Formation and Structure of Organized Molecular Films
for Organo-Modied Montmorillonite and Mixed
Monolayer Behavior With Poly(L-lactide)
Atsuhiro Fujimori, Jun-Ichi Kusaka, Rintaro Nomura
Graduate School of Science and Engineering, Yamagata University, Jonan 4-3-16, Yonezawa,
Yamagata 992-8510, Japan
We investigated the molecular orientation and surface
morphology of organized molecular lms with regard
to solid-state structures for organo-modied montmor-
illonites by surface pressure-area (p 2 A) isotherm, in-
plane and out-of plane X-ray diffraction (XRD), and
atomic force microscopy (AFM). From the results of
out-of plane XRD, formation of highly ordered layer
structure was conrmed in these clay Langmuir-Blodg-
ett (LB) lm. Further, two-dimensional lattice of long
alkyl chain of organo-modied parts packed hexago-
nally or orthorhombically in the lms. Surface morphol-
ogy of Z-type monolayers on solid of organo-modied
montmorillonites indicates heterogeneous modication
ratio in montmorillonite surface by AFM observation. In
addition, monolayer behavior on the water surface and
mesoscopic morphological formation on solid of mixed
lms of organo-modied montmorillonite and poly-(L-
lactide) (PLLA) were investigated by p 2 A isotherm
and AFM. Collapsed surface pressures are independent
on the mixed ratio, and indicate almost constant value
in their isotherms. This tendency is a peculiarity of im-
miscible system. From the result of AFM observation,
phase separated structure was conrmed in meso-
scopic scales. This phase separated morphology
remarkably varied with mixed ratio. POLYM. ENG. SCI.,
51:10991107, 2011. 2011 Society of Plastics Engineers
INTRODUCTION
Clay minerals, layered silicates, have played impor-
tant roles in the modern technology. These materials
have received considerable attention because of their
potential use in numerous technical applications, ranging
from nanocomposite materials to biomedical and perso-
nal care products. Clays are unique in the sense that they
consist of negatively charged aluminosilicate layers kept
together with exchangeable interlayer cations. These ena-
ble the clays to undergo ion exchange which makes it
possible to modify their surfaces by intercalation of a
Correspondence to: Atsuhiro Fujimori; e-mail: fujimori@yz.yzmzgata-
u.ac.jp
DOI 10.1002/pen.21912
Published online in Wiley Online Library (wileyonlinelibrary.com).
V
C 2011 Society of Plastics Engineers
POLYMER ENGINEERING AND SCIENCE-2011
cationic surfactant into the interlayer spaces. Hence, a
large number of alkylammonium-modied layered sili-
cates (organo-modied clays) have been developed,
which are now widely used to form a large variety of
nanocomposite materials [14] with enhanced material
properties [58] Organo-modied clay composites have
been extensively investigated in material science [9]. For
example, it was recently demonstrated that modied
clays can act as powerful compatibilization agents of
polymer blends [3] and behave in a synergistic manner
with standard ame retardant formulations to render a
large class of polymers self-extinguishing [5]. To
achieve the remarkable enhancement of the mechanical
and thermal properties, it was also demonstrated that the
clays must be exfoliated in the polymer matrix [57].
The process of exfoliation is very complex, but there is
general agreement that in order for it to occur, the sili-
cate platelets must rst be coated with surfactant to ena-
ble them to overcome strong ionic interactions. The next
factor is the interaction between the polymer chains and
the platelet surface and the degree of surface coverage
by the surfactant which will determine whether the clays
will be well dispersed or clustered within the polymer
matrix. In order to determine whether specic function-
alized clay will exfoliate in a matrix it is useful to deter-
mine these parameters. Numerous methods exist, which
can characterize the interaction between the polymer and
the surfactant [10, 11].
By the way, thin lms of clay minerals have been
studied in application to modied electrodes, sensors,
photochromic devices, nonlinear optical devices, and so
on [12]. The Langmuir-Blodgett (LB) method is one of
the most useful techniques to prepare ultra-thin lms [13].
In this method, oating molecular monolayers formed at
an air/water interface are deposited on a solid substrate in
a layer-by-layer way. Ultra-thin lms of clay minerals
prepared by the LB method have been reported [14].
Recently, the clay LB lms have been hybridized with
alkylammonium cations [15]. Smectite clay is exfoliated
into single clay sheets with the negative charge in an
aqueous suspension at a low concentration [16]. When a
