44 | Macromol. Symp. 2017, 371, 44–49 DOI: 10.1002/masy.

201600036

Effect of Sodium Bicarbonate in Fabrication of

Carbon Black-Filled Epoxy Porous for Conductive
Application
Anusha Leemsuthep, Nurul Ain Mohd Nayan, Zunaida Zakaria,
Du Ngoc Uy Lan*

Summary: Carbon black-filled epoxy porous (CBEP) was fabricated by using single
emulsion technique. Mixture of epoxy, polyamide hardener, sodium bicarbonate (as
blowing agent) and carbon black (as conductive filler) was dropped into a heated
corn oil at 160
C (containing free of polyunsaturated fatty acids). The epoxy-oil
system was stirred at 1000 rpm for 1 hour. Because of the immiscibility of epoxy
mixture and corn oil, droplets of epoxy mixture were formed. Initial epoxy droplets
were broken into small droplets due to the applied shear (from stirring). Receiving
heat from oil phase, the decomposition of sodium bicarbonate and the curing
reaction of epoxy and polyamide occurred simultaneously so CBEP was formed. It
was found that sodium bicarbonate exhibited a significant effect on the
morphology, thermal and conductivity properties of CBEP. Increase of sodium
bicarbonate’s content from 4 phr to 12 phr could produce larger epoxy particle size in
CBEP. However, CBEP using 20 phr of sodium bicarbonate’s content had the lowest
particle size. The content of 20 phr could induce an early and strong decomposition
reaction in the initial epoxy droplets, which broke them into smaller size; hence the
smaller particle size was obtained after curing. This fact was evident from the result
of bulk density, where higher sodium bicarbonate content induced lower bulk
density of CBEP. Furthermore, CBEP using higher sodium bicarbonate content also
exhibited better electrical conductivity.

Keywords: blowing agents; carbon black; conductivity; macroporous polymers;

polyamide-epoxy adduct

Introduction composites are the high dosage of conduc-

Conductive polymer composites are very
important nowadays due to the explosion
of electrical devices.[1,2] To prepare con-
ductive polymer composites, normally
conductive filler is directly dispersed into
polymer matrix. The conductivity behav-
iour of the composite, then depends greatly
on the dispersion of conductivity filler in
the polymer.[3,4] Most common problems
for preparation of conductive polymer
School of Materials Engineering, Universiti Malaysia
Perlis, Kompleks Pusat Pengajian Jejawi II, 02600 Arau,
Perlis, Malaysia
Fax: (þ04) 979 8178; E-mail: uylan@unimap.edu.my
tive filler required and the high density of
conductive filler, which could cause filler’s
sediment and poor dispersion. In solution,
conductive microsphere is considered as
one of the most advanced conductive
materials having low density and being
used at the low content in conductive
composites.[5] Conductive microspheres
attracted a considerable interest from
researchers and industry due to their
advantages such economic, low density
and better electrical properties.[6,7] They
have been widely used in electronic and
medical application.[8,9] One of the most
common conductive microspheres is metal
coated microsphere, which could be

