Journal of Colloid and Interface Science 352 (2010) 585592

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

FischerTropsch diesel emulsions stabilised by microbrillated cellulose and

nonionic surfactants
Anna Lif a,b,, Per Stenstad c, Kristin Syverud d, Magnus Nydn a, Krister Holmberg a
a

Chalmers University of Technology, Department of Chemical and Biological Engineering, SE-412 96 Gteborg, Sweden
AkzoNobel Surface Chemistry AB, SE-444 85 Stenungsund, Sweden
c
SINTEF Materials and Chemistry, N-7465 Trondheim, Norway
d
Paper and Fibre Research Institute, Hgskoleringen 6 B, NO-7491 Trondheim, Norway
b

a r t i c l e

i n f o

Article history:
Received 7 June 2010
Accepted 22 August 2010
Available online 31 August 2010
Keywords:
Emulsion
FischerTropsch diesel
MFC
Microbrillated cellulose
NMR diffusometry

a b s t r a c t
Water-in-diesel emulsion fuels have been prepared with a combination of sorbitan monolaurate and
glycerol monooleate as emulsier and with microbrillated cellulose (MFC) of different hydrophilic/
hydrophobic character as stabilizer. The MFC was treated with either octadecylamine or poly(styreneco-maleic anhydride), resulting in very hydrophobic brils. The most stable emulsion was achieved with
a combination of hydrophilic (untreated) and hydrophobic MFC and only minute amounts of the stabilizer gave a pronounced effect. Even with the optimized formulation the lifetime of the emulsion was
shorter than previously reported when a conventional polymeric stabilizer was used, however. The water
drop sizes in the emulsions were determined by three methods: optical images, light scattering, and NMR
diffusometry. All three methods gave water drops sizes of ca 2 lm. The NMR diffusometry indicated that
besides the micrometer-sized emulsion drops a signicant fraction of the water is present in small droplets of micelle size. The chemical exchange of water between these two populations of pools is believed to
be the reason for the relatively low stability of the system.
2010 Elsevier Inc. All rights reserved.

1. Introduction
Water-in-diesel emulsion fuels are known to give an improved
emission prole compared to regular diesel fuel in combustion in
internal combustion engines. We have previously shown that the
positive effect, in particular with respect to particulate matter, is
obtained for FischerTropsch diesel (FT-diesel), as well as for regular diesel of fossil origin [1]. Since FT-diesel can be produced from
biomass, water-in-FT-diesel emulsions constitute a hydrocarbon
fuel with an exceptionally low environmental impact.
Emulsion fuels have been prepared before with different types
of surfactants as emulsiers and polymers as stabilizers [2].
Various kinds of nonionic surfactants can be used, such as alcohol
ethoxylates, sorbitan monooleate and ethoxylated sorbitan
monooleate [16] but cationic gemini surfactants have also been
found useful as emulsier [7]. For the long term stability of the
emulsion a stabilizer needs to be added. The stabilizer prevents
the water drops to coalesce. Relatively low molecular weight nonionic surface-active polymers, such as poly(isobutylene)-succinic
anhydride ester of monomethyl-capped poly(ethylene glycol) have

Corresponding author at: Chalmers University of Technology, Department of

Chemical and Biological Engineering, SE-412 96 Gteborg, Sweden.
E-mail address: anna.lif@akzonobel.com (A. Lif).
0021-9797/$ - see front matter 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2010.08.052

been found useful for the purpose [1,2]. Particles may also be efcient emulsion stabilizers. Particle stabilised emulsions were described by Ramsden [8] and Pickering [9] already in the early
20th century and they are commonly referred to as Pickering emulsions. The particles that have been described for the purpose vary
from solid materials like silica [10,11] and clay minerals [12] to
parafn wax crystals [13].
During the last 10 years there has been a signicant and continuous interest in research on microbrillated (delaminated) cellulose (MFC). This relatively new material originates from the
disintegration of cellulose bres into sub-micron and nano-sized
brils and was introduced in the beginning of the 1980s [14,15].
The wood bres are built from microbrils with diameters of
approximately 3.5 nm [1618]. Mechanical brillation of the cellulose bres give a material consisting of brils in several size classes, with diameters typically ranging from 20 to 100 nm. Fig. 1
shows an example of a cellulose bre and a network of brils produced by brillation of such bres [19,20]. Having excellent
mechanical properties and high water adsorption capacity and
being based on a renewable feedstock, MFC constitutes an attractive new material. Several applications have been suggested for
this material, particularly for paper-making but also in food and
cosmetics. A relatively unexplored application of MFC, although
suggested already in 1983 [14] is as stabilizer of oil-in-water
emulsions.

