Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

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Journal of the Taiwan Institute of Chemical Engineers

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Polyimide/kaolinite composite lms: Synthesis and characterization of

mechanical, thermal and waterproof properties
Xiumei Qiu a, Hongquan Wang a, Chunyu Zhou a, Dan Li a, Yi Liu b, Chunjie Yan a,*
a
b

Engineering Research Center of Nano-Geomaterials of Ministry of Education, China University of Geosciences, Wuhan 430074, China
Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074, China

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 7 October 2013
Received in revised form 17 January 2014
Accepted 19 January 2014
Available online 8 February 2014

Polyimide (PI)/kaolinite composites were successfully synthesized via in situ polymerization using
kaolinitepotassium acetate intercalation compound (KKAc) as the intermediate. XRD patterns, FTIR
spectrum and SEM images revealed that polyimide have partially intercalated into the layers of kaolinite
by replacing KAc molecules. The mechanical, thermal and optical properties of the composite lms were
characterized by universal tester, TGA, and UVvis spectrometer. It was found that the introduction of
modied kaolinite led to signicant increase in tensile strength and elongation at break of PI matrix
when KKAc content was no more than 5 wt%. Electron microscopy characterization indicated that some
plate-like and clusters-like structure appeared in perpendicular to the fracture surface of composite
lms after tensile tests other than in pure PI lm, which meant stronger fracture resistance existing in
the composite lms. The introduction of modied kaolinite also resulted in improved thermal stability,
slight decrease in transmittance and marked decrease in water uptake ratio at low clay content (5 wt%).
Therefore, the polyimide/kaolinite composites have potential application in microelectronic devices.
2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords:
Polyimide
Kaolinite
Mechanical property
Thermal stability
Waterproof property

1. Introduction
Recently, extensive research has been devoted to develop
organicinorganic composites owing to their good thermal
stability, excellent mechanical strength, dielectric insulation,
and chemical resistance, such as composite membranes [1,2].
Particularly, lots of clay particles are continued to be interesting
ller materials into polymers in developing cost-effective high
performance materials, because the inclusion of clay alters the
structural, thermal and mechanical properties of the composites
and makes the composites have both the advantages of organic and
inorganic materials [38].
Aromatic polyimide (PI) has been well-known for its excellent
dielectric properties, mechanical properties, thermal stability,
physical and chemical properties [9], and widely applied for lms,
microelectronic devices, adhesives, aerospace engineering, and
membrane [10]. Various combinations of polyimide with inorganic
llers including silica, layered silicate, graphene, alumina have
been reported, showing that outstanding mechanical and physical
properties can be achieved when proper contents of ne llers are
incorporated. Especially, the layered silicate clay particles, such as

* Corresponding author. Tel.: +86 027 67885098; fax: +86 027 67885098.
E-mail address: chjyan2005@126.com (C. Yan).

montmorillonite or mica, when the layers of clay are organic,

exfoliated or intercalated [1113], they can be well dispersed and
much more effective to reinforce the performance of polymer. The
composites which prepared from polyimide and layered clay by
solution dispersion technique or in situ polymerization have been
found to display novel properties [1416]. It was noticed that the
introduction of well dispersed clay layers such as montmorillonite
(MMT) into a polyimide matrix has been proved to be extremely
effective in the improvement of mechanical, thermal and barrier
properties of the polyimide matrix [17,18]. The same as MMT,
kaolinite is one of the most ubiquitous layered clay minerals in the
earth, and it is a dioctahedral 1:1 phyllosilicate formed by
superposition of silicon tetrahedral sheets and aluminum octahedral sheets. But the adjacent layers of kaolinite are held together by
van der Waals forces and hydrogen bonds to form a distinct space
between the layers, which is different from that of MMT and results
in the low reactivity of kaolinite for intercalation of organic
polymer [19]. Therefore, the modication of kaolinite is necessary
for preparing polymer/kaolinite composites, for example, the
intercalation of small molecule. Nowadays, some novel polymer/
kaolinite nanocomposites have been prepared by using various
intermediates such as kaoliniteurea, kaolinitedimethylsulfoxide
(DMSO), kaolinitepotassium acetate (KAc), and so on [2022].
Kaolin is readily available and cost-effective mineral clay and has
been used to reinforce the polymers [23]. To our best knowledge,

http://dx.doi.org/10.1016/j.jtice.2014.01.012
1876-1070/ 2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