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Macromol. Symp. 2017, 371, 44–49
produced by mussel-inspired surface func-
tionalization.[10] The process involves do-
pamine oxidative self-polymerization and
electroless plating. Besides, copper coating
poly(vinylamine) hollow particles was also
reported to be fabricated by the electroless
plating technique.[11] Actually, the fabrica-
tion of these conductive microspheres
involves to two processes, firstly micro-
sphere preparation and coating process in
sequence. The prepartion of microsphere is
quite challenging.
Microspheres is commonly fabricated
from single emulsion technique. Because
of the immiscibility of two liquids, the
droplets of one liquid are formed and
being dispersed throughout the other as
called a single emulsion system. Bakar
et al. produced micro-balloons based on
phase separation of epoxy mixture and
silicone oil to form epoxy droplet dis-
persed in the heated silicone oil.[12]
Blowing agent was mixed with epoxy
mixture in advanced. These epoxy mixture
droplets formed sphere particles in sili-
cone oil, which had blown via the
decomposition of blowing agent and
simultaneously cured via crosslinking pro-
cess to form epoxy micro-balloons by
receiving heat from silicone oil. The use
of reversed ratios of epoxy and polyamide
as called polyamide-epoxy adduct induces
a low crosslink density of the cured matrix,
so that it was able to be cured and blown
simultaneously under decomposition of
the blowing agent to form epoxy
macroporous.
The purpose of this paper is to aim
production of conductive macroporous
in one in-situ process. It means that
both processes of forming microsphere
and dispersing the conductive filler
occurred simultaneously. The sodium
bicarbonate was used as blowing agent
and carbon black was used as conduc-
tive filler. This research proposes single
emulsion technique as a simple process
to produce conductive epoxy macro-
porous, which have cell wall containing
dispersed carbon black as conductive
filler.
ß 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
| 45
Experimental Section
Materials
Epoxy resin DER 331 and polyamide A062
from DOW chemical were used to produce
epoxy porous. Epoxy resin DER 331 has
epoxide equivalent weight of 182–192,
density and viscosity at 25
C of
1.16 g/cm3 and 11–14 Pas. Polyamide
A062 has equivalent weight per H active
of 110, density and viscosity at 25
C of
0.96 g/cm3 and 35–45 Pas, respectively.
White crystalline powder of sodium bicar-
bonate from HmbG Chemicals having
density of 2.22 g/cm3 was used as the
blowing agent. Corn oil was purchased
from Yee Lee Corporation Sdn. Bhd.,
which contained free of polyunsaturated
fatty acids. Carbon black N330 (HAF) was
purchased from Chemicals. Inc. Carbon
black has iodine absorption number of
82  5 g/kg and CTAB surface area of
79–87 103 m2/kg.
Preparation of Carbon Black Filled Epoxy
Porous (CBEP)
A reversed ratio of epoxy and polyamide
was used of 1:2 in weight (as called
polyamide-epoxy adduct). The total weight
of epoxy and polyamide was considered as
one hundred parts (100 phr). Epoxy was
mixed with sodium bicarbonate by using
over-head stirrer with the speed of 300 rpm
for 3 minutes. Carbon black N330 was
added and mixed at speed of 300 rpm for
another 3 minutes. Afterward, polyamide
was added and stirred for 2 minutes at the
same speed. Epoxy mixture was dropped
into corn oil heated at temperature of
160
C and stirred at 1000 rpm for 1 hour.
The volume ratio of epoxy mixture to corn
oil was 1:9. Foaming and curing process
were occurred in epoxy droplets during
being stirred in hot oil phase to produce the
epoxy porous. The mixture of epoxy porous
and corn oil was allowed to cool down to
80
C. The epoxy porous was filtered and
washed five times with detergent solution
at 60
C. The ratio of detergent to water is
1:20. The detergent solution was changed
every 15 minutes. Drying and post-cure
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46 | Macromol. Symp. 2017, 371, 44–49
process of epoxy porous were carried out at
80
C for 4 hours in a conventional oven.
Characterization
Bulk density of CBEP was measured
according to ASTM D7481-09. 100 ml of
CBEP was measured using cylinder of
100 ml. The mass of 100 ml CBEP was
weight. Bulk density was calculated by
using mass diving to volume. Bulk density
was reported as an average of five measure-
ments. Particle density of CBEP was
measured by using gas pycnometer density
analyser, AccuPyc II 1340 V1.0.5. The
testing was carried out at room tempera-
ture using the chamber of 10 cm3 and
Helium gas. The morphology of CBEP
was observed using a scanning electron
microscope, model JSM 6260 LE JOEL.
CBEP was coated with gold/platinum layer
to avoid electrostatic charging during
examination. Image J software was used
to analyze SEM images; and the average
diameter of CBEP was determined by
counting 100 particles. Differential scan-
ning calorimetry (DSC) of sodium bicar-
bonate and CBEP was done in temperature
range from 25–200
C with a heating rate
10
C/min under nitrogen atmosphere.
Thermo-gravimetric analyzer (TGA) of
CBEP was done by using Pyris Diamond
TGA from PerkinElmer in temperature
range from 25–600
C with a heating rate
at 20
C/min under a nitrogen flow of
50 ml/min.
For conductive testing, epoxy DER331
and polyamine was used as a binder.
Polyamine has equivalent weight per H
Figure 1.
DSC curves of sodium bicarbonate powder.
ß 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
active of 95, density and viscosity at 25
C of
1.03 g/cm3 and 3–6 Pas, respectively. The
weight ratio of epoxy and polyamine was
10:5. Amount of 20 phr CBEP was added
into 100 phr of epoxy-polyamine binder.
The mixture was casted into PP mold with
dimension of 24  20  4 mm and allowed
to harden at room temperature for 24
hours. Electrical conductivity test of CBEP
was obtained by using Keithley 4200
Semiconductor Characterization System.
The samples were measured using two
probes I–V measurement system. The
distance between two probes was 5 mm.
The voltage was varied from 0 to 10 V. A
control epoxy carbon black composite
(using equivalent carbon black content in
CBEP) was prepared and its conductivity
was also measured (Figure 1).
Results and Discussion
Thermal Behavior of Sodium Bicarbonate
Decomposed temperature of sodium bicar-
bonate was investigated by using differen-
tial scanning calorimetry and reported in
Figure 2. The decomposed curve started
from 120
C and had the peak temperature
at 160.69
C. Therefore, sodium bicarbon-
ate was expected to fully decompose at
160
C temperature of corn oil and CBEP
could be obtained. The decomposition of
sodium bicarbonate as shown in reaction
Figure 2.
SEM images of CBEP: (a) CBEP-4SD at 1000X
(b) CBEP-12SD at 1000X (c) CBEP-20SD at 1000X and
(d) CBEP-20SD at 3000X.
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Macromol. Symp. 2017, 371, 44–49 | 47
Table 1.
Effect of sodium bicarbonate content on the bulk density, skeleton density and particle size of carbon
black-filled epoxy porous (CBEP).
Composition CBEP-4SD CBEP-12SD CBEP-20SD
Bulk density [g/cm3] 0.208  0.003 0.174  0.004 0.168  0.002
Skeleton density [g/cm3] 1.188  0.002 1.208  0.004 1.237  0.004
Particle size [mm] 4.820  2.191 5.481  2.591 4.333  2.151