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A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592

Fig. 1. Field-emission SEM images of a cellulose bre (left) and microbrillated cellulose (right) produced from bres using mechanical brillation.

Cellulose microbrils are hydrophilic, with ability to form interbrillar hydrogen bonds and, hence, strong networks. The brils
may be modied so that their surface becomes hydrophobic. Every
glucose monomer in the cellulose chain has three hydroxyl groups
that are possible sites for modications. Hydrophobic microbrils
can be obtained by silylation [21], or by grafting of polymer
brushes and layers [22]. This opened for the use of hydrophobic
MFC as stabilizer for water-in-oil emulsions [23,24]. Very stable
water-in-toluene emulsions could be formed and stabilized by silylated MFC and an interesting feature of such systems was that the
emulsion remained stable also when the drops became very large.
Evidently, the hydrophobized MFC was an effective stabilizer of
water-in-toluene emulsions.
For fuel emulsions hydrophobization of the MFC by silylation is
not suitable. The silicon atom may poison the exhaust catalyst. For
that reason two other hydrophobization agents were explored in
this work, octadecylamine and poly(styrene-co-maleic anhydride).
Periodate oxidation was used to introduce aldehyde groups on the
cellulose bres [25,26]. The oxidation leads to a dialdehyde formed
by oxidative cleavage at the C2C3 diol of the glucose ring. Subsequent reductive amination with octadecylamine gave a hydrophobized MFC. The other hydrophobization procedure involved
direct reaction of the MFC with poly(styrene-co-maleic anhydride).
In this reaction glucose hydroxyl groups react with anhydride rings
of the copolymer, attaching the hydrophobic polymer to the MFC
by ester bonds. The two types of hydrophobized MFC were evaluated as stabilizer for water-in-diesel emulsions in combination
with different types of low molecular weight emulsiers. The
emulsions obtained were characterized by light microscopy, light
scattering and NMR diffusometry.
2. Experimental
2.1. Materials
Dried kraft softwood pulp was used as raw material for MFC
production. The kraft pulps were pre-treated in a Clain conical rener using approximately 2000 kW h/ton before homogenization
in order to reduce the bre length and improve the runnability
during the MFC production. The pulp concentration during Clain
rening was 3%. This pre-treatment was followed by mechanical
brillation using a homogenizer (Rannie lab 12.56H). The pulp concentration was 1%, the pressure drop was 1000 bar and the pulp
was passed four times through the homogenizer [27].
Sodium periodate, octadecylamine, sodium cyanoborohydride,
imidazole and triethylamine were purchased from Fluka. Poly(styrene-co-maleic anhydride) was from Aldrich. The surfactants were
all from AkzoNobel Surface Chemistry, Stenungsund, Sweden and
used as received. The FischerTropsch diesel used was kindly supplied by FramTidsbrnslen Sverige, Sundsvall, Sweden. The diesel
specication is presented in Table 1.

2.2. Preparation of hydrophobized MFC

2.2.1. Oxidation of MFC and coupling of octadecylamine
A mild oxidation of MFC was performed in an aqueous suspension of MFC using 5 mmol sodium periodate/g MFC. The reaction
was run at room temperature for 1 h. The samples were washed
three times with water and then three times with methanol.
Octadecylamine (500 mg/g MFC) was added together with sodium
cyanoborohydride (125 mg/g MFC) and the reaction was run in
methanol at 60 C for 16 h. The solid was washed three times with
methanol, three times with acetone, twice with octane and then
redispersed in octane. The hydrophobic MFC obtained is referred
to as ****MFC-ODA.
2.2.2. Coating with poly(styrene-co-maleic anhydride)
An aqueous suspension of MFC was solvent exchanged rst to
acetone and then to dry toluene by repetitive cycles of centrifugation and redispersion. Poly(styrene-co-maleic anhydride) Mw 
224,000 (GPC) with 7 wt% maleic anhydride was added
(500 mg/g MFC) to MFC dispersed in dry toluene. Triethylamine
(10 mmol/g MFC) was added as a catalyst, the mixture was ushed
with nitrogen for 5 min and the reaction was performed for 4 h at
60 C. The product was washed three times with toluene and three
times with octane and then redispersed in octane. The hydrophobic
MFC obtained is referred to as ***MFC-SMA.
2.3. Characterization of hydrophobized MFC
For contact angle measurement the MFC dispersion (13% MFC
in octane) was applied and spread on a microscope slide. After
evaporation of the solvent the lm of the untreated MFC was
smooth, but the hydrophobized MFCs gave very porous surfaces.
The contact angle was measured with deionised water, using a
FTA200 Dynamic Contact Angle Analyzer (First Ten Angstroms,
Portsmouth, VA, USA).