solution of an amphiphilic alkylammonium salt is spread
onto the clay suspension, the negatively charged clay pla-
telets in the suspension are adsorbed onto a oating
monolayer of the alkylammonium cation at an air-clay
suspension interface. The hybrid monolayers of the clay
platelets and the ammonium cations formed at the inter-
face can be transferred onto a solid surface to fabricate a
hybrid multilayer. Interestingly, a oating monolayer of a
water-soluble alkylammonium cation is stabilized at the
air-suspension interface by the hybridization with the clay
platelets [15]. The surface pressure-area (p 2 A) isotherm
of the hybrid monolayer is dependent on the clay concen-
tration in the suspension: as the concentration is higher,
the isotherm shifts to the larger area side [15]. This sug-
gests that structure and properties of the hybrid mono-
and multi-layers would be varied depending on the clay
concentration in the suspension. In addition, since the
organo-modied montmorillonites are post-petroleum
resources, it may be possible to form next generation eco-
material, for example, bio-chips implanted to human body
related to the phase separated structure at mesoscopic
scales. Namely, patterning surface intended to construct
the biological high-density memory devise is formed by
phase separation between biodegradable polymer and a
natural mineral. In this work, oating molecular mono- FIG. 1. (a) Illustration of structure of montorillonite before and after
layers and ultra-thin lms on solid of pre-formed organo- cation exchange reaction. (b) Chemical structure of quaternary ammo-
modied montmorillonites (MMTs) were constructed by nium regents; (A) dimethyl methylbenzile octadecyl (DMPO), (B) di-
LB method. These LB multilayers of organo-modied methyl dioctadecyl (DMDO), (C) methyl hydroxy ethyl octadecyl
(MHEO), and (D) trimethyl octadecyl (TMO) ammonium cations.
MMTs were characterized by the out-of plane and in-
plane X-ray diffraction (XRD) methods and atomic force
microscopic (AFM) observation. Further, monolayer behav- montorillonites are described in reference [8]. PLLA pel-
ior on the water surface and mesoscopic morphological for- lets with a high L-lactide content ([99%) were kindly
mation on solid of mixed organized moelcuar lms of supplied by Unitika. The weight-average molecular
organo-modied MMT and poly-(L-lactide) (PLLA) were weight (Mw), number-average molecular weight (Mn),
investigated by p 2 A isotherm and AFM in mesoscopic and the polydisperity index (Mw/Mn) were 20 3 104, 10
scales. The formation of phase separated surface between 3 104, and 1.94, respectively. Both the PLLA pellets
biodegradable PLLA and surface modied natural clays and the clay were dried in a vacuum oven at 1008C for
would be connected to construction of harmless surface 2 days and kept at room temperature in silica gel-dried
patterning related to newly biological memory devise. desiccators.
The organo-modied clays were spread from toluene
solution (
1024 M) onto distilled water (
18 MOcm),
EXPERIMENTAL
respectively. The p 2 A isotherms were measured by a
Natural Na-montmorillonite was kindly supplied by FACE lm balance (Kyowa Kaimen) at 158C. These
Kunimine with the cation-exchange capacity of 108.6 monolayers were transferred onto glass (XRD samples) or
meq/100 g. The organophilic clay was prepared by cation mica (AFM samples) substrates at 158C using the LB
exchange reactions of natural clay (aqueous dispersion) method. The PLLA were spread from chloroform solutions
with 20% aqueous solution of dimethyl methylphenyl onto distilled water. PLLA monolayers collapsed at about
octadecyl (DMPO), dimethyl dioctadecyl (DMDO), tri- 8 m Nm21 (Fig. 9a). Therefore, organo-modied clays and
methyl octadecyl (TMO), and methyl hydroxy ethyl octa- PLLA mixed monolayers itself were transferred onto mica
decyl (MHEO) ammonium chloride (Fig. 1). Four kinds substrates at 158C using the LB method below 5 m Nm21.
of quaternary ammonium cations based on long-alkyl The structures of the organo-modied MMTs in bulk
chain are used to hydrophobic parts of clays. To estimate and the layer structures of organized molecular lms
hydrophobisity and ability of formation of ordered organ- were characterized with a RAD-rA diffractometer
ized lm, organo-modication agent having one and two (RIGAKU; in the case of organized molecular lms,
alkyl-chains (TMO and DMDO), bulky phenyl group the out-of plane XRD method was used). Ni-ltered
(DMPO), and hydrophilic hydroxyl groups (MHEO) are CuKa radiation (wavelength k 0.154 nm) was gener-
applied. Procedures of these organo-modications of ated at 40 kV and 100 mA. The diffracted X-ray beam

