic Polymer-Clay

Nanocomposites
Among vinyl polymers, our group and Biasci studied
acrylic resin, and Lee studied PMMA.[54] Sogah also
succeeded in obtaining an exfoliated PMMA nanocomposite using living radical polymerization,[51b] but so far,
measurement of mechanical properties has not been
sufficient. Reports of these properties are eagerly awaited.
Among esters, ring-opening polymerizations between
clay layers were attempted.[55] Huang et al. obtained a
partially exfoliated polycarbonate (PC)-clay nanocomposite. Tripathy et al. obtained an exfoliated-intercalated
PET-clay nanocomposite containing a few aggregates. Lee
et al. tried to obtain a poly(butylene terephthalate)
(PBT)-clay nanocomposite but complete exfoliation could
not be attained, as for PC and PET. In all of these studies,
synthesis of several grams was performed to allow XRD
and TEM measurements, but there is no data yet on
Nitrile rubber (NBR), a co-polymer of butadiene (BD) and

acrylonitrile (AN), is oil-resistant and is used widely for
oil hoses and sealing materials in the auto industry. NBR
is usually reinforced using carbon black (CB), which
decreases its processability because it increases the
Mooney viscosity of the pre-vulcanized rubber as an
indicator. We tried to reinforce NBR using clay. MMT was
treated with a liquid rubber (LR) consisting of oligomer
NBR with two terminal amino groups, HycarATBN (Ube
Ind., M n 3 400, 17 mol-% AN), called LR-Mt. NBR,
Nipol 1042, (Nippon Zeon Corp., 33 mol-% AN), LR-Mt,
sulfur, zinc oxide, and other additives were roll-milled.
Vulcanization was done at 2 mm at 160 8C for 15 min.
Before vulcanization, though the Mooney viscosity
increases with carbon black, it decreased when clay was
used.[58] The nanocomposite was called RCH, and NBR
compounded with pristine MMT was called RCC. TEM
micrographs of RCH showed that the clay was not
completely exfoliated but several silicates were homogeneously dispersed. As shown in Figure 23, 10 wt.-% clay
had the same reinforcing effects as 40 wt.-% carbon black.
Optimization of the dispersion conditions of LR was
continued. We studied the exfoliation conditions of a LR of
Table 12. Properties of polyethylene-clay nanocomposites.

Sample
PE
PE-MA
PE1
PECH1
PECH2
PECH3
PECC
Tensile Strength
Elongation
Tensile Modulus
N2 Gas Permeability Coefficient
MPa
MPa
1013 cm3(STP) cm cm1 Pa1
7.3
9.3
7.510.5
9.4
12.5
7.9
>500
180
>500
>500
>500
155
>500
102
118
99
180
140
157
103
5.26
5.46
5.32
3.79
3.01
3.48
5.48
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1466
A. Okada, A. Usuki
Figure 25.
Figure 23. Storage modulus vs. filler content in NBR-clay

nanocomposite.
NBR without an amino group, HycarCT (Ube Ind., 10, 17

and 27 mol-% AN) and with long chain alkylammonium
salts (C 12, 14, 16 and 18). The results proved that only
the combination of LR containing 10 mol-% AN and
C12-MMT or C14-MMT gave complete dispersion. This
was another example of the need for optimum conditions
for complete exfoliation in all cases.[59] Longer chains do
not always lead to better exfoliation. This method is
promising for reinforcing NBR, and studies are currently in
progress.
Since ethylene-propylene-diene-methylene rubber
(EPDM), shown in Figure 24, has no double bond in
the main chain, it has excellent properties of weatherability, durability to cold and stability by various
chemicals, and so it is used for weather strips and water
hoses in automobiles.
Unlike polyolefins in which MAs can be introduced,
EPDM undergoes gelation due to its double bonds by MA
grafting in the side chain. Therefore, twin extrusion of
C18-MMT and EPDM Esprene 505 (Sumitomo Chem.)
was conducted, then roll-milled after adding sulfur, zinc
oxide, stearic acid and the vulcanization accelerator, and
press-molded under the same conditions as for the NBR
nanocomposite. The tested vulcanization accelerators are
shown in Figure 25.
Among the five accelerators, TS and PZ gave exfoliated
PCN but the other three gave products that were not
completely exfoliated. The reason for this difference has
not yet been clarified. The two EPDM-clay nanocomposites loaded with 4 wt.-% clay were improved in terms of
tensile strength at break, tensile elongation at break and gas
Figure 24.
Structure of EPDM.
www.mme-journal.de
Vulcanization accelerators.
barrier properties.[60] Butyl rubber (IIR) is a co-polymer of