Table 1
Diesel specication.
Property

Unit

FT-diesel

Aromatic content
Density at 15 C
Flash point
Initial boiling point
Final boiling point
Hydrogen:carbon (H/C) molar ratio
Net heat of combustion
Cetane number
Cloud point
Cold lter plugging point
Lubricity (WSD 1.4) at 60 C
Sulphur content

% (v/v)
kg/m3
C
C
C

<2
798
96
185
350
2.07
43
53
37
37
<300
<2

MJ/kg
C
C
lm
ppm (w/w)

A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592

2.4. Preparation of emulsions

The MFC, surfactant and FT-diesel were weighed into a glass
beaker. The mixing was performed with an Ultra-Turrax T25 Basic
at 24,000 rpm with a dispersing tool with 12.7 mm rotor diameter.
Water was added during high shear mixing. The emulsions were
stored in conical test tubes. Emulsions were prepared with two different water contents; 10% and 20% by weight (wt%). The nal
composition of the emulsions is given in Section 3. All values are
wt%.
2.5. Characterization of emulsions

gradient pulses. The NMR diffusometry method commonly used

for determining drops sizes in emulsions is based on the restricted
diffusion of water in the drops. The theory was developed by Murday and Cotts [30] and the equation derived (Eq. (4)) is based on the
Gaussian phase distribution approximation. Eq. (4) is tted to the
experimental data obtained from the STE-PFG NMR measurements.
In Eq. (4) an is the nth root of Eq. (5) and J is the Bessel coefcient
according to Eq. (5). The distribution in water drop radii is subsequently calculated by assuming that the drops are log-normal distributed in size. This approach yields the volume mean radius and
distribution width.
"

!
 1
2c2 g 2 X
a4
n
2 2
D
n1 R an  2









2 exp a2n DD  d  2exp a2n Dd  2exp a2n DD exp a2n DD d
 2d 
2
an D

I=I0 exp

2.5.1. Emulsion stability

The emulsion stability has been determined as the time in days
until free water is present at the bottom of the conical test tube.
The smallest detectable amount of water is of the order of 0.02% v/v.
2.5.2. Determination of drop size
Average drop sizes and drop size distributions were determined
by three different techniques; optical images, light scattering and
NMR diffusometry.
2.5.2.1. Direct images of the emulsions. Light microscopy imaging
was performed with a Nikon Labophot microscope connected to
a digital camera, Canon EOS 40D. The magnication was 100 times.
The drop diameters were manually counted and a number based
distribution of the drops was obtained. The number distribution
of the diameters was recalculated to a volume distribution by
use of the relation 4pr3/3, where r is the drop radius.
2.5.2.2. NMR diffusometry. NMR experiments were performed on a
600 MHz Bruker DMX600 spectrometer with a Bruker Diff30 diffusion probe. The gradient length (d) was 4 ms in all experiments and
the gradient strength (g) was varied in 64 steps between
0.02 T m1 up to a maximum of 11.0 T m1. The diffusion/observation time (D) was from 100 to 1000 ms. In all experiments a stimulated echo pulsed eld gradient pulse sequence (STE-PFG****)
with ramped gradients (10 ramps up and 10 ramps down with total ramping time of 0.1 ms) was used at 25 C [28,29]. All samples
were measured in Shigemi NMR tubes with 2.5 mm inner diameter
in order to minimize convective ow due to temperature gradients.
The normalised signal intensity I/I0, for non-restricted diffusion
in an NMR diffusometry experiment (STE-PFG) experiment is described by

