Polymer xxx (2014) 1e5

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Polymer
journal homepage: www.elsevier.com/locate/polymer

A novel synthesis method for an open-cell microsponge polyimide

for heat insulation
Jinuk Kwon a, *, Jinyoung Kim a, Dongmyung Park b, Haksoo Han a, *
a
b

Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsan-no, Seodaemun-gu, Seoul 120-749, South Korea
Production & Engineering Division, Hankook Tire, Keumsan, Chungnam 312-820, South Korea

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 18 March 2014
Accepted 23 June 2014
Available online xxx

A novel method for synthesizing a microsponge polyimide (PI) lm with excellent thermal stability,
chemical resistance, and heat insulation performance was developed. The synthesized microsponge PI
lm has open cells with sizes between 1 and 10 mm and a porosity of 76%. Furthermore, the lm contains
several layers overlapping in multiple grid structures, which complicates the heat transfer paths. Thus,
the heat transfer coefcient of the microsponge PI lm is 67% less than that of existing polyimide lm
(0.054 vs. 0.16 W/m$K). This reduced heat transfer coefcient results in excellent heat insulation performance of the microsponge PI lm. The thermal decomposition (pyrolysis) of the microsponge PI starts
at 498
C and its glass transition temperature is 317
C, which indicates excellent thermal stability.
However, its Young's modulus, an indicator of mechanical strength, is nearly 74% less than that of
conventional PI lm (26 vs. 100.2 MPa).
2014 Elsevier Ltd. All rights reserved.

Keywords:
Polyimide
Microsponge
Heat insulation

1. Introduction
Polyimide (PI) is widely used in a variety of elds due to its
excellent mechanical properties, heat resistance, and chemical
resistance [1e4]. For example, PI is used for fabricating specialpurpose heat insulators that require high thermal and chemical
resistances. Thus, sponge PI lm has been commercialized and
widely used in the chemical industry and many types of installation industries for reducing energy consumption [4e7]. Several
methods are available for machining polymers into sponges, such
as the addition of blowing agents [8,9], pyrolysis of a thermally
inferior polymer after mixing of thermally strong and weak
polymers, [10] or addition of ceramic components [11] or porogens
[12,13]. These methods use additives to generate pores. The phase
inversion method uses solvents instead of additives, and wet
phase inversion is commonly used to fabricate various types of
polymer sponges [14,15]. This method is widely used for the
fabrication of polymer membranes. Furthermore, wet phase
inversion can be used for the fabrication of PI from a soluble PI
[16,17]. The PI backbone of common PIs resists the solvent; however, a sponge can also be formed using dry phase inversion

* Corresponding authors.
E-mail addresses: akito98@yonsei.ac.kr, akito98@naver.com (J. Kwon), hshan@
yonsei.ac.kr (H. Han).

proposed by Echigo et al. [18] Dry phase inversion is easily

applicable to highly efcient Kapton (DuPont Co.)-structured
polymers containing pyromellitic dianhydride and 4,4oxidianiline. This method involves polymerizing pyromellitic dianhydride (PMDA) and 4,4-oxidianiline (ODA) with poly(amic acid)
s in a tetrahydrofuran-methanol solvent to cast a lm, followed by
inducing phase inversion by adding water, and formation of a
microporous structure during curing into PI. Sponge PI with
microscale pores can be fabricated using this method. In the
present study, we developed a novel method for fabricating Kapton-structured microsponge lm using a simpler method than
conventional dry phase inversion. The fabricated microsponge PI
lm demonstrated superior heat insulation performance with an
excellent heat transfer coefcient of 0.054 W/m K.
2. Experimental section
2.1. Materials
Pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA)
were purchased from Tokyo Chemical industry Co. Ltd.. Acetone
and anhydrous 1-methyl-2-pyrrolidinone (NMP) were purchased
from Duksan Pure Chemicals Co., Ltd.. All the chemicals were used
as received without further purication. A bolt closure type autoclave (ILSHIN AUTOCLAVE) was used to perform the experiments at
11.7 MPa, 250
C.

http://dx.doi.org/10.1016/j.polymer.2014.06.090
0032-3861/ 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Kwon J, et al., A novel synthesis method for an open-cell microsponge polyimide for heat insulation, Polymer
(2014), http://dx.doi.org/10.1016/j.polymer.2014.06.090

J. Kwon et al. / Polymer xxx (2014) 1e5

2.2. Synthesis of microsponge PI

Fig. 1 illustrates the fabrication procedure. Poly (amic acid)s
were synthesized via a polymerization reaction between PMDA and
ODA.
The following is the microsponge PI fabrication procedure:
PMDA-ODA poly(amic acid) solution was prepared under a nitrogen
atmosphere by slowly adding PMDA (2.1812 g, 1 mmol) to ODA
(2.0024 g, 1 mmol) in NMP (30 mL). The reaction mixture was
stirred with a magnetic bar at 20
C for 24 h. The poly(amic-acid)s
solution glass plate is subjected to spin coating and placed into the
acetone-lled autoclave, which is then sealed airtight. The autoclave is then placed into the oven and the open-cell microsponge PI
is fabricated under increasing processing temperature/time from
150
C/30 min to 200
C/30 min and 250
C/120 min at a ramp rate
of 2
C/min and then a cooling rate of 2
C/min. The glass plate is
then retrieved from the autoclave, and a pure microsponge PI lm is
obtained by drying in an oven at 80
C.