1100 POLYMER ENGINEERING AND SCIENCE-2011 DOI 10.1002/pen

was monochromatized by a pyrographite monochromatic
system and monitored by a scintillation counter.
The crystalline morphology of the organo-modied
clays was characterized with a SAXS instrument
(M18XHF, MAC Science) comprised of an 18 kW rotat-
ing-anode X-ray generator with a Cu target (k 0.154
nm) operated at 50 kV and 300 mA [17]. This instrument
was equipped with a pyrographite monochromator, pin-
hole collimation system (/
0.3, 0.3, 1.1 mm), vacuum
chamber for the scattered beam path, and two-dimensional
imaging plate detector (DIP-220).
The surface morphologies of the transferred mono-
layers were observed using a scanning probe microscope
(Seiko Instrument, SPA300 with SPI-3800 probe station)
at tapping mode utilizing microfabricated rectangular Si
single crystal cantilevers with integrated pyramidal tips
with a constant force of 1.3 Nm21.
The in-plane spacing of the two-dimensional lattice of
the lms was determined by analysis using an in-plane
X-ray diffractometer [18, 19] for two-dimensional geo-
metrical arrangements (Bruker AXS, MXP-BX, CuKa
radiation, 40 kV, 40 mA, an instrument specially made
to order) equipped with a parabolic graded multilayer
mirror.

RESULTS AND DISCUSSION

Figure 2 shows the p 2 A isotherms of monolayer
on the water surface of organo-modied MMTs. From
these isotherms, we recognize formation of extremely
stable monolayers. In this measurement, we represent
two-type expression as compression percentage vs.
surface pressure and mean area per repeating units
vs. surface pressure plots. In this case, we use the
expression of mean area per repeating units in a
horizontal axis on the assumption that surface modi-
cation ratios of organo-clays are always 100% cover-
age. However, surface modication ratios of individual
organo-clays are not always 100% coverage and a con-
stant value each other. Therefore, the isotherm of
mean area per repeating units vs. surface pressure
plot is adaptation of a stopgap expression followed by
academic custom, and an expression of compression
percentage is also adopted as an independent value of
surface coverage.
Figure 3 shows the AFM images of Z-type monolayer
on solid transferred by LB method of organo-modied
MMTs. From this measurement, it is found that surface
morphology of these monolayers of organo-modied clays
indicates heterogeneous modication ratio on montmoril-
lonite surface.
Figure 4 shows comparison between wide-angle XRD
proles in bulk and LB lms of organo-modied MMTs.
In the case of LB lm, this measurement corresponds to
out-of plane XRD along the layer axis of molecules
(c-axis). In the bulk state (Fig. 4a), all four organo-modi-
ed MMTs indicate single diffraction peak around 20 A
FIG. 2. p 2 A isotherms of monolayers for organo-modied clays on
the water surface (158C); (a) compression percentage vs. surface pressure
and (b) mean area per repeating units vs. surface pressure.
on these proles. Based on the results of SAXS measure-
ment in bulk (Fig. 5a), it is found that all WAXD peaks
around 20 A correspond to rst order diffraction peaks
along the c-axis (001).
From the results of out-of plane XRD at low angle
region (Fig. 5b) to the LB lm, it is found that organo-
modied MMTs indicate long spacings around 60 A.
Therefore, diffraction peaks conrmed at wide-angle
region (Fig. 4b) correspond to higher order diffraction.
These results are summarized in Table 1. Comparison
between regularity of layer structure in bulk and their LB
lms, organo-modied MMTs form the extremely devel-
oped layered organization in their LB multilayers. Figure
6 shows schematic illustration of layer structural forma-
tion of organo-modied clays in bulk and in their LB
lms.
By the way, the peaks due to (002) and (003) reec-
tions of out-of plane XRD prole of DMPO-MMT LB
lm are absent and clearly present, respectively. On the
other hand, (002) reection of DMDO-MMT LB lm is
stronger than their (003) reection. It seems that this tend-
ency is caused by extinction law (rule of absent reec-
tion). An odd-even effect of diffraction intensity is often
conrmed in out-of plane XRD proles of several ordered
LB lms. For example, LB lm of cadmium stearate is
well-known as a standard material in this academic eld.
In this case, (00l) reection in out-of plane XRD prole

