94 | Macromol. Symp. 2017, 371, 94–100 DOI: 10.1002/masy.

201600047

Preparation of Epoxy Composite Hollow

Microspheres (ECHM) Using Toluenesulfonyl
Hydrazide (TSH) as Blowing Agent
Nurul Ain Mohd Nayan, Anusha Leemsuthep, Zunaida Zakaria,
Du Ngoc Uy Lan*

Summary: The epoxy composite hollow microspheres (ECHM) was prepared by

single emulsion technique. Porofor Toluenesulfonyl hydrazide (TSH) 75 was used as
blowing agent. Carbon black was used as filler for polyamide-epoxy adduct matrix,
which was reverted ratio of 1:2 epoxy to polyamide. The epoxy mixture (internal
phase) was dropped and stirred into a heated corn oil (external phase) to form
spherical droplets. These epoxy droplets underwent two simultaneous mechanisms
of curing and foaming and became hollow microspheres. As expected, higher TSH
content produced lower density of ECHM because of more expansion in ECHM. This
fact was also evident from the size of hollow microspheres observed by using
scanning electron microscope. In addition, high TSH content of 16 phr induced higher
thermal properties of ECHM compared to those of ECHM using 8 phr and 12 phr TSH.

Keywords: epoxy; blowing agent; carbon black; hollow microspheres; emulsion technique

Introduction and 80 mm, but diameters in ranging from

Hollow microspheres is often used as void-
template in order to produce syntactic
foam for light weight structural application,
which exhibits isotropic physical properties
and low thermal expansion coefficient.[1–2]
The common microsphere used are glass
microspheres, cenospheres, carbon and
polymeric microsphere. Glass microbal-
loons are strong while polymeric
microspheres/hollow microspheres are
normally lighter and exhibit better adhe-
sion to polymer matrices.[3] Polymeric
microspheres/hollow microspheres have
reported made from unsaturated polyester
resin, silicone resin, polyvinyl chloride,
polystyrene, polyvinyl alcohol, polypropyl-
ene and epoxy resin.[2,4] The average
diameter of common microspheres/hollow
microspheres is generally between 30 mm
School of Materials Engineering, University Malaysia
Perlis, Kompleks Pusat Pengajian Jejawi II, 02600 Arau,
Perlis, Malaysia
Fax: (þ04) 979 8178; E-mail: uylan@unimap.edu.my
5 mm to 300 mm are possible to prepare by
using typical manufacturing methods.[3]
Hollow microspheres (as micro-balloon)
are commonly prepared using the alkali
swelling procedure (ASP), the dynamic
swelling method (DSM), the Shirasu po-
rous glass (SPG) membrane technique and
the water in oil in water (W/O/W) emulsion
polymerization technique.[5] The latter
process involves the use of organic solvents
or oil and is one of the effective method to
produce polymeric microspheres with con-
trollable diameter. However, organic sol-
vents normally raise a concern on
environment issue due to their volatile
organic content (VOC). Besides, the selec-
tion of oil should be taken the cost effect
into consideration. Normally, silicone oil is
quite costly compared to other regular oil
such as corn oil. In addition, the choice of
blowing agent used is another important
factor that affects the production of micro-
balloons. Porofor toluenesulfonyl hydra-
zide (TSH 75) is an exothermic organic
blowing agent which has decomposition