isoprene and isobutene and is used in hoses for vapor
fixation of the refrigerant HFC-134 in air conditioners.
Liang et al. studied IIR nanocomposites, but exfoliation
was insufficient;[61] IIR was modified with MA, then
vulcanized using PZ, as for EPDM, and an IIR-clay
nanocomposite loaded with 5 wt.-% clay was obtained.
Gas barrier property increased by two times compared to
the original IIR.[62]
5.2 Other Thermoset Polymer-Clay

Nanocomposites
5.2.1 Epoxy Resin-Clay Nanocomposites
Pinnavaia et al. prepared epoxy resin-clay nanocomposites
using Epon-828 (Shell), m-phenylenediamine as a crosslinker and C18-MMT, cured by heating, and the basal
spacing increased to 815 nm. This rubbery epoxy resin
containing 5 wt.-% of clay showed increased tensile
strength and the tensile modulus increased by three times
compared to ordinary epoxy resin.[63] As it was in a
rubbery state, the modulus was in the order of MPa; this is
very low compared with plastics, which have moduli of
some GPa, as for nylon 6. Sometimes epoxy resin contains
inorganics such as glass beads, more than polymer itself, as
in the case of IC package resins, and the modulus and
strength of the composite is held by conventional inorganic
fillers.
5.2.2 Phenol Resin-Clay Nanocomposites

There are two types of phenol resins. One is novolac-type
resin, which is cured by using a crosslinking agent such as
hexamethylenetetramine. Choi et al. reported the preparation of a novolac-type resin-clay nanocomposite.[64] The
other type of phenol resin is the self-curing resol-type,
which we studied. Phenol resin-clay nanocomposites
(PRCN) were prepared as follows: 40 g of resol resin
Sumikon PM (Sumitomo Bakelite Co. Ltd.) and 5 g of
organized clay were blended, and then 40 g of glass fiber
and 10 g of carbon black were added, and the mixture was
1467
kneaded at 8090 8C. The product was compressionmolded into test pieces of 4 10 80 mm3 for the flexural
test. Although, among many organized clays, only
C18-MMT could be completely dispersed in the resin,
the flexural strength of PRCN was lower than that of PR,
and the nanocomposite reinforcing effect was not
observed. However, heat resistance was improved. The
heat-resistance properties of PRCN were evaluated by the
following method: the test pieces were kept at 200 8C in a
dry oven and flexural strength was measured at fixed
intervals; strength retention was then compared with the
initial strength. The strength retentions of PRCN and of PR
were plotted against time (Figure 26(a)).
The retention of flexural strength by this PRCN at 500 h
and 1 000 h at 200 8C was significantly higher than that of
the PR. In order to investigate the reason for this, we
measured the penetration of O2 gas by electron probe
microanalysis (EPMA). Depth profiles for oxygen atom
distribution in the PRCN as a function of exposure time are
shown in Figure 26(b), along with profiles of PR. In the PR
sample, oxygen atoms of oxidized PR reached the center of
the test piece by 1 000 h, but in PRCN, these oxygen atoms
were distributed to a depth of about 600 mm but stopped at
700 mm at 1 000 h. In other words, the gas barrier property
of clay suppressed oxidation of the polymer.[65]
6. Nanocomposite Hydrogels (NC gels)