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE-2011 1101

 FIG. 3. AFM images with the height information of Z-type monolayers of organo-modied clays:
(a) DMPO-MMT, (b) DMDO-MMT, (c) MHEO- MMT, and (d) TMO-MMT (transferred at 15 m Nm21,
1 3 1 lm2 scales).
clearly indicates odd-even effect related to extinction law
are inuenced by weaken interference [18]. Generally, an
intensity of (00l) reections gradually weakens in the high
2y angle side in XRD prole. However, these are systems
without occurrence of extinction law. In other words, low
regularity system is applies to this case. Therefore, it seems
that regularity of layer structure along the c-axis of LB
lm of DMPO-MMT is superior to one of DMDO-MMT.
Figure 7 shows in-plane XRD proles of LB lms of
organo-modied MMTs. To estimate the packing mode of
long alkyl chain in the organo-modied part, these meas-
urements are carried out at the region related to sub-cell
formation of hydrocarbons (2y 10
308). The organo-
clay of only DMPO-MMT indicates single peak at 4.5 A
and other organo-modied clays show double peaks at 4.1
and 4.5 A in the proles of LB mulitlayers. Figure 8
shows schematic illustration of packing models for hydro-
carbons in organo-modied parts on montorillonite in the
LB lms. In the two-dimensional plane, alkyl-chains of
DMPO-MMT packed hexagonally in their LB lm. On
1102 POLYMER ENGINEERING AND SCIENCE-2011
the other hand, hydrocarbons of DMDO-MMT, MHEO-
MMT, and TMO-MMT commonly form the two-dimen-
sional orthorhombic lattice in the lm plane. This structural
change may show the inuence on the existence of bulky
phenyl groups in DMPO regent and its steric hindrance.
These experimental ndings show the formation of
highly order layered organization of organo-modied
MMTs constructed by LB method. In this case, hydrocar-
bons in organo-modied part are closely packed as two-
dimensional lattice. None of surface coverage of these
organo-modied clays shows higher value. However,
hydrocarbons of a little region of organo-modied parts in
the LB lms form the higher order arrangement at a sub-
nanometer scales.
Figure 9 shows p 2 A isotherm of monolayer on the
water surface of neat PLLA and corresponding surface
morphology of their LB monolayer transferred at sev-
eral surface pressures estimated by AFM observation.
From the results of this p 2 A isotherm, clearly phase
transition behavior from monolayer to three-dimensional
DOI 10.1002/pen
 TABLE 1. Values of long spacings of organo-modied clays in the
bulk and LB lms.

Values in Bulk

2y (degree) d-spacing (A) hkl

DMPO-MMT 4.84 18.3 001
DMDO-MMT 3.98 22.2 001
MHEO-MMT 4.22 20.9 001
TMO-MMT 4.84 18.3 001
Values in LB lms