I=I0 expkD

587

In Eq. (3) I is the observed signal intensity, I0 the signal intensity in

the absence of eld gradient pulses, D the self-diffusion coefcient,
and k = c2g2d2(D  d3), where c is the gyromagnetic ratio, g the gradient strength, d the gradient length, and D the time between the

an RJ 03=2 an R  1=2J 3=2 an R 0

2.5.2.3. Light scattering. The drop size was measured by low angle
laser light scattering using a Malvern Mastersizer Microplus from
Malvern Instruments, Malvern, UK. The analysis of the light scattering measurements was performed assigning a refractive index
of 1.3 for the water drops and 1.4 for the continuous phase. The value given is the volume mean diameter D [4,3].
2.5.3. Viscosity and density
Viscosity was measured with an AR-G2 rheometer from TA
instruments, using a measuring unit with cone and plate geometry.
The cone diameter was 60 mm and the angle between the surface
of the cone and plate 1. The density was measured with a Mettler
Toledo DA-100 M density meter.
3. Results
3.1. Characterization of the MFC
Films made from untreated MFC on glass slides were smooth
and gave low contact angles, with an average of 38. Films prepared from MFC hydrophobized with octadecylamine gave much
higher contact angles but accurate values are difcult to obtain because the surface becomes very porous. Fig. 2 shows water drops
on the MFC-ODA surface. The measured contact angle is over
120. The same behaviour was seen with MFC hydrophobized with
poly(styrene-co-maleic anhydride); i.e., a porous surface and a
contact angle of 115120. The porous lms obtained with the
hydrophobized MFC is probably due to the reduced number of
hydrogen bonds between the microbrils and thus a poorly developed lm.

Fig. 2. Water drops on a surface of MFC hydrophobized with octadecylamine.

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A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592

Fig. 3. Dispersions of untreated MFC (top image) and MFC-ODA (bottom image) in
water, toluene, EU-diesel, dodecane, and FT-diesel (from left to right).

3.2. Formulation of emulsions

A water-in-FT-diesel emulsion with reasonable stability was
not formed when MFC untreated or hydrophobized was used
as the only additive. A surfactant is needed in order to reduce
the interfacial tension. On the other hand, surfactants alone are
not sufcient either. Some kind of emulsion stabilizer is needed.
The variations in contact angles of the different MFC samples
are likely to result in differences in dispersibility and this was studied in some detail. Fig. 3 visualises the dispersibility of untreated
MFC and MFC-ODA in EU-diesel and FT-diesel, as well as in water,
toluene and dodecane. Whereas FT-diesel is purely parafnic, EUdiesel contains ca 30% aromatic hydrocarbon and this difference
in composition will inuence hydrocarbonwater interfacial tension. For comparison, the interfacial tensions of dodecanewater
and of toluenewater are 53 mN/m [31] and 37 mN/m [32], respectively. As can be seen, the two types of MFC differ considerably
with respect to dispersibility. The untreated MFC is readily dispers-

ible in both water and toluene but forms lumps in the other organic solvents. MFC-ODA, on the other hand, is not at all dispersible in
water, but readily dispersible in all the organic solvents. This difference in character is reected in the ability of the two MFCs to
stabilise the emulsions.
A large number of surfactants of nonionic type were tested. Anionic and cationic surfactants were deliberately avoided in order
not to introduce any element that could be detrimental to the
engine or the exhaust catalyst, such as sulphur, phosphorus, and
halide ions. Among the tested surfactants were ethoxylates such
as ethoxylated fatty alcohols, fatty amines, fatty acids, and fatty
amides, as well as non-ethoxylated nonionics such as glycerol esters, sorbitan esters, and alkyl glucosides. Only the ester type surfactants were successful in forming emulsions and the best results
were obtained with combinations of one glycerol ester and one
sorbitan ester. Reasonably stable emulsions were obtained with
combinations of glycerol monooleate (GMO) and sorbitan monolaurate (SML). Also combinations of glycerol monolaurate (GML) and
SML and of GML and sorbitan monooleate (SMO) provided relatively good stability. The GMOSML combination was studied in
detail with respect to relative amount of the two components
and total amount of surfactant needed. The emulsion stabilizer,
i.e., the untreated or the hydrophobic MFC, was also introduced
in the optimization of the formulation. The three types of MFC
were tested independently and in combinations.
Emulsions were prepared with two different water concentrations, 10% and 20%, and with untreated MFC as stabilizer. The
MFC concentration was from 0% to 0.026% and the surfactant combination was SML + GMO with 0.28% SML and 0.72% GMO (corresponding to a molar ratio of ca 30:70). The high water content
emulsions were more stable than the emulsions with low water
content, see Fig. 4. In addition, the sedimentation rate was considerably faster in the emulsions with the lower water content.
Evidently, untreated MFC is a more efcient stabilizer of the
emulsions with higher water contents.
Fig. 4 shows that the MFC concentration is critical. At a concentration of 0.005% or less the emulsions undergo rapid phase separation. A maximum in stability is found around 0.01% MFC, which
is a remarkably low value. The gure also shows experiments with
higher surfactant loading, 1% each of SML and GMO, corresponding
roughly to a 50:50 M ratio. This leads to somewhat more stable
emulsions but the maximum in stability is still around a MFC level
of 0.01%.