Polymeric hydrogels, especially those composed of
poly(N-isopropylacrylamide), (PNIPA) have attracted
much interest over the last two decades, since, as well
as absorbing large amounts of water, it undergoes volume
changes, absorption and release of materials, and change of
light transparency with external stimuli. Application to
drug delivery systems (DDS), sensors, and actuators have
been well studied.[66a] So far, conventional PNIPA gels
(OR gels) have been prepared with chemical crosslinking,
typically using N,N-methylenebisacrylamide (BIS). OR
gels have two fatal defects: they are mechanically weak
and very brittle, and they show very slow response to
stimuli. The rate of response is inversely proportional to the
square of the gel dimensions, and ca. 10 mm-thick gel
films[66b] and porous gel fibers of ca. 10 mm pore size[66c]
have been fabricated.
Recently, Haraguchi et al. developed a breakthrough
method for solving these two problems simultaneously by
construction of an organic-inorganic network using clay;
this was named NC gel.[67] The NC gel is novel, and
destroys the prevailing common sense on conventional
PNIPA gels (OR gels). Here, NC-gel (made of PNIPA) will
be introduced with reference to its structure (Figure 27),
properties and formation process.
Hectorite, as a clay, was dispersed homogeneously in
water, and in situ radical polymerization of NIPA was
www.mme-journal.de
Figure 26. Retention of flexural strength after heat resistance:

(a) retention vs. exposure time, and (b) distribution of oxygen
from sample surface after exposure.
performed in the presence of clay to give a transparent gel

(NC gel). The polymerization yield was nearly 100%.
Thermogravimetric (TG) measurements proved that the
ratio of clay to polymer in the product agreed with the
initial ratio. The properties of NC gels are summarized in
Table 13 along with those of OR gels.
While OR gel becomes opaque with increasing amounts
of BIS, NC gel is transparent even with increased clay
content. Strikingly, the tensile strength and elongation of
NC gels are rather higher than those of common industrial
rubber, while the tensile modulus is somewhat lower. In
other words, NC gel is a soft and flexible yet tough
material. On the contrary, OR gel was not durable for
testing, being too brittle and weak. NC gels show breaking
energy more than 1 000 times that of OR gels. Their
excellent mechanical properties and changes are shown in
1468
A. Okada, A. Usuki
Figure 28.
Figure 27.
Structure of nanocomposite gel.
Figure 27. The deformation of elongation is illustrated by a

micro-expander model, as shown in Figure 28.
In the 1980s, we attempted to make a soft actuator from
polymer hydrogels of sodium acrylate and BIS, bending the
gel using an electric field. But the gel was too weak and
brittle, so we made a composite gel of sodium acrylate and
crystalline polyvinyl alcohol using repeated freeze-dry
cycles in order to make the gel strong enough as an actuator.
With this method, we made a robot hand that moved in air
and a goldfish swimming in water.[68] Therefore, we can
understand very well what Haraguchi et al. achieved.
In OR gels, the Tg of PNIPA increases with the amount
of BIS used, while NC gels have the same Tg as linear
PNIPA, which indicates that there is little restriction in
NC gels. From the results it is deduced that a very homogeneous organic-inorganic three-dimensionally crosslinked gel is formed using clay layers. As seen for NCH
(Figure 9), silicates work as multi-functional crosslinkers,
Elongated structure of nanocomposite gel.
and specific network structures may be formed. Observation by XRD, TEM and DSC of dried NC gels proved that
silicates are homogeneously dispersed in PNIPA.
NC gels showed a clear change in transparency and
volume around the lower critical solution temperature
(LCST, ca. 32 8C). A reversible change in transparency
was obtained independently of the clay content from
15 wt.-%, in contrast to OR gels (Figure 29). Here the
size of all samples was 26 mm (35 mm in length).
Shrinking speed is critically important for application in
a DDS or as an actuator. NC gels showed much higher
shrinking speeds than OR gels. While OR gels took one
month to shrink, NC gels completed shrinkage in about
10 min, as shown in Figure 30. Here, the sample size was
5.5 mm in diameter 30 mm in length.
NC gels have overturned the conventional wisdom of
hydrogels. They have been released from their traditional
limitations, and are expected to be used widely for many
applications which were previously thought impossible.
Coupled with micro-fabrication techniques,[66b,c] hydrogels are expected to be useful as practical materials.
Table 13. Properties of nanocomposite and organic gels.