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Macromol. Symp. 2017, 371, 94–100
temperature of approximately between
105 C. [2] It contains 75% toluene sulfonyl
hydrazide (solid content), 25% paraffinic
mineral oil, so it is suitable for mixing with
epoxy and polyamide. TSH 75 generates
high volume of nitrogen of the hydrazide
group in elementary form and has 0.3%
max.[6] The selection of blowing agent is
based on its decomposition temperature
and its releasing gases. Azodicarbonamide
(ADC) has thermal decomposition at
200–210 C. Besides, diazoaminobenzene
may cause dermatitis and dinitrosopenta-
methylenetetramine gives off unpleasant
odor in some applications.[7]
Recently, composite microspheres are
interested to use as additives to prepare
polymer composite for specific application
thanks to their advantages of reduction in
filler’s content, overcoming filler’s sediment
(high density filler) and improvement in
filler’s dispersion for the final composite.[8,9]
Metal coated cenosphere is an effective
example, which could be obtained by several
methods such as magnetron sputtering depo-
sition,[8] sol gel auto combustion,[9] heteroge-
neous precipitation, electroless-plating and
physical/chemical vapour deposition.[8,10,11]
Though, production of metal coated ceno-
sphere was a complex process, which involved
two stages by producing cenosphere at first
and followed by coating them with metal. In
this research, single emulsion system method
to carbon black-filled epoxy composite
microsphere/hollow microspheres (ECHM)
is proposed. A free of polyunsaturated fatty
acids corn oil is selected as the oil phase in
single emulsion system because of its low cost
and no VOC caution. Blowing agent 
Porofor Toluenesulfonyl hydrazide (TSH)
75 is exploited to break initial droplets into
smaller droplets and expand them via its
decomposition reaction. The simultaneously
curing process is to stabilize the droplet
morphology; and epoxy composite micro-
sphere and hollow microsphere (ECHM) are
obtained. Carbon black filler would be
dispersed and located on the ECHM’s wall.
The ECHM is potential to use as an additive
in preparation of conductive composites with
the cost effectiveness by using low filler’s
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| 95
content, and the improvement on composite
properties by preventing the problem of
filler’s sediment and obtaining the better
filler’s dispersion.
Materials
Epoxy resin DER 331, polyamide A062 and
polyamine are obtained from Euro Chemo-
Pharma Sdn. Bhd. Epoxy resin is a clear
liquid with density and viscosity at 25 C of
1.16 g/ml and 11–14 Pas, respectively. Poly-
amide has density and viscosity at 25 C of
0.96 g/ml and 35–45 Pas. Corn oil from Yee
Lee Corporation Sdn. Bhd. has viscosity at
25 C of 50 mPas and free of polyunsaturated
fatty acids. Carbon black as conductive filler
is supplied from Chemicals Inc.. Porofor
Toluenesulfonyl hydrazide (TSH) 75 as
blowing agent is purchased from Bayer
Chemical with density at 25 C of 1.25 g/ml.
Preparation of Epoxy Composite Hollow
Microspheres (ECHM)
The basic recipe for the preparation of
ECHM can be seen in Table 1. Reversed
stoichiometric ratio of epoxy and polyam-
ide was used of 1:2 in weight. The Porofor
TSH75 used was 8 phr, 12 phr and 16 phr,
while carbon black of 20 phr was main-
tained for all formulas. The carbon black
was used as conductive fillers. At first,
epoxy was pre-mixed in sequence of
blowing agent, followed by carbon black
by using overhead stirrer with the speed of
300 rpm for 3 minutes. After that, polyam-
ide was added and mixed at the same speed
for another 3 minutes. Epoxy mixtures was
dropped into a heated corn oil beaker by
using a funnel with outer diameter (OD)
Table 1.
Basic recipe of epoxy composite hollow
microspheres.
Materials Part per hundred resins
Epoxy 33.3
Polyamide 66.7
Blowing agent 8, 12, 16
Carbon black 20
phr: part per hundred resins of total content of epoxy
and polyamide.
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96 | Macromol. Symp. 2017, 371, 94–100
Figure 1.
The schematic illustration of ECHM formation.
5 mm  20 mm length stem at 140 C under
stirring condition of 600 rpm for one hour.
The weight ratio of epoxy to oil was 10: 90.
The mixture was then allowed to cool down
to 80 C. The epoxy composite hollow
microspheres were filtered and washed
out the oil with detergent solution at
80 C. The detergent solution was changed
every 15 minutes until the oil was clean.
Drying and post-cure of hollow micro-
spheres was carried out at 80 C for two
hours in a conventional oven.
Characterization
The density of ECHM was measured by
Density Pycnometer. The morphology was
observed under scanning electron micro-
scope (SEM). Thermo-gravimetric ana-
lyzer (TGA) was analyzed using TA
equipment under flowing oxygen heated
from 25 C to 600 C at 20 C min1. Glass
transition temperature was analyzed by
using Differential Scanning Calorimetry
(DSC) in nitrogen at the heating rate of
10 C/min in heat range of 30 C  200 C.
The basic recipe for the preparation of
ECHM is displayed in Table 1.
Formation of Epoxy Composite Hollow
Microspheres (ECHM)
The formation mechanism of epoxy com-
posite hollow microspheres could be sug-
gested as Figure 1. The epoxy mixture
formed spherical droplets dispersing in the
corn oil due to the immiscibility between
epoxy and oil phases. The mechanical
ß 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
stirrer accelerated the emulsification by
providing a shear force to breakdown large
initial epoxy droplets into smaller epoxy
droplets by dispersing in oil phase.[2]
Curing reaction between epoxy and poly-
amide occurred, and the epoxy droplets
started to gel and form a cured outer skin.
Subsequently, Porofor TSH75 blowing
agent decomposed and produced an
expanding gas inside the gel epoxy droplet.
The decomposed gas was held inside the
epoxy by the cured wall leading to the
formation of epoxy composite hollow
microspheres (ECHM). Completely curing
would stabilize the ECHM’s shape.
Density and Morphology of Epoxy
Composite Hollow Microspheres (ECHM)
The relationship between density and size of
ECHM is indicated in Figure 2. The density
value for TSH8, TSH12 and TSH16 are
found to be 1.1791, 1.1686 and 1.1396 g/cm3,
Figure 2.
The relationship of density and average diameter of
ECHM at different Porofor TSH75 content.
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Macromol. Symp. 2017, 371, 94–100 | 97