(R1) as below[13]: content from 4 phr to 12 phr causes CBEP’s

2 NaHCO3 ! CO2 þ H2 O
þ Na2 CO3
Morphology Analysis
During emulsion, shear stress from high
stirring speed would split the initial epoxy
drop into many small droplets dispersing
in oil phase. Receiving heat from corn oil,
both curing reaction of epoxy and poly-
amide as well as the decomposition of
sodium bicarbonate would occur simulta-
neously. The decomposition of sodium
bicarbonate produced a growing decom-
posed gas, which induced an internal
pressure inside epoxy droplets. This inter-
nal pressure (depending on the blowing
agent content) would expand the epoxy
droplets or could burst them out into many
smaller ones flocculating each other. They
were solidified after the curing reaction
completed. As seen in Figure 2, CBEP
composed of many microspheres and
micro hollow sphere, which adhere to
each other.[14] This assumption was evi-
dent from the particle size of CBEP, which
increased from CBEP-4SD to CBEP-
12SD (expanding) but reduced in CBEP-
20SD (bursting) (as Table 1). The
suggested mechanism is also supported
from the epoxy particle in rod morphology
of CBEP-20SD (Figure 2(d)). The rod
type – epoxy particle could present the
spreading out epoxy droplets due to the
high content decomposed gas of CBEP
using 20 phr sodium bicarbonate.
bulk density decrease obviously. CBEP-
12SD also has larger particles compared to
ðR1Þ
CBEP-4SD. It means higher blowing agent
content produces the greater number of
epoxy hollow micro-spheres. However,
using above 12 phr sodium bicarbonate,
CEBP’s bulk density is slightly reduced. A
comparison on volume of all CBEP in a
same mass was carried out. In which, the
mass of 100 ml CBEP-20SD (having the
lowest bulk density) was measured, and
the volumes of CBEP-4SD and CBEP-
12SD in the same mass were measured by
using 100 ml cylinders. Figure 3 showed the
small particle size of CBEP-20SD could
occupy more volume compared to the
others. In contrast, particle density of
CBEP increases with higher sodium bicar-
bonate content. This indicated that the
sodium carbonate by-product of decompo-
sition reaction of blowing agent could
remain inside CBEP.

Density Analysis
The bulk density and particle density of
CBEP demonstrates in Table 1. It shows Figure 3.
that increase in sodium bicarbonate Volume of CBEP in a same mass.