Properties
Unit
NC1 NC2 NC3 OR1 OR2
Transparency at 1 8C
%
98
94
96
94
4
71
48
29 14
Swelling Ratio
Ww/Wdry 110
Tensile Strength
kPa
27
69
88
Elongation
%
1 308 1 112 1 035
Tensile Modulus
kPa
1
4
8
Tg of Dried Gela)
8C
141 141 142 145 152
a)
Tg of linear polymer(PNIPA) was 142 8C.
Figure 29.
www.mme-journal.de
Temperature dependence of transparency.

1469
Figure 30.
De-swelling kinetics after transferring from 20 to 40 8C.
7. Liquid Crystal-Clay Composites

We have described the characteristics and properties of
PCNs, in which silicates are dispersed randomly and homogeneously on a molecular level, mainly with reference to the
aim of producing high-performance structural polymers
with high strength, modulus and barrier properties. In this
section we will describe the preparation and structure and
novel memory effects of liquid crystal-clay composites
(LCC). Although we tried to prepare liquid crystal-clay
nanocomposites, we could not obtain exfoliated nanocomposites but only intercalated-type liquid crystal-clay composites. However, it was found that these showed novel
memory effects. Liquid crystal molecules are known to form
self-assembled domains and show optical anisotropy. They
are liable to be affected by solid surfaces, as seen in the
effect of orientation of super-twisted nematic (STN) liquid
crystal molecules by rubbing of the surface. We were
interested in whether they would show interaction with
silicate surfaces. We describe here the new phenomenon of
liquid crystal-clay composites.
5CB (Merck) which is a nematic liquid crystal at room
temperature and a liquid crystal showing two-frequency
addressing, DF-05XX (Chisso Co.) were used, as shown in

Figure 31.
5CB shows positive dielectric anisotropy from 1
20 000 Hz, and is aligned parallel to the applied
electric field. In contrast, DF-055XX, a mixture of the two
compounds shown in Figure 31(b), is a two-frequencyaddressing liquid crystal (TFALC). The alignment of
TFALC can be controlled by changing the applied electric
field. TFALC has positive as well as negative dielectric
anisotropy, as shown in Figure 32. Also, TFALC, in the
presence of a small amount of salts, exhibits a dynamic
light scattering (DS) effect when subjected to an electric
field whose frequency is near its crossover point (f0) or
slightly higher than f0. (Regime II of Figure 32).
Representatives of the prepared LCC samples are
presented in Table 14. Organic ammonium ions were
selected, as they were expected to show affinity with liquid
crystals.
A typical procedure for preparing LCC is as follows:
0.0181 g of 2(CNBPC11)M (see organic modifier in
Table 14) was dispersed into DMAC and mixed with 1.0 g
of DF-05XX, and the mixture was mechanically stirred;
DMAC was then removed in vacuum at 50 8C for 10 h to
Figure 31. Structures of liquid crystals: (a) 5CB, and (b)

DF05-XX (blend of two compounds).
Figure 32. Dielectric anisotropy depending on frequency of

DF05-XX.
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1470
A. Okada, A. Usuki
Table 14. Liquid crystal clay composites.
Figure 33.
shear.
Transmittance change of LCC(5CB)CNBPC4M by electric field and
www.mme-journal.de
1471
Figure 34.
Schematic model of LCC(5CB)CNBPC4M.
yield a white liquid pasty composite, LCC (DF-05XX)