2.3.5. Fourier transform infrared spectroscopy (FT-IR)

FT-IR spectra were obtained with an FT/IR-460 Plus spectrometer (Jasco, Japan) within a spectral range of 600e4000 cm1.
2.3.6. Thermogravimetric analysis (TGA)
TGA analysis was performed using a Q50 (TA instrument, USA).
The sample was placed in a platinum sample pan and characterized
by performing a scan from 30 to 800
C at a rate of 10
C/min in a
nitrogen atmosphere.
2.3.7. Differential scanning calorimetric (DSC) analysis
The glass transition temperature was investigated in a temperature range of 30e375
C using a Q10 (TA Instruments, USA) at a
scanning rate of 10
C/min in a nitrogen atmosphere.

2.3.1. Field emission scanning electron microscopy (FE-SEM)

The surface morphology was characterized using an S-900 eld
emission scanning electron microscope (Hitachi, Japan). The sample was coated with a conductive layer of osmium.

2.3.8. Heat transfer coefcient analysis

Heat transfer coefcients were measured by a laser ash
method with an LFA 447 NanoFlash, InSb Sensor (NETZSCH, Germany) according to ASTM E1461 (Standard Test Method for
Thermal Diffusivity by the Flash Method). The thermal conductivity was obtained by multiplying the thermal diffusivity, specic
heat, and density. The specic heat was measured with DSC
equipment after maintaining the temperature at 0
C for 5 min,
followed by ramping to 45
C at a rate of 5
C/min and holding at
45
C for 5min.

2.3.2. Surface area analysis

The surface area was measured according to the BrunauereEmmetteTeller (BET) theory. Analysis of the sample was
performed using a BEL-mini device (BEL Inc., Japan) in which nitrogen adsorption was measured at liquid nitrogen temperature
(77 K) after sufcient thermal treatment of each sample at 300
C.

2.3.9. Analysis of mechanical properties

Modulus and elongation were investigated using a Multitest
5-I (Mecmesin, UK) according to ASTM D882-91 (Standard Test
Method for Tensile Properties of Thin Plastic Sheeting). Measurements were made on ve different samples to ensure the
accuracy.

2.3. Characterization of the microsponge PI

2.3.3. Porosity analysis

An AccuPyc II 1340 density analyzer (Micrometrics Inc., USA)
and Autopore IV9500 (Micrometrics. Inc., USA) were used to measure the real density and apparent (bulk) density, respectively, and
the porosity was obtained as a percentage by subtracting the
apparent density value from the real density value and multiplying
the difference by 100 (Porosity (Real density  Apparent density)/Real density  100%).
2.3.4. Pore size distribution
The pore size distribution was analyzed with an Autopore
IV9500 mercury intrusion porosimeter (Micrometrics Inc., USA).
The contact angle of mercury on the microparticles was 130
and
the mercury surface tension was 485 dyn/cm.

Fig. 1. Preparation of the open-cell microsponge PI.

3. Results and discussion

3.1. Morphological characterization
The microsponge PI form was ascertained by investigating its
surface with an SEM and digital microscope. Fig. 2 (a), (b), and (c)
are FE-SEM images of the microsponge PI surface, which reveals a
large number of 5-mm diameter, open-cell pores.
As shown in Fig. 2 (d) and (e), open cells were evenly
distributed throughout the microsponge PI surface. Fig. 2 (b) and
(c) show multiple layers in the grid structure, which has the
effect of complicating the heat transfer paths from one surface to
the other, thus efciently preventing and delaying the heat
transfer. These heat-blocking membranes, which have not yet
been presented in other studies investigating microsponge PI
[10e14,16,18e20], are formed in a way that is highly effective for
blocking heat transfer. This heat-blocking effect was quantied
using a laser ash method, and the measurements results are
outlined in Table 1.
These values prove the extremely low thermal conductivity of
the microsponge PI, which was as low as 67% that of the PI lm
fabricated with a conventional solvent evaporation method.
In order to verify the porosity and pore distribution of such
open-cell microsponge PI, the bulk density and pore size distribution was measured using a mercury intrusion porosimeter. The
real density was measured with a density analyzer. The measurements revealed the porosity, real density, and bulk density to
be 75.9%, 1.162 g/m3, and 0.28 g/m3, respectively. The pore size
distribution data illustrated in Fig. 3 reveal the pore size as
1e10 mm and the representative pore size was approximately 5mm, similar to the FE-SEM results in Fig. 2. The BET-based surface
area measurement yielded a value of 10.6 m2/g.