2y (degree) d-spacing (A) hkl

DMPO-MMT 1.42 61.4 001
2.78 31.8 002
4.90 18.0 003
DMDO-MMT 1.44 62.2 001
2.78 31.1 002
4.90 18.0 003
7.02 12.6 005
MHEO-MMT 1.53 57.9 001
4.62 19.1 003
TMO-MMT 1.47 60.0 001
4.40 20.0 003

crystal based on the appearance of plateau region was

FIG. 4. (a) X-ray powder diffraction proles and (b) Out-of plane XRD pro-
les of LB lms (20 layers, 15 mN/m, 158C) for organo-modied clays: (A)
DMPO-MMT, (B) DMDO-MMT, (C) MHEO-MMT, and (D) TMO-MMT.
conrmed. This plateau means an equilibrium state at
the interface and is corresponding to the phase transi-
tion on the water surface. Although this type behavior
generally corresponds to a collapse of monolayer and
formation of piled up lm, these straight chain-type
polymers may form the lamellae (made by folded chain
unit) like a three-dimensional structure at this plateau
region in the isotherm. Characteristics of morphological
formation of organized molecular lms of PLLA are a
bundle like texture (Fig. 9b). In this gure, the remark-
able surface pressures related to two-dimensional phase
transition are chosen and monolayers are transferred
onto solid substrate at each surface pressure. Extrapo-
lated images from the isotherm are corresponding to

FIG. 5. (a) SAXS pattern and prole of DMPO-MMT in bulk and (b) FIG. 6. Schematic illustration of layer structural formation of organo-
Out-of plane XRD prole of LB lm for DMPO-MMT. modied clays (a) in bulk and (b) in their LB lms.

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE-2011 1103


FIG. 7. In-plane XRD proles of LB lms (20 layers, 15 m Nm21,
158C) for organo-modied montorillonites: (a) DMPO-MMT, (b)
DMDO-MMT, (c) MHEO-MMT, and (d) TMO-MMT.
FIG. 8. Two-dimensional lattice formed by long alkyl chain of organo-modied montorillonites in their LB lms.
1104 POLYMER ENGINEERING AND SCIENCE-2011
result of AFM observation of their monolayers on solid.
The lamellar features are parallel to the LB lm deposi-
tion direction. The orientation of the lamellae suggests
that the shape persistent features behave like rigid rod
polymers. According to the pseudo-orthorhombic unit
cell of this polymer [20], each 103 helix has a linear
dimension of 2.78 nm. Hence a single chain of PLLA
will be 50 nm long if the entire chain is in a perfect
103-helical conformation. The value of 50 nm is well
corresponding to bundle thickness estimated by line
prole of AFM observation. The similarity between the
calculated chain length and the lamellar dimension from
AFM images suggests that individual PLLA chains exist
as 103 helices that persist over nearly the entire length
of the chain with disordered chain ends. This result well
correspond to previous report [21].
Figure 10a shows p 2 A isotherms of DMPO-MMT:
PLLA mixed monolayer on the water surface at several
mixed ratio. Further, Fig. 10b shows plot of the collapsed
surface pressure versus mixed ratio with DMPO-MMT in
this system. In the case of mixed monolayer of DMPO-
MMT: PLLA, transition point is almost independent on
DOI 10.1002/pen
 FIG. 9. (a) p 2 A isotherms of monolayer on the water surface for PLLA (158C). (b) AFM images of
PLLA LB lms transferred at several surface pressures: (A) 15 m Nm21, (B) 10 m Nm21, (C) 7.7 m Nm21,
and (D) 4 m Nm21 (5 3 5 lm2).
the mixed ratio and indicates constant value in their iso-
therms. That is to say, this is immiscible system and
phase separation may occur in the two-dimensional lm