2(CNBPC11)M. While pure DF-05XX is in a homogeneous and transparent state, the prepared LCC has
microdomain structures and caused strong light scattering.
This was explained by the fact that organized clay has a
strong interaction with liquid crystals, causing the formation of microdomain structures. Optical polarized
micrographs of the isotropic LCC(DF-05XX)2(CNBPC11)
M at 140 8C showed white spots a few micrometers in size.
These are aggregates of silicates. In the nematic state of
LCC, very fine structures of a similar size were observed.
The texture results from very small domains of liquid crystal. In TEM micrographs of LCC, monolayers and stacks of
several layers of silicate were observed, but the composite
was not exfoliated like PCN. When 5CB and CNBPC4M
(see organic modifier in Table 14) were used instead, giving
LCC(5CB)CNBPC4M, observation of optical polarized
micrographs of the LCC showed the same results as those of
DF-05XX2(CNBPC11)M. Both pure liquid crystals

did not show such fine textures but had homogeneous
structures.
Clay is considered to induce multi-domain structures
in LCCs. The electro-optical properties of LCC(5CB)
CNBPC4M were measured in a cell with ITO electrodes
with a gap of 12 mm, as shown in Figure 33.[69]
The initial cell was opaque but when an electric field
(60 Hz/50 V) was applied, the cell became transparent in
50 ms. When the field was switched off, the cell remained
transparent with a slight decrease in transparency. The
transparency was maintained for six months, and the
composite did not return completely to the initial state, but
the cell returned to the initial scattering state when one
electrode was dislocated with shear. This memory effect
indicates a strong interaction between LC and organized
clay. An XRD study of the cell in the memory state showed
a peak indicating 2.9 nm basal spacing, which means that
Figure 35. Transmittance change of LCC(DF05-XX)2(CNBPC11)M by two

addressing electric fields.
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1472
A. Okada, A. Usuki
Figure 36.
field.
Schematic model of LCC(DF05-XX)2(CNBPC11)M by electric
exfoliation was not in existence, but that the stacked

silicates were randomly arranged. A schematic representation is shown in Figure 34. However, pure 5CB is always
transparent, with or without an electric field, and this did
not show a memory effect.
If LCC is applied to a device such as a display, it is
desirable that the two states, opaque and transparent, may
be switched only by electric fields without shear. This was
realized by using LCC(DF-05XX)2(CNBPC11)M,
derived from a TFALC, with addition of a slight amount
of tetrabutylammonium bromide salt. The change in light
transparency of the cell is shown in Figure 35.[70]
In this case also, the initial cell was opaque, and when an
electric field (60 Hz/50 V) was applied, the cell became
transparent in 50 ms (on-state I). When the field was
switched off, the cell remained transparent (memory state
I). When a high field (1.5 kHz/100V) causing DC was
applied, memory state I was cancelled and the cell became
opaque (on-state II) in 50 ms. When the field was switched
off, the opaque state was maintained (memory state II). The
result fulfilled the criteria of changing from transparent to
opaque states, and vice versa, simply by changing the
electric field. A schematic representation is shown in
Figure 36. In this case the TFALC feature of DC was

utilized, in which turbulence is caused by a high electric
field. For pure DF05-XX, transparent and opaque states
were achieved, but there was no memory effect.
Although the details are omitted, the difference between
the two states (transparent and opaque) depends largely on
the organized clay used.
8. Introduction of a Layered Microdomain

Structure in Block Co-Polymer by Clay
We have described PCNs of homopolymers and random
co-polymers. From these we learned that clay can be
dispersed randomly and homogeneously, even in polyolefins, by grafting of MA. In the preceding chapter we also
learned that clay can cause formation of microdomains in
LC. Therefore, it was interesting to investigate what kind of
structure clay brings to block co-polymers which already
contain microdomains. An ABA-type co-polymer, polystyrene-block-poly(ethylene-co-butene)-block-polystyrene
(SEBS), Taftec H1030 (Asahi Kasei Corp.) was used.
SEBS and 5 wt.-% C18-MMT were compounded, giving
Figure 37. TEM dyed with RuO4: (a) SEBS, and (b) SEBS-CN; black line (with a white
arrow) indicating silicate, gray PS and white PEB domain.
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1473
Figure 38.
Enlarged TEM of SEBS-CN.
SEBSCN pellets. XRD measurements showed that the