X. Qiu et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

2022

rare references about polyimide/kaolinite composite materials

have been reported before.
In this work, polyimide/kaolinite composite lms have been
prepared via in situ polymerization, which featured the virtue of
low cost to improve the performance of polyimide. The kaolinite
particles were intercalated by KAc rstly. The relationship between
structure and properties of composite lms was well described.
The effect of clay content on the mechanical, thermal, optical and
waterproof properties of PI/kaolinite composites were systematically investigated through various techniques and for comparing,
the properties of pure PI were also tested.
2. Experimental and methods
2.1. Materials
Kaolin particles used in this study were purchased from
Guangdong (China) and received as nely divided white powders
of high purity. The chemical composition of this kaolin was
presented in Table 1. Pyromellitic dianhydride (PMDA) and 4,40 oxydianiline (ODA) of chemical reagent grade were supplied by
Tianjin Bodi Chemical Co. (Tianjin, China). N,N-Dimethylacetamide
(DMAc) of analytical grade was obtained from Sinopharm
Chemical Reagent Co. Ltd. (China). Potassium acetate (KAc) was
provided by Tianjin Chemical Reagent Co. Ltd. (Tianjin, China). All
agents were dried or distilled before use.
2.2. Preparation of kaoliniteKAc compound (KKAc)
KaoliniteKAc compound (KKAc) was prepared from kaolinite
and KAc through dry grinding: 5 g of kaolinite containing 5 wt%
moisture and 1.5 g of KAc were placed in an agate mortar and
thoroughly grinded for 40 min at room temperature. After that,
KKAc was obtained by dried the mixture in a vacuum oven at 95 8C
for 12 h.
2.3. Preparation of pure PI lm and PI/kaolinite composite lms
The PI/kaolinite composite lms were prepared via an in situ
polymerization. Different content of KKAc (0 wt%, 1 wt%, 3 wt%,
5 wt%, 7 wt%, 9 wt% of two monomers content) were thoroughly
dispersed in 45 mL DMAc with the help of vigorous stirring in a
100 mL three-necked ask. To this solution, 3.00 g of ODA was
added and then 3.32 g of PMDA was slowly placed into the mixed
solution. The mixture was stirred vigorously for about 30 h to
obtain a yellow, viscous, translucent mixed poly(amide acid)/clay
solution. The solution was cast onto a glass plate for naturally
drying to remove air-bubble, and then were thermally treated at
60, 100, and 250 8C for 2 h separately, and 300 8C for 20 min in a
high temperature oven heating. Finally, pure PI and PI/kaolinite
composite lms were obtained.

Germany) with Cu Ka radiation. The data were collected from

3 to 50 8 2u with a scan rate of 0.5 8/min. The morphologies of
surface and cross-section of samples were observed by eld
emission scanning electron microscopy (FE-SEM, SU8010,
Hitachi Japan) with an acceleration voltage of 1.0 kV, 3.0 kV,
5.0 kV and 15.0 kV, respectively. A Malvern 2000 particle size
analyzer (Britain) was used to analyze the particle size
distribution (PSD) of kaolin and the kaolin powder was dispersed
in deionized water and vibrated 10 min before PSD analysis.
Fourier Transform infrared spectroscopy (FTIR) was conducted
on a Perkin-Elmer 983 FT-IR spectrometer between 4000 and
400 cm1 at 25 8C. The mechanical properties of samples were
measured with a GP-TS2000S/10 K universal testing machine at a
loading rate of 5 mm/min and a clip distance of 20 mm. The test
lms were cut into dumbbell of 50 mm  5 mm  0.05 mm.
Thermal stabilities of lms were examined by thermogravimetric
analysis (NETZSCH STA 409 PG/PC instrument, Germany),
employing a heating rate of 10 8C/min from 30 to 800 8C and a
nitrogen ow rate of 60 mL/min. Water absorption of all lms
was measured by soaking a certain weight of sample (dimension
of 20 mm  30 mm) in 25 mL water at 25 8C for 1 h, then 100 8C
for 1 h and weighed. Water uptake ratios of samples were
calculated by formula (1).
Water uptake ratio %

100W 2  W 1
W1

(1)