plane at the macroscopic scales.
Figure 11a shows representative p 2 A isotherm of
DMPO-MMT: PLLA 1:1 mixed monolayers on the
water surface. Further, Fig. 11b shows changes in surface
morphology of DMPO-MMT: PLLA 1:1 mixed mono-
layer transferred at various surface pressures corresponded
to p 2 A isotherm. These images indicate typical phase
separated morphology between organic and inorganic
parts. In this system, morphology of this mixed mono-
layer indicates clay particles surrounding line shaped
PLLA texture. This tendency is conrmed in almost all
transferred surface pressures. As a result of this observa-
tion, we describe schematic illustration of phase separated
structure of mixed lm of PLLA and DMPO-MMT in
Fig. 11c. In this case, continuous phase of organic PLLA
(as a sea region) and condensed phase of organo-modi-
ed inorganic clay (as an island region) coexist.
Figure 12 shows morphological changes in AFM
images of PLLA: DMPO-MMT mixed monolayers at
several mixed ratios before and after transition (trans-
FIG. 10. (a) p 2 A isotherms of DMPO-MMT: PLLA mixed mono-
layer on the water surface at several ratio. (b) Plot of the collapsed sur-
face pressure versus mixed ratio of DMPO-MMT in mixed monolayers.
DOI 10.1002/pen
ferred at 5 and 10 m Nm21). From the result of this obser-
vation, phase separated structure was also conrmed at the
mesoscopic scales in the both phases. This phase separated
morphology remarkably varied with mixed ratios. Compari-
son between morphology transferred at higher and lower
phase, line-shaped growths of PLLA texture are shown in
high surface pressure state. The two-dimensional dispersion
of clay particles in PLLA matrix within mixed monolayer
plane improve with polymer content although occulation
effect promote to aggregation of clay particles each other in
the case of high content of organo-clays [22, 23]. Anyway,
these like microscopic phase separated surfaces are possible
to apply the harmless surface patterning intended to the
high-density memory devises.
Figure 13 shows schematic illustration of morphologi-
cal changes in mixed monolayer surface of PLLA and
DMPO-MMT at several ratios. The control of phase sepa-
rated structure is carried out by organo-clay contents in
mixed lm. Although mesoscopic morphological forma-
tion of this mixed system is based on the phase separa-
tion, miscibility between organo-modied clay and PLLA
may be modied by high coverage of organo-modied
regent on montmorillonite surface.
As mentioned previously, it is possible to control
the surface morphologies of the mixed monolayers for
organic polymer and inorganic materials by organo-modi-
cation of clay surface and the method of organized
molecular lms. It is possible to apply this type patterned
thin lm material made by bio-degradable organic poly-
mers and mining natural clays as next generation eco-
material, for example, bio-chips implanted to human body.
CONCLUSION
We investigated monolayer behavior on the water sur-
face and mesoscopic morphological formation on solid
POLYMER ENGINEERING AND SCIENCE-2011 1105
 FIG. 11. (a) p 2 A isotherm of DMPO-MMT: PLLA 1:1 mixed monolayers on the water surface (158C).
(b) Changes in surface morphology of DMPO-MMT: PLLA 1:1 mixed monolayer at various surface pres-
sure: (A) 4 m Nm21, (B) 7.7 m Nm21, (C) 10 m Nm21, and (D) 15 m Nm21 (5 3 5 lm2). (c) Illustration
of phase separated structure of mixed lm of PLLA and DMPO-MMT.