25

Stability (days)

20

15

10

0
0.000

0.005

0.010

0.015

0.020

0.025

0.030

MFC (wt-%)
Fig. 4. Stability in days of emulsions prepared with a combination of sorbitan monolaurate and glycerol monooleate as emulsier and with untreated MFC as stabilizer. Open
squares: 0.28% SML + 0.72% GMO and 10% water, lled squares: 0.28% SML + 0.72% GMO and 20% water, open triangles: 1.00% SML + 1.00% GMO and 10% water. The stability
refers to the time in days until free water is present in the bottom of the conical test tube.

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A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592
Table 2
Stability of emulsions made with different combinations of the two surfactants, sorbitan monolaurate and glycerol monooleate, and with a
combination of untreated MFC and the hydrophobic MFC-ODA as stabilizer. The water content is 10 wt%. The stability refers to the time in days until
free water is present in the bottom of the conical test tube.
No.

MFC in wt%

1
2
3
4

Surfactant in wt%

Stability days

Untreated MFC

MFC-ODA

Total

SML

GMO

Total

0.012
0.012
0.012
0.010

0.0038
0.0038
0.0038
0.0091

0.016
0.016
0.016
0.019

0.28
0.5
1
1

0.72
0.5
1
1

1
1
2
2

The two types of hydrophobized MFC, MFC modied with

octadecylamine and MFC treated with poly(styrene-co-maleic
anhydride), were also investigated as stabilizer of the waterin-FT-diesel emulsion. Both increased the emulsion stability but
less so than the untreated MFC. Most likely the MFC had become
too hydrophobic. The good dispersibility of MFC-ODA in the diesel,
see Fig. 3, can be seen as an indication of a pronounced hydrophobic character of the stabilizer. It is well-known that the most
effective particulate stabilizers are those with intermediate hydrophobicity [33].
In an attempt to optimize the hydrophobicity of the stabilizer,
combinations of untreated MFC and the hydrophobic MFC-ODA
were investigated. The water content was 10% and the ratio between the more hydrophilic sorbitan monolaurate and the more
hydrophobic glycerol monooleate was varied. The results are collected in Table 2 and the stability values can be compared with
the values obtained when only untreated MFC was used as stabilizer (Fig. 4). Table 2 shows that a small addition of hydrophobized
MFC is advantageous. The table also shows that with this mixed
stabilizer an increased amount of emulsier leads to a decrease
in stability of the emulsion, which is contrary to the result with
only untreated MFC as stabilizer, see Fig. 4. It is obvious that there
is an interplay between the hydrophiliclipophilic balance of the
emulsier combination and that of the stabilizer.

