Journal of Dispersion Science and Technology

ISSN: 0193-2691 (Print) 1532-2351 (Online) Journal homepage: http://www.tandfonline.com/loi/ldis20

Rheological Properties and Stability of Emulsion

Explosive Matrix

Kaiming Zhang & Ouqi Ni

To cite this article: Kaiming Zhang & Ouqi Ni (2015) Rheological Properties and Stability of
Emulsion Explosive Matrix, Journal of Dispersion Science and Technology, 36:7, 932-937, DOI:
10.1080/01932691.2014.942315

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Published online: 25 Jul 2014.

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 Journal of Dispersion Science and Technology, 36:932937, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2014.942315

Rheological Properties and Stability of Emulsion

Explosive Matrix
Kaiming Zhang and Ouqi Ni
Department of Chemistry, Nanjing University of Science and Technology, Nanjing, Jiangsu Province,
P. R. China

GRAPHICAL ABSTRACT
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An investigation was performed into the rheological properties and stability of emulsion explosive
matrix with different surfactants. The surfactants were oligomers of the polyisobutylene succinic
anhydride (PIBSA) based on different head group and relative low molecular weight sorbitan
monooleate (Span 80). The viscosity, shear stress, and storage modulus of emulsion explosive
matrix depend on the nature of surfactants. It was shown that the matrix formed by Span 80
has a lower viscosity, shear stress, and storage modulus, compared with the PIBSA-based surfac-
tants, especially the blended surfactant of Span 80 and PIBSA-TEA. The result of the precipi-
tation of ammonium nitrate (AN) and the change of storage modulus with time show that the
strength of interfacial lm formed by Span 80 is weak. This allows the crystal of AN to pass
through the interfacial lm more easily; thus, the stability of the matrix is decreased. However,
the storage modulus in aging was approximately constant and the ratio of the precipitation of AN
is the lowest when the matrix was stabilized by blended surfactant. It shows that the matrix
formed by blended surfactant has a better stability than single surfactants.
Keywords Emulsion explosive matrix, storage modulus, surfactant, viscosity

1. INTRODUCTION
Emulsion explosive is used a popular industrial explosive
worldwide. It has been developed from the early 1980s and
is widely accepted by customers for its advantages of being
waterproof, non-trinitrotoluene (non-TNT), high safety,
and good explosion performance. Emulsion explosive is
manufactured in two steps. First, oil phase and water phase
Received 3 June 2014; accepted 3 July 2014.
Address correspondence to Ouqi Ni, Department of Chemistry,
Nanjing University of Science and Technology, 200 Xiaolingwei,
Nanjing 210094, Jiangsu Province, P. R. China. E-mail: cggzkm@
163.com
Color versions of one or more of the gures in the article can be
found online at www.tandfonline.com/ldis.
are mixed into the emulsion explosive matrix, and then the
matrix is made into emulsion explosive by mixing with
hollow glass spheres (microspheres) or air bubbles.[1]
Emulsion explosive matrix is a typical highly concen-
trated water-in-oil emulsion. The dispersed phase droplets
consist of a supersaturated aqueous solution of inorganic
oxidizer salts, which are primarily, but not limited to,
ammonium nitrate (AN). The volume concentration of
the dispersed phase exceeds the limit packing volume
fraction (app. 0.74) so that the droplets are compressed
and transformed into polyhedrons. The droplets are not
monodisperse and their size distribution is rather wide.[24]
The emulsion explosive matrix possesses some peculiari-
ties of rheological properties due to the special structure