Here, W1 and W2 are the initial dry and nal wet matter weights
of lms, respectively. An UV-1801 spectrophotometer was
performed between 350 and 800 nm to measure the transmittance
of lms with the same dimension of 10 mm  20 mm and
thickness of 0.05 mm.
3. Results and discussions
3.1. Characterization of kaolinite and KKAc
The particle size distribution and morphology of raw kaolinite
are shown in Fig. 1. It exhibits ne particles and narrow particle
size distribution, and the particles content of 01 mm is 100 wt%.
The inserted FE-SEM image reveals that the particles of kaolinite
are in the range of microns and exhibit smoother surface with
pseudo-hexagonal edge.
KaoliniteKAc compound (KKAc) was prepared as an intermediate by dry grinding from kaolinite and KAc rstly. FTIR spectra of
raw kaolinite and KKAc are demonstrated in Fig. 2. The peaks
around 10001050 cm1 and 469 cm1 are the characteristic
absorption bands of the SiO from the silicate in kaolinite (see
Fig. 2a). Three characteristic bands at 3694, 3664, and 3649 cm1
for inner-surface hydroxyl stretching are found in raw kaolinite,

2.4. Measurement and characterization

X-ray diffraction (XRD) was recorded on a D8-Focus type
X-ray powder diffractometer (XRD, D8-FOCUS, Broker AXS
Table 1
Chemical composition of raw kaolinite.
Component

Content (%)

Component

Content (%)

SiO2
Al2O3
TFe2O3
MgO
CaO
Na2O

48.28
36.03
1.01
0.033
0.13
0.030

K2O
TiO2
P2O5
MnO
LOI
Total

0.010
0.70
0.20
0.003
13.60
100.026

Fig. 1. Particle size distribution and FE-SEM micrograph (inserted image) of raw
kaolinite.

X. Qiu et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

2023

3.2. Distribution of kaolinite in PI matrix

Fig. 2. FTIR spectra of (a) kaolinite, (b) KKAc, (c) PI/kaolinite composite lm and (d)
pure PI lm.

Fig. 3. XRD patterns of (a) kaolinite, (b) KKAc, (c) pure PI lm and (d)(g) PI/kaolinite
composite lms containing 3, 5, 7, 9 wt% KKAc.

which shift to 3692, 3662, and 3646 cm1 in KKAc sample (Fig. 2b)
due to the inuence of interlamellar modications [24,25].
Compare KKAc with raw kaolinite (see Fig. 2b and a), two
additional bands at 1418 and 1604 cm1 which attributed to the
vibration peaks of symmetric and antisymmetric stretch vibrations
of CH3COO have respectively appeared in the spectra of KKAc
sample [26]. The coupling of CO vibration and OH deformation
are marked by the new band at 1346 cm1. The band at 3606 cm1
provides the interaction between the inner surface OH of
kaolinite and the hydrogen bond of CH3COO. In addition, XRD
patterns of raw kaolinite and KKAc are illustrated in Fig. 3a and b.
The characteristic maxima of raw kaolinite is observed at
2u = 12.368 (very sharp, intense, and narrow), which corresponds
to the basal spacing of kaolinite (0.71 nm). After intercalation of
KAc, as expected, the XRD pattern of raw kaolinite is dramatically
modied. The peak at 2u = 12.368 of original kaolinite, assigned as
the rst basal peak, d001, greatly shifts to small reection angles
(2u = 6.238) during the intercalation, which is produced by the
presence of intercalated KAc (1.41 nm) [27,28]. It can be concluded
that KAc molecules have been intercalated into the layers of
kaolinite with an intercalated ratio of 90% which calculated
according to the reports [29,30].