2.2 nm peak of C18-MMT increased to 3.3 nm and that
it was an intercalated composite. TEM stained by RuO4
of the pristine SEBS shows segregated microdomains
(Figure 37(a)): gray areas are PS microdomains, which are

more susceptible to staining by RuO4 than poly (ethyleneco-butene) (PEB) microdomains.
In contrast, the TEM micrograph of SEBSCN
(Figure 37(b))[71] exhibits an ordered and layered microdomain structure in which a black layer shown with a white
arrow is a silicate, a gray one is PS attached to silicates, and
white ones are PEB. Figure 38 shows a more wide-range
TEM of SEBSCN. Layers of approximately 10 and 150 nm
in ordered block structures may be observed.
The reason why layered structures are formed is the
difference in affinity for silicates between the two blocks.[72]
That is to say that C18-MMT can intercalate into PS[50a] but
not into PEB, which is a polyolefin,[41] so PS is attached to a
silicate, followed by PEB, and two layered blocks are formed
in turn. Figure 39 illustrates schematic phase structures of
SEBS and SEBSCN.
SEBS was grafted with MA and then compounded with
C18-MMT, giving SEBS-MACN. XRD and TEM measurements showed that SEBS-MACN was an exfoliated
nanocomposite while SEBSCN was an intercalated one.
This means that silicate has more affinity with PEB-MA
than PS and that most silicates are homogeneously dispersed into PEB-MA of SEBS-MACN while they are
dispersed in marked contrast into PS of SEBS-CN
with stacked layers. TEM stained by RuO2 of SEBSMACN shows segregated microdomains similar to SEBS
(Figure 37(a)). The disappearance of silicate stacked layers
(the arrow of Figure 37(b)) in SEBS-MACN causes the
disappearance of the layered microdomain structure. Studies
of other block co-polymer nanocomposites are now in
progress.
Conclusion
Based on twenty years of research on polymer-clay nanocomposites, the following conclusions may be drawn:
A. Titration, NMR, GC-MS, and detailed XRD results
revealed that PCN is an entirely new chemical species
and not just a composite. The first applied PCN
material was a nylon 6-clay hybrid (NCH), the properties of which were so eminent that passenger cars
containing a NCH timing belt cover were launched
into the market within four years (1989).
B. Addition of only a small amount of clay to pristine
polymers imparts the following characteristics to the
resultant PCN:
Figure 39. Schematic models of micro-domain: (a) SEBS, and

(b) SEBS-CN.
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1.
2.
3.
4.
5.
6.
Increases in tensile strength and modulus;

Large increase in HDT;
Increase in gas barrier property;
Increase in smoothness and paint ability;
Increase in transparency; and,
Similar recyclability.
1474
A. Okada, A. Usuki
Conversely, addition of higher amounts of clay did

destroy exfoliated nanocomposite structure and deteriorate
these characteristics, and the toughness in particular
decreased.
G. Research on liquid crystal-clay composites (LCC) has

proven the ability of clay to control the structure and
properties of low-molecular-weight organic compounds by controlling the layers of block co-polymers.
C. The following properties of PCN, among others,

are superior to those of glass fiber-reinforced composites:
More new findings on the effects of clay in controlling

structure and property improvement in polymers and
organic compounds are expected. This may expand into
new science and new applications. We will finish this
article by expressing our hope that many more scientists
become interested in the development of PCN.
1. Notable weight saving;