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48 | Macromol. Symp. 2017, 371, 44–49
Table 2.
Thermogravimetric analysis of CBEP with different sodium bicarbonate content.
Composition Tonset [
C] T50%wt [
C]
CBEP-4SD 218.16 432.25
CBEP-12SD 227.61 446.59
CBEP-20SD 230.94 464.26
Thermo-Gravimetric Analyzer (TGA)
Table 2 shows thermal resistance behav-
iour of CBEP prepared from different
contents of sodium bicarbonate. The
results of TGA weight loss and derivative
thermograms (DTG) of CBEPs are
reported in Figure 4(a) and (b), respec-
tively. Based on Figure 4(a), no decom-
posed peak of sodium bicarbonate at
around 160
C is also detected (similar to
the DSC curves of CBEPs, which proves
that all blowing agent had decomposed
during emulsion stage). Thermal behaviour
of CBEP exhibits two decomposition
stages. The first stage is around
240–320
C and the second stage is around
400–550
C. It shows that an increase of
sodium bicarbonate content enhanced the
thermal resistance of CBEP on the onset
degradation temperature and the
Figure 4.
(a) Degradation weight of CBEPs as a function of
temperature. (b) Derivative weight loss of CBEPs as a
function of temperature.
ß 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Residual mass [%] TDTG at 1st peak [
C] TDTG at 2nd peak [
C]
11.604 314.00 508.99
12.465 314.99 512.61
15.767 313.65 518.24
temperature at 50% weight loss. The
enhancement could be originated from
higher porosity of CBEP using higher
blowing agent content. As shown in
Figure 4(b), significant degradation in the
first peak of CBEP-4SD is detected. The
first degradation peak temperature belongs
to the dehydration of —OH groups and
degradation of C¼O of epoxy structure.
The second degradation peak could be
carbon backbone of epoxy structure.
Conductivity behavior of CBEP filled
epoxy – polyamine matrix
The electrical conductivities of epoxy
composite filled CBEP (epoxy/CBEP)
and epoxy composite filled carbon black
(epoxy/CB) in equivalent weight as control
are reported in Figure 5. As proposed,
conductivity of epoxy/CBEP was signifi-
cant higher than that of control epoxy/CB
composite. Actually, the equivalent weight
of CB was 3.33%. Therefore, the conduc-
tive of the control epoxy/CB composite was
low, which had written as the common
problem in the introduction. In epoxy/
CBEP, carbon black was dispersing on the
CBEP surface and established the inter-
connection to conduct the electrical
Figure 5.
Electrical conductivity of epoxy/CBEP and control
epoxy/CB composite in equivalent carbon black
content.
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Macromol. Symp. 2017, 371, 44–49
current. Therefore the conductivity of
epoxy/CBEP composites was enhanced.
It is proven from the higher volume
occupied of CBEP-20SD (compared to
others in the same mass as seen in Figure 3)
meaning better carbon black dispersion in
CBEP-20SD. Hence, CBEP-20SD per-
formed the higher electrical conductivity
compared to CBEP-4SD and CBEP-12SD.
Conclusion
Carbon black filled epoxy porous as
sphere-packing of epoxy micro-particles/
epoxy hollow micro-sphere was prepared
via single emulsion technique. In details,
initial epoxy drops were split into small
epoxy droplets dispersing in heated corn oil
by the stirring shear stress. Because of
decomposed gas of blowing agent, these
droplets were able blown at low content of
sodium bicarbonate (4–12 phr), but further
burst into smaller droplets at high content
of sodium bicarbonate (20 phr). Completed
curing was to solidify these droplets and
form the epoxy porous particles. It was
found that, the higher the sodium bicar-
bonate content, the greater the number of
epoxy micro-particles and the lower bulk
density was. CBEP with lower bulk density
exhibited better thermal properties of
CBEP. The advantage of CBEP was
proven from the electrical conductivity
performance. The epoxy composite using
CBEP improved significantly the electrical
conductivity compared to epoxy composite
filled carbon black in an equivalent content.
Further work using higher temperature to
ß 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
| 49
produce epoxy porous to accelerate the
gelling time will be investigated.
Acknowledgement: The authors would like to
acknowledge Ministry of Higher Education
Malaysia for providing the ERGS grant (grant
no: 9010-00030) that has made this work
possible.
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