The PI/kaolinite composites were prepared on the basis of the

two-step synthetic method of pure polyimide [31]. The solution
system exhibited homogeneous indicating good dispersion of
kaolinite particles in polymer solution. This phenomenon was
similar to PI/MMT composites prepared by Li et al. [32].
Fig. 3cg illustrates the XRD patterns of PI/kaolinite composites with different kaolinite contents (09 wt%). On the patterns
of pure PI in the range of 2u = 12288 a broad centered at about
188 occurs (Fig. 3c). The signicance of this broad band is that
pure PI is amorphous. It is obvious that the peak at 2u = 6.238
corresponding to the intercalation of KKAc disappears completely
in composite lms (Fig. 3dg). Furthermore, when KKAc content
is not exceeded 5 wt%, the intensity of characteristic diffraction
peak (d001) decreases sharply in Fig. 3d and e. The obvious
decrease in the basal spacing indicates that the polyimide chains
have intercalated into the layers of kaolinite by replacing KAc
molecules, which results in almost disappearing of the interlayer
spacing (d001) of kaolinite. Fig. 3d and e exhibits that most
kaolinite layers are delaminated, whereas some layers retain
their basal spacing [33]. The results above show that the PI/
kaolinite composites are successfully prepared. The layers of
kaolinite have dispersed into polyimide matrix and lost their
original structure resulting from the intercalation of polyimide.
But when KKAc content exceeds 5 wt%, diffraction peak (d001)
increases sharply in intensity due to the aggregation of kaolinite
particles (see Fig. 3f and g).
Fig. 2c and d exhibits the FTIR spectra of PI/kaolinite composite
lm containing 5 wt% KKAc and pure PI lm. The presence of
characteristic group frequencies of polyimide and kaolinite can be
observed. A few characteristic absorption bands at 1378 cm1 (C
NC stretching, imide II), 1720 cm1 (asymmetric CO stretching,
imide I), 1777 cm1 (symmetric CO stretching, imide I),
3071 cm1 (NH stretching of R-NH3), and 3475 cm1 (polymeric
OH stretching) of PMDA/ODA polyimide are indicated in Fig. 2d.
For PI/kaolinite composite lm containing 5 wt% KKAc (see Fig. 2c),
characteristic frequencies of polyimide and kaolinite are still
present, but the peaks at 3694, 3664 and 3649 cm1 assigned to
inner-surface hydroxyl stretching bands of raw kaolinite nearly
disappear, which is resulted from the intercalation of polyimide
chains into layers of kaolinite [34]. Meanwhile, according to FTIR
spectra of KKAc, the peak at 3606 cm1 for CH3COO has
disappeared, conrming that the polyimide molecules have
substituted KAc molecules and intercalated into the interlayer
of kaolinite. A possible mechanism of preparing PI/kaolinite
composite lms has been illustrated in Fig. 4. Larger layer spacing
of KKAc particles resulted from the intercalation of KAc molecule is
benecial for polyimide intercalating into the layer of kaolinite by
substituting KAc molecules [13].
The surface morphologies of pure PI and PI/kaolinite composite
lms are measured by FE-SEM, as shown in Fig. 5. Rough and
porous surface of Pure PI is exhibited in Fig. 5a, which is
detrimental to its performance. When the content of KKAc is less
than 5 wt%, kaolinite particles are homogeneously dispersed in
polyimide matrix and the introduction of kaolinite make the
surface of PI/kaolinite composite lms smoother than pure PI lm,
as exhibited in Fig. 5bd. But when the introduced content of KKAc
exceeds 5 wt%, lots of concave convex and holes have appear due to
the aggregation of kaolinite particles, as shown in Fig. 5e and f,
which has quite a serious effect on the properties of composite
lms. Kaolinite particles play an important role in polyimide
matrix, so some differences may be found in the properties of
composite lms. Therefore, the mechanical and thermal property,
water absorption property, and transparency of all lms are
thoroughly investigated below.

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X. Qiu et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

Fig. 4. Schematic representation of preparation of PI/kaolinite composite lms.

Fig. 5. FE-SEM images of the surface of (a) pure PI, (b) PI/1 wt%KKAc, (c) PI/3 wt%KKAc, (d) PI/5 wt%KKAc, (e) PI/7 wt%KKAc and (f) PI/9 wt%KKAc.

X. Qiu et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

Fig. 6. Tensile strength and elongation at break of PI/kaolinite composite lms with
different KKAc content.

3.3. Mechanical properties of PI/kaolinite composites

Polyimide lms are usually used in the areas of microelectronics, high temperature and aviation aerospace. An excellent
mechanical property is critical characteristics for polyimide lms.
Fig. 6 presents the relationship between KKAc content and
mechanical properties of the composite lms. Apparently, the
incorporation of 1 wt% KKAc in polyimide results in the increased
tensile strength and elongation at break of composites lms,

2025

comparing to those of pure PI lm. Further increasing the KKAc

content, the tensile strength of composite lms increases from
87.21 MPa for pure PI lm to 141.23 MPa for PI/kaolinite
composite lm containing 5 wt% KKAc. It is also observed that
the elongation at break of composite lm containing 5 wt% KKAc
(39.59%) is obviously higher than that of pure PI lm (10.24%).
Upon the incorporation of 5 wt% KKAc, however, both the tensile
strength and elongation at break of composite lm decrease. This
can be explained by the oriented growth of polyimide chains in the
interlayer of kaolinite, as shown in Fig. 4, and the layer structure of
kaolinite limit the motion of their chains. When KKAc content is
less than 5 wt%, good dispersion of clay particles in polyimide
matrix leads to an efcient stress transfer and avoids excessively
rapid growth of micro-cracks [35]. There is an obvious orientation
effect for polyimide molecules chains. Consequently, the tensile
strength and elongation at break of composite lm are signicantly
improved. However, when the KKAc content exceeds 5 wt%,
kaolinite particles are partially reunited and unevenly dispersed,
and the polyimide molecules partly stretch out of the layer of
kaolinite. So the tensile strength and elongation at break of the
composite lms decrease. Ye et al. [36] revealed that the clay
particle acted as a barrier to avoid the motion of polymer
molecules, and the data of their mechanical properties indicated
the same rules as our research.
Fig. 7 shows the FE-SEM micrographs of a cross-section of pure
PI and PI/kaolinite composite lms containing 19 wt% KKAc after
tensile tests. Fig. 7a exhibits the fracture surface of pure PI lm is
extremely smooth, but some plate-like and clusters-like structure
are found in perpendicular to the fracture surface for PI/kaolinite