28
30
10
19

3.3.1.1. Microscopy. From the microscope images the drop diameters were manually counted and a number based distribution of
the drops was obtained. For the emulsion with untreated MFC
the log-normal distribution equation (Eq. (1)) was tted to the data
from the counting, and for the emulsion with untreated MFC in
combination with MFC-ODA, Eq. (2), the normal distribution equation, was used to t the data. The two ts along with the experimental data are shown in Fig. 5. The number mean drop
diameters were found to be 1.1 lm for the emulsion with untreated MFC and 1.9 lm for the emulsion with untreated MFC in
combination with MFC-ODA. The number distribution was also
converted into a volume distribution, which gave 1.5 lm and
2.0 lm as volume mean for the two emulsions, respectively.
2

N 1
ln x  l
y p
exp 
x
2r2
r
2p
N 1
x  l2
y p exp 
2r2
2p r

!
1

!
2

3.3.1. Water drop size determination

The water drops size and the size distribution were analysed by
three different methods: optical images, light scattering, and NMR
diffusometry. Two emulsions were investigated, both with 10%
water in FT-diesel. One emulsion was made with the emulsier
combination 0.28% SML + 0.72% GMO and with 0.013 wt% untreated MFC as stabilizer. The other emulsion was made with the
same emulsiers but had a combination of untreated MFC and
MFC-ODA as stabilizer, 0.012 and 0.0038 wt%, respectively.

3.3.1.3. NMR diffusometry. The normalised signal intensities, often

referred to the echo-decay, for water in the two emulsions are plotted vs k in Fig. 6 for D = 100 ms. The change in the slope at low kvalues shows that water undergoes two distinctly different diffusive motions, one fast (large slope) and one slow (smaller slope).
This indicates that the water is present in aggregates with different
sizes. The small aggregate with fast diffusion is believed to be
water-swollen reversed micelles, from here on referred to micellar
water, and the larger aggregate the emulsion drops.

normalized number of drops

normalized number of drops

3.3. Characterization of emulsions

3.3.1.2. Light scattering. In the analysis of the light scattering measurement the result is given as the volume mean diameter D [4,3].
The values obtained were 2.0 lm for the emulsion with untreated
MFC and 2.1 lm for the emulsion with untreated MFC in combination with MFC-ODA.

0,0

0,5

1,0

1,5

2,0

2,5

drop size, m

3,0

3,5

4,0

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

drop size, m

Fig. 5. Manually counted drop diameter distributions of emulsions of 10% water in FT-diesel stabilized with MFC (left) and MFC in combination with MFC-ODA (right).

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A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592
Table 3
Viscosity and density of different emulsions with 10% water at 40 C.

MFC

Surfactant (wt%)

Viscosity

Density

Kinematic viscosity

(wt%)

SML

GMO

Total

(m Pas)

(g/cm )

(mm2/s)

0.010
0.013
0.013

0.16
0.28
1.0

0.44
0.72
1.0

0.6
1.0
2.0

2.76
3.03
3.04

0.805
0.806
0.808

3.43
3.76
3.76

I/I0

0,0

13

12

5,0x10

13

1,0x10

1,5x10

k
Fig. 6. Echo-decays of the water signal in emulsions prepared with a combination
of sorbitan monolaurate and glycerol monooleate as emulsier and two different
MFCs as stabilizer. Open squares: untreated MFC. Filled triangles: untreated
MFC + MFC-ODA.

The fraction of micellar water is determined from a simple twocomponent t (Eq. (6)) to the echo-decay data. In Eq. (6) p1 is the
fraction of micellar water and D1 is the diffusion coefcient for that
aggregate. p2 and D2 are the fraction and diffusion coefcient,
respectively for the water in the emulsion drop. Although it should
be noticed that the two-component t is not absolutely correct in
this case it is a simple and rather accurate way to obtain the relative volume fractions on the two aggregates. The results show that
the relative amount of micellar water is 24% and 28% for the emulsion with untreated MFC and for the emulsion with untreated MFC
and MFC-ODA, respectively. The size of the micellar water aggregates can be calculated from the StokesEinstein equation (Eq.
(7)), assuming spherical aggregates, giving a radius of 5.6 nm and
5.8 nm respectively.