932
 RHEOLOGICAL PROPERTIES AND STABILITY OF EMULSION EXPLOSIVE MATRIX
and thus has attracted much attention. Otsubo studied the
effect of interfacial tension on the rheology of emulsion
matrix.[5] Princen and Kiss showed that the rheological
properties are characterized by elasticity at low shear stres-
ses and the existence of yielding behavior.[68] Masalova
and Malkin found that the rheological behavior of an
emulsion matrix can change, that its Newtons ow region
can be reduced, and that apparent viscosity can increase
and show its yield characteristics during shelf life.[9,10]
Mudeme et al. studied the dynamic emulsifying process
of concentrated emulsion matrixes and found that emulsi-
ers with small molecules favor an accelerated emulsi-
cation process and reduced energy consumption.[11]
Another property that has been studied in some papers
is the instability of emulsion explosive matrix, which is
thermodynamically unstable and will separate into its con-
stituent phases with time. Ghaicha and Leblanc investi-
gated the effect of monolayer properties of different head
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group polyisobutylene succinic anhydride (PIBSA)-based
surfactants on the stability of matrix.[12] Masalova showed
that the instability of matrix was caused by the crystalliza-
tion of supersaturated solution of the dispersed phase.[13]
Reynolds et al. studied the inuence of the structure of
interface layer on the stability of matrix.[14,15].
In this work, rst we studied the rheological properties
of emulsion explosive matrix formed by different surfac-
tants; second, the change of storage modulus and the
precipitation of AN with aging were studied to investigate
the stability of emulsion explosive matrix.
2. EXPERIMENTAL
2.1. Samples
Emulsion explosive matrix is a water-in-oil type highly
concentrated emulsion. The concentration of the dispersed
phase is 93.5% by mass, which is composed of 77.5 wt%
AN and 16 wt% water. The mineral oil (5 wt%) used was
base oil (viscosity 34.2 mm2=s, 40 C) produced by SINO-
PEC (China Petrochemical Corporation, Beijing, China).
Two PIBSA-based surfactants with different head groups
but the same carbochain were used. The concentration of
surfactant is 1.5% by mass. The details of surfactants are
listed as follows:
1. PIBSA-TEA: PIBSA reacted with triethanolamine (1:2)
at 150 C to a condensed ester head group. The mole-
cular weight of this emulsier is 1360.
2. PIBSA-IMIDEA: PIBSA reacted with tetraethylene
pentamine (2:1) at 150 C to a condensed imide head
group. The molecular weight of this emulsier is 2150.
Sorbitan monooleate (Span 80), as a usual nonionic surfac-
tant, also was used in this paper. Its molecular weight is
428. The mixture of Span 80 and PIBSA-TEA taken in
933
the ratio 3:7 was used to investigate the effect of blended
surfactant on the rheological properties and stability of
emulsion explosive matrix.
The emulsication process was conducted in 300 g
batches by LDF1-55 mixer (Fluko, Essen, Germany).
The oil phase consisting of surfactant was placed in the
bowl rst, mixed evenly, and heated to 80 C. Then, the
hot AN solution (90 C) was slowly added, while stirring
was maintained to ensure emulsication. Rapid mixing at
1000 rpm=min of mixer was carried out subsequently for
all formulations.
2.2. Rheological Studies
All rheological studies were conducted using a rota-
tional rheometer physical MCR 101 (Anton Paar, Graz,
Austria), with a PP50 at and 1 mm gap. Experiments were
carried out at 25 C.
The experiments were conducted in the following two
deformation modes:
. Scanning shear rate measurements with decreas-
ing shear rate from 100 to 0.01 s1 to test the
change of shear stress and viscosity.
. Amplitude sweep oscillations in the range of
strains from 0.1% to 200% at the constant fre-
quency of 1 Hz. The viscoelastic properties were
tested in this mode.
2.3. Storage Stability Studies
The precipitation of AN of emulsion explosive matrix
with time was measured to study the storage stability of
emulsions. The emulsions that experienced different time
were stored in a bowl containing 100 ml deionized water
for 10 hours. Then, the concentration of AN of the
deionized water was measured by titration.
3. RESULTS AND DISCUSSION
Some previous studies pointed out that the emulsion
explosive matrix behaves as a shear-thinning uid and pre-
sents clear non-Newtonian behavior.[9,10,16] The same result
was obtained in this paper. A typical ow curve of emul-
sion explosive matrix is shown in Figure 1. The viscosities
of emulsions decrease, whereas the shear rate increases.
The results show that different surfactants display different
viscosities at low shear rate. However, their viscosities at
high shear rate are close to each other. From Figure 1,
we can nd that the emulsion stabilized by Span 80 has
lower viscosity compared to PIBSA-based surfactants.
The viscosity values (g) can be considered as functions of
droplet size (D) and concentration. The dependence of g
on D1 is linear. This type of relation was suggested by
Princen and Kiss and Masalova and Malkin.[8,10] Thus,