2. Considerable increase in usage lifetime;
3. Outstanding increase in smoothness and paint
ability;
4. Increase in transparency; and,
5. Increase in recyclability.
D. Later, polymers other than nylon 6 were used to prepare
polymer-clay nanocomposites, and their usefulness has
been verified. Initially, research on PCN was restricted
since it could not be produced by polymerization
methods. However, after the development of compounding methods using a twin-screw extruder,
research on PCN has become more extensive. Thus,
the number of papers about PCN exceeded 500 in 2005
alone, according to WOS. Nevertheless, to date, only
nylon-clay nanocomposites have been manufactured;
these are used in industrial products such as automotive
parts, food packaging and electrical products. This may
be attributed to the difficulty in obtaining molecularlevel dispersion of hydrophilic clay and mostly hydrophobic polymers. Polymers in which silicates are completely exfoliated and randomly and homogeneously
dispersed are limited to nylons, PI and polyolefins
under the optimum conditions. We could expect that
also commodity polymer nanocomposites would be
industrialized.
E. Although PCN attracts significant attention due to the
properties mentioned above, the discovery of revolutionary fire retardant properties without deterioration of
polymer properties and toxicity will further improve
research on PCN. We are strongly convinced that use of
PCN will undergo significant development to include
polymers other than nylons, as a result of combining
research on their synthesis, property measurements and
processing. However, this research must be focused on
exploiting specific features of PCN, since an improvement in modulus could easily be attained using conventional fillers.
F. There was a remarkable improvement in many properties of nanocomposite hydrogels (NC gels), produced
from hydrogels using clay as crosslinkers instead of
conventional chemical crosslinkers. Significant development of NC gels is expected, similarly to the development of PCN, with major applications in DDS and as
soft actuators.
www.mme-journal.de
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Feature Article

In 1997, Gilman found revolutionary fire retardancy in NCH.

SEM of etched NCH film.

Twenty Years of Polymer-Clay Nanocomposites

Macromol. Mater. Eng. 2006, 291, 14491476

2.1.4 Structure and Reinforcement Mechanism of

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

5.2.1 Epoxy Resin-Clay Nanocomposites

8. Introduction of a Layered Microdomain Structure in

7. Liquid Crystal-Clay Composites

development and describe the significance of PCN to as

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Twenty Years of Polymer-Clay Nanocomposites

showed an example of a nylon matrix containing

edges adjoin, the upper limit of their content vol.-%

Macromol. Mater. Eng. 2006, 291, 14491476

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Comparison of size of glass fiber and montmorillonite in NCH.

same, indicating they are parallel to the silicate. From C8 to

NCH15, NCH30, NCH50, or NCH70 based on the wt.-%

Basal spacing vs. carbon number of amino acid.

Macromol. Mater. Eng. 2006, 291, 14491476

The M n calculated from Equation (1) (dotted line) and

Twenty Years of Polymer-Clay Nanocomposites

Conceptual picture of preparation of NCH.

spacing was in good agreement with that from the TEM

designate it as exfoliated PCN. In practice, NCH with over

Table 1. Analysis of NCHs.

From end group analysis.

Macromol. Mater. Eng. 2006, 291, 14491476

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Concentration of terminal groups in NCH.

historically on the border between conventional composite and PCN.

2.1.2 Wet Polymerization Methods

M n vs. R (nylon 6/12-Mt).

Macromol. Mater. Eng. 2006, 291, 14491476

NCH images: (a) TEM, and (b) SEM after etching.

high temperatures. The reason we used dried 12-Mt was

Twenty Years of Polymer-Clay Nanocomposites

Table 2. Mechanical properties of NCHs.

the test piece just by using a nail repeatedly, although the

method gave a co-polymer of nylon 6 and rubber-like nylon

Table 3. Mechanical properties of diamine-modified NCH5s.

hexamethylenediamine (HMDA) to the COOH group and

As mentioned before, we presented NCH for the first

Numbers of laminated layers.

Macromol. Mater. Eng. 2006, 291, 14491476

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Twenty Years of Polymer-Clay Nanocomposites

Table 5. Mechanical properties of NCH by compounding methods.

good recycling characteristics, a long lifetime, high

2.1.3 Compounding Methods

Table 6. Mechanical properties of NCH by Singh.

Macromol. Mater. Eng. 2006, 291, 14491476

well as NCH produced by polymerization methods.[25] The

2.1.4 Structure and Reinforcement

Table 7. Mechanical properties of NCHs with a variety of clays (5 wt.-%).

Heat distortion temperature

nium) and HMDA (neutral nitrogen) are summarized in

silicate can freely exchange with other NH

Crosslinking of nylon molecules by a silicate.

Macromol. Mater. Eng. 2006, 291, 14491476

N-chemical shift of intercalated glycine.

Twenty Years of Polymer-Clay Nanocomposites

1013 cm3(STP) cm cm1 Pa1