Figure 3.
SEM micrograph of ECHM with different Porofor TSH75 content.

respectively. Higher Porofor TSH75 content features could interfere the curing of epoxy
decreased the density of ECHM whilst and weaken the cured skins of epoxy
increase the size of the ECHM. The fact of droplets so that they could expand to form
larger particles having lower density indi- the hollow microspheres. In addition, a
cated that more expansion in ECHM weak skin causing the blooming of epoxy
occurred. This fact is evident in SEM composite hollow microspheres, which
micrograph (Figure 3), where the higher generated smaller microspheres surround
content of Porofor TSH75 shows a larger size it. Similar observation was reported by
of generated hollow microspheres. Bakar et al.[2]
The SEM micrograph exhibited the
difference in size of hollow microspheres Glass Transition Temperature (Tg) of
due to the increase of Porofor TSH75 Epoxy Composite Hollow Microspheres
loading. Small microspheres and less (ECHM)
expanded microspheres are observed in Figure 4 showed the decomposition tem-
TSH8 (Figure 3(a)). This is because gas perature of Porofor TSH75 at 110.54 C,
nucleation at TSH8 was too low to expand
the epoxy droplets. More expanded micro-
spheres to form hollow microspheres are
presented in TSH12 and TSH16 due to
more gas formation (Figure 3(b) & (c)).
The hollow microspheres are confirmed in
cross section of an ECHM-TSH16 dis-
played in Figure 3(d), which shows the
hollow core and ECHM’s wall. Higher
blowing agent induces earlier and faster
foaming process as well as stronger expan- Figure 4.
sion pressure inside epoxy droplets. These DSC curve of Porofor TSH75.