we can speculate that the droplet size of matrix, which
 934
FIG. 1. Viscosityshear rate curves for fresh matrix with different
surfactant.
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FIG. 2. Viscosityshear rate curves for fresh matrix with blended
surfactant.
is stabilized by Span 80, is the greatest among these
surfactants. Span 80 has a lower interfacial tension com-
pared with PIBSA-based surfactants. It is easy to arrive
at the interface of oil phase and aqueous phase and form
a monolayer. This enables Span 80 to have a high degree
FIG. 3. PIBSA-based surfactants chemical structure.
K. ZHANG AND O. NI
of emulsication efciency. Masalova pointed out that
Span 80 can promote the renement of droplet of the
disperse phase.[13] But no same result was seen when Span
80 was used as a single surfactant to stabilize the matrix.
To understand the rening impact of Span 80, the
viscosity of emulsion explosive matrix stabilized by the
mixture of Span 80 and PIBSA-TEA was conducted. The
result is shown in Figure 2. It is obvious that the viscosity
of matrix stabilized by the blended surfactant is higher
compared to the single surfactant. It illustrates that Span
80 has the ability of rening the dispersed phase of matrix
when it is mixed with PIBSA-based surfactant. The
difference in renement effect between Span 80 and its
blended surfactant could be expected based on the follow-
ing reasons. During the emulsication process two opposite
effects tend to take place: fragmentation of the bulk liquids
into the resulting drops and the possible coalescence of
such drops.[17] So, on the one hand breakup of drops
occurs when the capillary number, which is the ratio
between two competitive stresses, namely, hydrodynamic
stress and interfacial stress, exceeds a critical value.
The hydrodynamic stress tends to stretch the droplet into
a lamentary shape, whereas the interfacial stress tends
to contract the droplet into a sphere of radius.[18] Although
Span 80 has a strong ability to decrease the interfacial
tension, its viscosity is much lower compared to PIBSA-
based surfactants. This made the contact of droplets
easier. The interfacial tension was decreased signicantly
when Span 80 was mixed with PIBSA-TEA. This increases
droplet breakup. But, on the other hand, the viscosity
kept constant so that the coalescence rate was decreased
during emulsication, thus reducing the contact of droplets.
It was found that the viscosity of matrix formed by
PIBSA-IMIDEA was lower than PIBSA-TEA in the low
shear rate region (Figure 1). Although the length of the alkyl
chain of PIBSA-IMIDEA (which has double alkyl chain,
Figure 3) is longer than that of PIBSA-TEA, the renement
effect is poorer. This could be affected by the different
anchoring phenomena between PIBSA-TEA and
PIBSA-IMIDEA. Some authors pointed out that the
polarity of the PIBSA-based surfactant head group is impor-
tant and affects the anchoring of molecules at the interface
and greater polarity implies stronger adsorption.[19,20] The
polarity is a consequence of the electronegativity difference
among carbon, oxygen, and nitrogen. The greater the
 RHEOLOGICAL PROPERTIES AND STABILITY OF EMULSION EXPLOSIVE MATRIX
electronegativity difference, the stronger the polarity. This
implies that groups containing carbonoxygen bonds are
more polar than those containing carbonnitrogen bonds.
So, it is reasonable to assume that the head group of
PIBSA-IMIDEA is less polar compared with PIBSA-TEA.
This led to the weaker adsorption of polar head groups at
the interface. Thus, the interaction with AN is decreased,
which in turn decreases the renement effect.
The stressshear rate curve is shown in Figure 4. Con-
trary to viscosity, the stress increases with the increase of
shear rate. The emulsion explosive matrix is a kind of Bing-
ham plastic body, and there is a yield stress. When the
applied stress is less than the yield stress, the emulsion can-
not ow. The ow curves in both low and high regions
were approximated using the HerschelBulkley equation:
r ry Kcn
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where r is the shear stress, ry is the yield stress, c is the
shear rate, and K and n are characteristic parameters of a
ow curve. The evolution of the yield stress is one of the
most characteristic rheological properties of emulsions.
Similar to viscosity, the renement inuences the yield
stress of emulsions, because rheological properties depend
on the droplet size, and this observation surely corresponds
to the known effect of the increase of yield stress with the
decrease of droplet size.[10,13] The analogous effect is
observed in the measurement of the elastic modulus, G0 ,
and the increase of elastic modulus as a consequence of
the decrease of droplet size.[13] However, unlike viscosity,
the yield stress and G0 are proportional to D2. It is a reec-
tion of the droplet surface area as a factor determining
elasticity. Compared to Span 80, the other three surfactants
FIG. 4. Shear stressshear rate curves for fresh matrix with different
surfactant.
935
had a higher shear stress due to their better renement
effect.