I=I0 p1 expkD1 p2 expkD2

D0

kB T
6pgRH

The observation time D (the time between the gradient pulses) in

the pulse sequence was varied in order to investigate if different de-

gree of diffusion restriction affected the echo-decay appearance,

which in turn may affect the size of the emulsion drops obtained
from the t of Eq. (4). The results obtained from varying D from
100 ms to 1000 ms are displayed in Fig. 7. For the emulsion with
untreated MFC a diameter of 2.15 lm was obtained and for the
emulsions with a combination of untreated MFC and MFC-ODA
2.20 lm was obtained at D = 100 ms. For longer observations times
the diameter becomes larger. This effect will be discussed in some
detail below.
3.3.2. Viscosity
The viscosity is one of the fuel parameters regulated in the
EN590 diesel standard, with a target range of 2.04.5 mm2/s. The
dynamic viscosity was measured for three emulsions, with varying
amounts of MFC and surfactant. All fuels showed a Newtonian
behaviour and the kinematic viscosity was calculated according
to m = lq, where m is the kinematic viscosity, l the dynamic viscosity, and q the density. The increase in surfactant concentration is
reected in an increased viscosity, as is shown in Table 3. However,
all values are well within the stipulated range. The kinematic viscosity of FT-diesel is 2.9 mm2/s.
4. Discussion
Particles are known to be efcient stabilizer of emulsions if they
adsorb at the oilwater interface. They may then prevent the drops
from coalescing and the effect on emulsion lifetime can be very
pronounced. The degree of hydrophobicity of the particles is the
most important parameter for their efciency as stabilizer of the
emulsion but the size and shape of the particles also play a role.
The best effect is usually obtained when the particles have a contact angle of around 90 at the oil/water interface [34]. If the contact angle is less than 90, the particles are primarily in the water

4.00
3.80
3.60

diameter (m)

3.40
3.20
3.00
2.80
2.60
2.40
2.20
2.00
0

200

400

600

800

1000

(ms)
Fig. 7. Water drop sizes versus diffusion time D for emulsions prepared with a combination of sorbitan monolaurate and glycerol monooleate as emulsier and two different
MFCs as stabilizer. Open squares: untreated MFC. Filled triangles: untreated MFC + MFC-ODA.

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A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592

phase and if the contact angle is above 90 the particles are in the
oil phase. At 90 the energy required to stabilize the system is at its
minimum.
The contact angles determined on the MFC-coated surfaces of
different hydrophobicity indicate that the untreated MFC is too
hydrophilic and the modied MFCs too hydrophobic. However, because of the structured surface the measured contact angles are
probably higher than the actual contact angle of the hydrophobized MFC. It is well-known that micrometer- and nanometer-scale
roughness, along with a low surface energy material, often leads to
high apparent water contact angles [35].
It was found that a mixture of the two MFCs gave the best result
in terms of emulsion stability. However, one must also take the
emulsiers into account. It is likely that the low molecular weight
surfactants interact with the MFC. The hydrophobized MFC, in particular, is likely to bind strongly to the surfactants. The MFC with
hydrophobic side chains can be regarded as a hydrophobically
modied polymer, although of unusually large size. Nonionic surfactants are known to interact strongly with such polymers, forming mixed polymersurfactant aggregates [36]. It is therefore likely
that when hydrophobized MFC is used, the oilwater interface is
covered with MFC-surfactant aggregates rather than with the modied MFC only. The wetting characteristics of such aggregates will
obviously depend on the physicalchemical character of both the
emulsiers and the stabilizer. The situation is less obvious when
untreated MFC is used as stabilizer. Unmodied MFC is hydrophilic
and is not likely to interact strongly with low molecular weight
amphiphiles. It has been shown, however, that cellulose interacts
with nonionic surfactants [37]. In analogy, one may expect that
there will be some kind of attractive interaction between the untreated MFC and the surfactants used in this work, i.e., SML and
GMO. It is probable that the reason why such a good stabilizing effect was obtained also with the untreated, and thus very hydrophilic, MFC is that it forms aggregates with the surfactants
present in the formulation. Films made from such aggregates
may exhibit a contact angle very different from that obtained with
only MFC.
One of the most interesting ndings of this work is that there is
a pronounced optimum in the amount of MFC added as stabilizer
of the emulsion. Beyond the very low amount of 0.0100.015%
MFC, with a constant loading of 1% emulsier, the stabilizing effect
goes down. A higher amount of MFC most probably gives rise to a
too hydrophilic MFC-surfactant aggregate at the oilwater interface. Further studies, with more variations of the amounts of both
the MFC and the surfactants are needed in order to verify this
hypothesis.
The water drop size determination, by use of the MurdayCotts
equation to t the data from STE-PFG experiments, shows an increase in drop size when the observation time is increased. There
are at least two possible explanations for this behavior. Firstly,
the exchange of water between the nano-sized aggregates (micellar water) and the micrometer-sized emulsion drops. Such an exchange leads to an increase of the part of the echo-decay that
has a small slope as the observation time increases. The Murday
Cotts equation then gives an erroneously large drop size. The full
picture of the exchange of water between these two differently
sized compartments is not provided in this study because this