Fig. 7. FE-SEM images of fresh cross-sections of (a) pure PI, (b) PI/1 wt%KKAc, (c) PI/3 wt%KKAc, (d) PI/5 wt%KKAc, (e) PI/7 wt%KKAc and (f) PI/9 wt%KKAc.

X. Qiu et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

2026

Table 2
The thermal, waterproof and optical properties of pure PI and PI/kaolinite composite lms.
MMT content (wt%)
a

T5 (8C)
T10 (8C)b
Water uptake rate (%)c
Water uptake rate (%)d
Onset/80% wavelength (nm)e
a
b
c
d
e

506.5
531.5
0.88
1.52
453/566

533.2
559.2
0.84
1.15
439/660

565.3
582.5
0.83
1.06
456/745

576.6
591.6
0.78
0.96
445/795

579.0
596.5
0.77
0.96
462/800

580.4
597.0
0.77
0.95
465/

Temperature at 5% weight loss from TGA measurement, scan rate: 10 8C/min, N2 protection.
Temperature at 10% weight loss from TGA measurement, scan rate: 10 8C/min, N2 protection.
The sample was soaked in water at 25 8C for 1 h.
The sample was soaked in water at 25 8C for 1 h, 100 8C for 1 h.
Transmission onset and 80% transmittance wavelength from UVvis spectra.

composite lms (Fig. 7bf) [37]. It indicates that a fracture

resistance exists in the composites, which is in a microstructure
consisting of clay and polymer matrices because of the presence of
the possible interaction between kaolinite and PI matrix. It
observes that the roughness of the fracture surface is increased
with increasing KKAc content and reaches the largest when KKAc
content is 5 wt%. The results of mechanical testing reveal that the
introduction of kaolinite particles can reinforce the mechanical
properties of PI matrix at low clay content.
3.4. Thermal properties of PI/kaolinite composites
The TGA curves of pure PI and PI/kaolinite composite lms with
different clay content are shown in Fig. 8. With increasing of
temperature the curves of all lms are nearly the same until about
400 8C. The thermal stability of composite lms is improved with the
increasing of KKAc content and becomes constant when the content
of KKAc exceeds 5 wt%. Table 2 lists the thermal property data of PI/
kaolinite composites with various KKAc contents. The decomposition temperature at 5% and 10% weight loss are increased with

Fig. 8. TGA curves of kaolinite, pure PI and PI/kaolinite composite lms.

Fig. 9. The cross-sectional morphology of (a) PI/3 wt%KKAc, (b) PI/5 wt%KKAc, (c) PI/7 wt%KKAc and (d) PI/9 wt%KKAc.