FIG. 12. Changes in AFM images of PLLA: DMPO-MMT mixed monolayers with several mixed ratio
transferred at (a) 5 m Nm21 and (b) 10 m Nm21 (5 3 5 lm2).

FIG. 13. Schematic illustration of morphological changes in mixed monolayer surface of PLLA and
DMPO-MMT at several ratio: (a) 5:1, (b) 3:1, (c) 1:1, and (d) 1:3.

1106 POLYMER ENGINEERING AND SCIENCE-2011 DOI 10.1002/pen

substrate of mixed organized moelcuar lms of organo-
modied montmorillonite and PLLA by p 2 A isotherm
and AFM observation. From the results of p 2 A iso-
therm of neat PLLA monolayer, clearly phase transition
behavior from two-dimensional monolayer to three-
dimensional crystal was conrmed with plateau region at
relative low surface pressure. Generally, straight rob-like
helical polymers may form the lamellae like three-dimen-
sional structure at this transition point though this type of
behavior corresponds to a collapse of monolayer and a
formation of piled up lm. In the case of mixed mono-
layer with organo-modied montmorillonite, this phase
transition point is independent on the mixed ratio and
indicates almost constant value in their isotherms. There-
fore, this mixed monolayer indicates immiscible system.
From the result of AFM observation, phase separated
structure was conrmed in mesoscopic scales. This mor-
phological formation related to phase separation remark-
ably varied with mixed ratio. Resultant microscopic phase
separated surface based on the immiscibility between
PLLA and organo-modied montmorillonite is possible to
use harmless surface patterning.
ACKNOWLEDGMENTS
Authors sincerely appreciate Mr. K. Kurosaka and Dr.
M. Kubota of Research Center of Kunimine for their kind
collaboration and useful discussion.
REFERENCES
1. R.A. Vaia, R.K. Tenkolsky, and E.P. Giannelis, Chem.
Mater., 6, 1017 (1994).
2. W. Xie, Z.M. Cao, W.P. Pan, D. Hunter, A. Singh, and R.
Vaia, Chem. Mater., 13, 2979 (2001).
3. J.W. Lee, Y.T. Lim, and O.O. Park, Polym. Bull., 45, 191
(2000).
4. E. Haokett, E. Manias, and E.P. Giamelis, J. Chem. Phys.,
108, 7410 (1998).
DOI 10.1002/pen
5. M. Si, J. Hefter, A. Song, M.H. Rafailovich, and J.C. Soko-
lov, J. Adhesion Sci. Technol., 19, 1459 (2005).
6. M.Y. Gelfer, C. Burger, B. Chu, B.S. Hsiao, A.D. Drozdov,
M. Si, M. Rafailovich, B.B. Sauer, and J.W. Gilman, Mac-
romolecules, 38, 3765 (2005).
7. X. Wang, Y. Gao, K. Mao, G. Xue, T. Chen, J. Zhu, B. Li, P.
Sun, Q. Jin, and D. Ding, Macromolecules, 39, 6653 (2006).
8. X. Li, T. Kang, W.-J. Cho, J.-K. Lee, and C.-S. Ha, Macro-
mol. Rapid Commun., 22, 1306 (2001).
9. T.J. Pimavaia, J.-R. Butruille, G. Alberti, and T. Bein, Eds.,
Comprehensive Supramolecular Chemistry, Vol. 7, Chapter
7, Elsevier, Oxford, (1996).
10. B.B. Khatua, D.J. Lee, H.Y. Kim, and J.K. Kim, Macromo-
lecules, 37, 2454 (2004).
11. M. Si, T. Araki, H. Ade, A.L.D. Kilcoyne, R. Flsher, J.C. Soko-
lov, and M.H. Rafailovich, Macromolecules, 39, 4793 (2006).
12. A.J. Bard, T. Mallouk, and R.W. Murray, Ed., Techniques of
Chemistry Series, Vol. 22, Chapter 6, Wiley, New York (1992).
13. G.L. Gaines Jr., Insoluble Monolayers at Liquid-Gas Interfa-
ces, Wiley Online Library, New York (1966).
14. Y. Hotta, M. Taniguchi, K. Innkai, and A. Yamagishi,
Langnuir, 12, 5195 (1996).
15. Y. Umemura, A. Yamagishi, R. Schoonheydt, A. Persoons,
and F. De Schryver, Thin Solid Films, 388, 5 (2001).
16. B.K.G. Theng, The Chemistry of Clay-Organic Reactions,
Adam Hilger, London (1974).
17. A. Fujimori and Y. Hayasaka, Macromolecules, 41, 7606
(2008).
18. A. Fujimori, Y. Sugita, H. Nakahara, E. Ito, M. Hara, N.
Mtsuie, K. Kanai, Y. Ouchi, and K. Seki, Chem. Phys. Lett.,
387, 345 (2004).
19. A. Fujimori, T. Araki, H. Nakahara, E. Ito, M. Hara, H. Ishii,
Y. Ouchi, and K. Seki, Chem. Phys. Lett., 349, 6 (2001).
20. T. Miyata and T. Masuko, Polymer, 38, 4003 (1997).
21. S. Ni, W. Yin, M.K. Ferguson-McPherson, S.K. Satija, J.R.
Morris, and A.R. Esker, Langmuir, 22, 5969 (2006).
22. P.H. Nam, A. Fujimori, and T. Masuko, e-Polymers, 5, 1 (2004).
23. P.H. Nam, M. Kaneko, N. Ninomiya, A. Fujimori, and T.
Masuko, Polymer, 46, 7403 (2005).
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