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98 | Macromol. Symp. 2017, 371, 94–100

which indicates that TSH could fully

decompose at the preparation temperature
of 140 C. The result of the differential
scanning calorimetry for ECHM can be
observed in Figure 5. No decomposition
peak of Porofor TSH75 is detected
meaning that all blowing agent decom-
posed. Glass transition temperature (Tg)
of ECHM increases from TSH8 (at
80.5463 C) to TSH12 (105.067 C) and
Figure 5.
TSH16 (at 138.469 C). This behaviour
DSC curve of ECHM with different loading of Porofor
TSH75.
originates from the thermal conductivity

Figure 6.
(a) TGA curve of ECHM with different loading of Porofor TSH75. (b) DTG curve of ECHM with different loading of
Porofor TSH75.

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Macromol. Symp. 2017, 371, 94–100
Table 2.
TGA data of ECHM in air.
a
Samples T5% ( C) T10%b( C) T50%c( C)
TSH8 262.01 309.45 426.53
TSH12 270.87 321.01 431.94
TSH16 283.38 328.59 429.50
a
Temperature of 5 wt% of weight loss. bTemperature of 10 wt% of weight loss. cTemperature of 50 wt% of
weight loss. dFirst peak of decomposition temperature from DTG curves. eSecond peak of decomposition
temperature from DTG curves.
of ECHM responding to their size and
hollow morphology. Solid epoxy particles
could have higher thermal conductivity, or
in other words, more expanding hollow
microspheres would have lower thermal
conductivity due to their hollow core. The
results of Tg are well agreement with
morphology results of ECHM. In details,
TSH16 exhibits the highest Tg because of
its highest expansion and low density.
Thermal Properties of Epoxy Composite
Hollow Microspheres (ECHM)
Figure 6(a) & (b) showed TGA and DTG
thermograms while the analysing data
was reported in Table 2. Similar to DSC
results, there is no decomposition of TSH
in TGA, which proved that blowing agent
decomposed completely during the foam-
ing process. Distinguished TGA curve of
TSH8 from that of TSH12 and TSH16 was
observed. It is due to the difference
morphology, density and particle size of
TSH8 compared to those of the others.
The degradation of ECHM displayed a
two-stage process. The first step degrada-
tion occurred between 250 C – 425 C and
the second step degradation underwent
between 425 C–500 C. First degradation
stage could be due to the dehydration
of –OH side groups, –C═O in amide
groups of cured epoxy, which possess
oxygen in the structure. The second
degradation could be assigned to epoxy
backbone. The remaining residue after
600 C belonged to carbon black filler.
TGA and DTG curves reflect well the
morphology of ECHM. Smaller particles
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| 99
Decomposition ( C)
Peak Id Peak IIe Residues (%, 600 C)
377.73 447.23 32.171
379.50 450.63 26.830
347.81 442.57 28.007
and less expansion of TSH8 could conduct
better heat transfer and degraded at an
earlier temperature and decomposed in a
faster rate. As seen in Figure 6 (b), TSH8
was found to degrade majority on the first
stage and less in the second stage. The
higher onset degradation temperature of
TSH16 compared to that of THS12 also
proved the high pore content in ECHM –
TSH16. More hollow microspheres in
TSH16 decrease the thermal conductivity
hence enhanced the thermal resistance of
ECHM.
Conclusion
A single emulsion technique to produce
epoxy composite hollow microspheres is
reported. It is found that high blowing
agent content produces more expansion
and larger hollow microspheres, while low
agent content produces smaller solid
microspheres. Glass transition thermal
characteristic and thermal properties are
well reflecting the morphology of epoxy
composite hollow microspheres. In details,
larger hollow microspheres exhibited lower
thermal conductivity resulting in higher
glass transition and better thermal resis-
tance of ECHM.
Acknowledgement: We are sincerely grateful for
the financial support from the Ministry of Higher
Education Malaysia for providing the Exploratory
Research Grant Scheme (ERGS) 9010-00030 that
has made this work possible.
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100 | Macromol. Symp. 2017, 371, 94–100
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