X. Qiu et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 20212028

increasing KKAc content. For example, the T5 and T10 measured by

TGA are improved from 506.5 and 531.5 8C for pure PI lm to 576.6
and 591.6 8C for PI/kaolinite lm containing 5 wt% KKAc. This
phenomenon is linked by the fact that the nanoscale compounding
of the clay particles can improve the thermal stability of polymer/
clay nanocomposites [38,39]. Kaolinite possesses high thermal
stability, its layer act as an insulator to avoid the polyimide chains
contacting with oxygen and limit the continuous decomposition of
the PI matrix. Fig. 9 illustrates the cross-sectional morphology of PI/
kaolinite composite lms contained 3 wt%, 5 wt%, 7 wt%, 9 wt% KKAc
at high magnication. Two different forms, polyimide matrix and
kaolin particles coexist in PI/kaolinite composite lms. At low clay
loading (3 wt%), few discrete kaolin particles are visible in polyimide
matrix, but the amount of exfoliated clay is not enough to enhance
the thermal stability. When increasing the clay concentration
(5 wt%), much more exfoliated clay is formed, more easily and
effectively and consequently promotes the thermal stability of
the composites. At even higher clay loading level (up to 9 wt%), the
intercalated clay structure is the dominant population, and the
morphology of the composite probably does not allow for
maintaining a higher thermal stability. So, the introduction of
kaolinite particles (5 wt%) can signicantly improve the thermal
stability of PI matrix.
3.5. Water absorption of PI/kaolinite composites
Moisture or water absorbed in a polymer matrix can lead to a
wide range of effects, including debonding at llermatrix
interfaces, structural damage, and chemical degradation of the
matrix during long-term exposure to water [40]. In response to the
effects of water in polymers, their application properties can be
signicantly affected. It is well known that polyimides absorb
moisture or water. Although the moisture absorption characteristic of polyimide lms is widely used in sensor applications [41], the
presence of moisture in the lms affects the electrical properties
[42] in some other applications. Water absorption is dependent on
the chemical structure of the polyimide control or composite lms,
temperature and duration of exposure [43].
In general, the water absorption of PI is very high because the
water molecules can easily diffuse into and form hydrogen bonds
along polymer chains. Kamal et al. [44] found that the diffusion of
water molecule became different for a composite that contained
laminated ller. Table 2 lists the water uptake ratios of control lm
and composite lms with different KKAc content. It is noted that
the water uptake ratios of composite lms are lower than those of
pure PI lm and signicantly decrease with increasing KKAc
content until 5 wt%. Introduction of kaolinite leads to an obvious
decrease in water absorption of PI/kaolinite composite lms. For
instance, the water uptake ratio is reduced from 0.88% (25 8C) and
1.52% (100 8C) for pure PI lm to 0.78% (25 8C) and 0.96% (100 8C)
for PI/kaolinite composite lm containing 5 wt% KKAc. Because the
layers of kaolinite act as a barrier to water diffusion into the
polyimide lm and separate the polyimide and water molecules
[45]. Better clay dispersions make composite lms possess lower
water absorption [46].
3.6. Optical properties of PI/kaolinite composites
Optical appearance is an acceptable and convenient method in
judging the dispersion of inorganic phase in polymer matrix. If the
polymer/inorganic composite are transparent, the inorganic phase
can be well dispersed in the polymer matrix [47]. The variation of
transparency values with wavelength for PI and PI/kaolinite
composite lms is shown in Fig. 10a. It is found that the composite
lms lose their transparency when the clay content further
increases. Two quantities, the transmission onset and the 80%

2027

Fig. 10. UVvis spectra of pure PI and PI/kaolinite composite lms with various
KKAc content.

transmission wavelength are usually used to evaluate the

transparency of these lms [48,49], as listed in Table 2. They
range from 453 to 465 nm for the onset wavelength, and from 566
to 800 nm for the 80% transmission wavelength. The transmittance
of all lms at 780 nm is given in Fig. 10b. With KKAc content
increases from 1 to 7 wt% in polyimide matrix, the transmittance of
composite lms slightly decreases. But when KKAc content is more
than 7 wt%, the transparency of lms rapidly decreased. This is an
evidence for a poor dispersion of KKAc particles in polyimide
matrix, and this phenomenon is consistent with the results of SEM
(Figs. 5f and 9d).
4. Conclusions
A series of composite lms that consist of polyimide and
modied layered kaolinite clay have been successfully prepared
via in situ intercalation polymerization. Kaolinitepotassium
acetate (KKAc) was used as an intermediate in this system. The
structures, morphologies and properties of PI/kaolinite composite
lms were systematically described. Results of XRD, FTIR, and SEM
revealed that polyimide chains have partially intercalated into the
layers of kaolinite by replacing KAc molecules and the kaolinite
particles showed well dispersion in polyimide matrix at low clay
content (5 wt%). The composite lms exhibited more excellent
performances than those of pure PI lms by means of universal
tester, TGA, and UVvis spectrometer. The tensile strength,
elongation at break and thermal stability of the composite lms
were signicantly improved until KKAc content exceeded 5 wt%.
The absorption behavior of PI/kaolinite lms suggested a
dramatically better waterproof property than pure PI lm. With
the increasing of KKAc content in polyimide matrix, the transmittance of the PI/kaolinite composite lms slightly decreased.
Acknowledgments
This work was supported by the Fundamental Research Funds
for the Central Universities (CUGL100407) and the National
Natural Science Foundation of China (50903077, 20872044), the
Natural Science Foundation of Hubei Province (2009CDB163,
2008CDZ065).
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