Please cite this article in press as: Kwon J, et al., A novel synthesis method for an open-cell microsponge polyimide for heat insulation, Polymer
(2014), http://dx.doi.org/10.1016/j.polymer.2014.06.090

J. Kwon et al. / Polymer xxx (2014) 1e5

Fig. 2. (a), (b), (c) FE-SEM image of the microsponge PI surface (1,500x/2,500x/6,000x magnication). (d), (e) Digital microscope image of the microsponge PI surface (470x
magnication).

3.2. Thermal properties

3.4. Mechanical characterization

To test whether the microsponge PI has excellent thermal

properties equivalent to that of dense PI lm fabricated with the
solvent evaporation method, poly(amic acid)s were also prepared
with the solvent evaporation method under the same temperature
conditions. The glass transition temperature (Tg) was veried using
DSC. The 1 and 10% thermal decomposition temperatures (Td1%,
Td10%) were veried using TGA. Figs. 4 and 5 conrm that the
microsponge PI and PI lm demonstrate similar thermal properties.
TGA and DSC data prove that the microsponge PI fabricated using
the novel method underwent sufcient imidization reactions and
that it can be applied efciently in environments requiring high
thermal resistance.

Under the assumption that the open-cell sponge structure of the

microsponge PI might have reduced its mechanical properties
compared to the dense PI lm, the modulus and elongation were
measured to verify the degree of reduction. As shown in Table 2,

3.3. Structural characterization

FT-IR measurements shown in Fig. 6 were performed to verify
the physico-chemical compositions of the microsponge PI and PI
lm.
Symmetric and asymmetric absorptions of the imide carbonyl
group were observed near 1710 and 1666 cm1, respectively.
Furthermore, CeNeC stretching vibration of the imide ring was
observed near 1342 cm1 [21]. FT-IR data proved that the microsponge PI and PI lm have the same physico-chemical composition.

Table 1
Thermal conductivity of the microsponge PI and PI lm.
Item

Thermal conductivity [W/m$K]

Film thickness [mm]

Microsponge PI
PI lm

0.054
0.164

98
54

Fig. 3. Pore size distribution of the microsponge PI.

Please cite this article in press as: Kwon J, et al., A novel synthesis method for an open-cell microsponge polyimide for heat insulation, Polymer
(2014), http://dx.doi.org/10.1016/j.polymer.2014.06.090

J. Kwon et al. / Polymer xxx (2014) 1e5

Fig. 4. TGA data for the microsponge PI and PI lm.

Fig. 6. FT-IR spectra of the microsponge PI and PI lm.

compared to the conventional PI lm, the modulus was reduced by

76% during the microsponge shape process, whereas the elongation
did not show any signicant reduction.
The low modulus can be ascribed to the measurement of parts
that were unlled with PI because the modulus was measured
when the interior of the microsponge PI lm had a similar porosity
value as when the lm thickness was corrected using the tensioner.
This is indirectly supported by the elongation that was measured
without correction of the lm thickness that maintained a similar
value to that of the conventional PI lm.

4. Conclusions
A pilot experimental method designed to fabricate microsponge
PI was simpler and more versatile, irrespective of the PI type,
compared to the existing methods for polymer sponge fabrication,
i.e., the use of additives or a wet/dry phase inversion. The fabricated
microsponge PI demonstrated a high heat-blocking effect and an
excellent heat transfer coefcient of 0.054 W/m$K. This is admittedly inferior to a silica aerogel blanket (0.015e0.02 W/m$K)

Table 2
Mechanical properties of the microsponge PI and PI lm.
Item

Modulus [MPa]

Elongation [%]

Microsponge PI
PI lm

100.2 8
26.0 3

46.9 2
50.2 12

[22e26], which is the best heat insulator, however this is

compensated by the extremely simple production method that
circumvents complicated production processes such as supercritical drying. Microsponge PI is expected to nd various applications
such as an efcacious and cost-effective sound absorber or polymer
lter.
Acknowledgments
This work was supported by two National Research Foundation
of Korea grants funded by the Korean government (MEST) (NRF2009-C1AAA001-0092926, No. 2011e0016750).
References

Fig. 5. DSC data for the microsponge PI and PI lm.

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(2014), http://dx.doi.org/10.1016/j.polymer.2014.06.090