The storage modulus and loss modulus of emulsion
explosive matrix are shown in Figure 5. An elastic domain
was observed during the amplitude sweep test, which was
characterized by a constant plateau zone over a wide range
of strain deformation. This constant plateau region indi-
cates the structure of the sample is stable and not disturbed
by shear. The emulsion shows elasticity and can absorb
external energy. This type of external energy can be com-
pletely released when the external force is withdrawn. At
that low strain, the storage modulus G0 is greater than
G00 , which indicates that at this low strain region, the
material shows more viscoelastic solid behavior. Above
a certain value of strain, the elasticity decreased as the G0
curve began to fall below the G00 curve, indicating the emul-
sions approached a more viscous uid behavior. In terms
of surfactant type, the following trend for G0 is seen:
Mixture > PIBSA  TEA > PIBSA  IMIDEA > Span80
It is well known that emulsion explosive matrix is an
instable system and its instability (with aging) has two
possible causes. First, dispersed particles contain over-
cooled aqueous inorganic salt solutions and therefore they
are thermodynamically unstable. Second, the interfacial
lm formed by surfactant, which absorbs on the interfacial
lm, resulting in a decrease in interfacial tension and then
preventing contact between dispersed droplets, cannot
prevent the coalescence of droplets caused by the instability
of the dispersed particles.[10]
Changes in rheological properties of emulsion explosive
matrix with time are shown in Figure 6 by measurement of
storage modulus. It is clear that aging results in the increase
FIG. 5. Viscoelasticity curves of fresh matrix with different
surfactants.
 936 K. ZHANG AND O. NI
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FIG. 6. Storage modulus curves of matrix with time.
of storage modulus of emulsion explosive matrix. It shows
the increase of solid-like properties of emulsion explosive
matrix with aging, which can be treated as an
emulsion-to-suspension transition. In the four surfac- has good stability. The interfacial lm formed by the
tants of this work, Span 80 shows the most obvious
solid-like phenomenon. The value of storage modulus
increases markedly with aging. From Figure 7, no elastic
domain region can be seen in the storage modulus curve
of Span 80. The value of storage modulus increases mark-
edly and decreases very quickly with the increase of strain.
The low molecular weight and short carbochain of Span 80
could be the reason. The strength of monolayer formed by
Span 80 is weak. The crystal of AN can pass through the
interfacial lm more easily and contact each other, com-
pared with PIBSA-based surfactants. The G0 of matrix sta-
bilized by the blended surfactant was approximately
FIG. 7. Storage modulus curves of matrix after 10 weeks.
constant after 10 weeks (Figure 7). It shows that this matrix
blended surfactant is tough enough to prevent the breakage
of dispersed droplets formed by the crystal growth of AN.
To demonstrate the different interfacial strength of surfac-
tants, precipitation of AN in aging was conducted. It is a
simple, practical, and quantized method to measure the
number of ANs passing through the interfacial lm and
then dissolving in water. The greater the ratio of AN, the
lower strength of surfactant monolayer is. From Figure 8,
it is clear that the ratio of AN of emulsion explosive matrix
stabilized by Span 80 is the maximum. Thus, the strength
of Span 80 monolayer is weak so that the stability of matrix
is decreased.
 RHEOLOGICAL PROPERTIES AND STABILITY OF EMULSION EXPLOSIVE MATRIX
FIG. 8. The precipitation of AN with time.
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4. CONCLUSIONS
The systematic experimental study of the rheological
properties and stability of emulsion explosive matrix allows
us to come to some conclusions. First, the viscosity of emul-
sion explosive matrix behaves as a shear-thinning uid and
presents clear non-Newtonian behavior. The role of surfac-
tant nature in viscosity is substantial. The viscosity of matrix
formed by blended surfactant of Span 80 and PIBSA-TEA is
the highest. Second, the stressshear rate curve shows that the
stress increases with the increase of shear rate. An elastic
domain was observed during the storage modulus curve of
emulsion explosive matrix. This constant region means that
the structure of the sample is stable and not disturbed by
shear. Finally, the stability of emulsion explosive matrix with
aging is inuenced by the nature of surfactants. The result of
the increase of storage modulus with time shows the increase
of solid-like properties of emulsion explosive matrix. A mark-
edly high rate of the increase of G0 was observed when the
matrix was stabilized by Span 80. The precipitation of AN
with aging shows that the interfacial lm formed by Span
80 is weaker compared to the other three surfactants.
937
FUNDING
The authors thank the testing laboratory of Nanjing
University of Science and Technology for the support of
this study.
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