would require a comprehensive investigation of the echo-decays

at different observation times. This will be the subject for future
studies. From the existing echo-decays it can, however, be concluded that the exchange of water between the reversed micelles
and the drops is not very fast.
Secondly, the Brownian motion of the emulsion drops adds to
the total diffusive displacement of the water, which again makes
calculations according to the MurdayCotts equation result in too
large sizes because the equation assumes non-moving drops during the observation time. The effect of the Brownian motion of
the emulsion drops can be estimated by the relation in Eq. (8),
describing the displacement, Z, of a freely diffusing particle as
function of the observation time, D, and the diffusion coefcient,
D0. The diffusion coefcient can conveniently be obtained from
the StokesEinstein equation (Eq. (7)) by assuming a solvent viscosity, g, of 3.4 m Pas and by assuming that the light microscopy
images correctly describe the average sizes. These assumptions result in emulsion drop displacements of 92 nm for D = 100 ms and
292 nm for D = 1 000 ms. For D = 100 ms this corresponds to less
than 5% of the drop size and for D = 1000 ms it represents 15% of
the drop size. Thus, the Brownian motion of the drops seems to
give only a small contribution to the increase in drop size seen
as the observation time is increased.

hZ 2 i 2D0 D

Taken together, it seems that the increase in apparent drop size

seen in the NMR diffusometry experiments when the observation
time is increased can mainly be attributed to an exchange of water
between the two different water compartments. The Brownian motion of the drops works in the same direction but gives only a marginal contribution. It is likely that the exchange of water between
the nanometer-sized reversed micelles and the emulsion drops is
an important element in the macroscopic phase separation of the
emulsions studied in this work. The small reversed micelles facilitate rapid transport of water between the emulsion drops, making
the drops grow in size, thereby increasing the rate of phase separation [38].
The mean diameters of the emulsion drops obtained by the
three different characterization methods have been summarized
in Table 4. In this compilation, the emulsion drop sizes obtained
by the NMR method at the shortest observation time are in good
agreement with both light scattering and light microscopy.
5. Conclusions
In an attempt to nd a fuel for diesel vehicles giving low emissions of both soot and nitrogen oxides and with additives based on
renewable raw material we have evaluated untreated MFC and
hydrophobized MFC as stabilizer for water-in-FT-diesel emulsions.
Different types of hydrophobized MFC have been used and it was
found that the amount of surfactant used to form the emulsions
could be kept low. Determination of the drop size by three different methods resulted in similar values independent of the technique used. The NMR diffusometry measurements clearly showed
presence of a signicant amount of water in aggregates of sizes
in the low nanometer region in addition to the emulsion drops in
the low micrometer size region. As the observation time in the

Table 4
Water drops sizes, as mean diameters in lm, for two different water-in-FT-diesel emulsions with 10% water, determined with different techniques.
Emulsion composition

Light microscopy

Light scattering

NMR

Untreated MFC

MFC-ODA

SML

GMO

Number

Volume

Volume

Volume

0.013
0.012

0
0.0038

0.28
0.28

0.72
0.72

1.1
1.9

1.5
2.0

2.0
2.1

2.15
2.20

592

A. Lif et al. / Journal of Colloid and Interface Science 352 (2010) 585592

STE-PFG NMR experiment was increased the apparent emulsion

drop sizes increased. This effect is probably mainly caused by an
exchange of water between the two domains. It is likely that the
exchange of water between the nanometer-sized reversed micelles
and the emulsion drops is an important element in the relatively
fast macroscopic phase separation of the emulsions studied in this
work.
Acknowledgments
AL wishes to thank AkzoNobel Surface Chemistry AB and the
Knowledge Foundation through its graduate school YPK for nancial support. This project was also supported by the Research
Council of Norway, Sdra Cell, AkzoNobel and Jotun. Gary Chinga-Carrasco is thanked for acquiring the FE-SEM images.
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