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J Surfact Deterg (2015) 18:373382

DOI 10.1007/s11743-014-1659-1

ORIGINAL ARTICLE

Detergency of Vegetable Oils and Semi-Solid Fats Using


Microemulsion Mixtures of Anionic Extended Surfactants: The
HLD Concept and Cold Water Applications
Linh D. Do Chodchanok Attaphong
John F. Scamehorn David A. Sabatini

Received: 29 June 2014 / Accepted: 21 November 2014 / Published online: 14 December 2014
AOCS 2014

Abstract In spite of the increasing interest in cold temperature detergency of vegetable oils and fats, very limited
research has been published on this topic. Extended surfactants have recently been shown to produce very promising detergency with vegetable oils at ambient
temperature. However, the excessive salinity requirement
(414 %) for these surfactants has limited their use in
practical applications. In this work, we investigated the
mixture of a linear C1018PO2EONaSO4 extended surfactant and a hydrophobic twin-tailed sodium dioctyl sulfosuccinate surfactant for cold temperature detergency of
vegetable oils and semi-solid fats. Four vegetable oils of
varying melting points (from -10 to 28 C) were studied,
these were canola, jojoba, coconut and palm kernel oils.
Anionic surfactant mixtures showed synergism in detergency performance compared to single surfactant systems.
At temperatures above the melting point, greater than 90 %
detergency was achieved at 0.5 % NaCl. While detergency
performance decreased at temperatures below the melting
point, it was still superior to that of a commercial detergent
(up to 80 vs. 40 %). Further, results show that the experimental microemulsion phase behaviors correlated very

L. D. Do  C. Attaphong  D. A. Sabatini (&)


School of Civil Engineering and Environmental Science,
University of Oklahoma, Norman, OK, USA
e-mail: sabatini@ou.edu
L. D. Do  C. Attaphong  J. F. Scamehorn  D. A. Sabatini
Institute for Applied Surfactant Research, University of
Oklahoma, Norman, OK, USA
J. F. Scamehorn
School of Chemical, Biological Engineering and Material
Science, University of Oklahoma, Norman, OK, USA

well with predictions from the hydrophiliclipophilic


deviation concept.
Keywords Microemulsion  Vegetable oil  Semi-solid
fats  Cold detergency  Extended surfactant  Hydrophilic
lipophilic deviation

Introduction
It has been reported that heating water accounts for more
than 80 % of energy consumption during the laundry
process [1]. A reduction of washing temperature from 40 to
10 C is projected to result in 5065 % energy savings [1,
2]. However, cold water detergency of vegetable oils and
semi to solid fats presents a critical challenge to the
laundry process. Vegetable oils are mixtures of triglyceride
oils which comprise to more than 95 % of the oil content.
Below their melting points, vegetable oils are semi-solid
fats, also known as waxy soils. These waxy soils are
mixtures of liquid oils and solid fats where the liquid oils
are entrapped in the crystalized structure of solid fats,
causing them to poorly interact with surfactants in solution
[3]. Further, above their melting points, vegetable oils or
oily soils are also difficult to remove due to their highly
hydrophobic nature and bulky triglyceride structure. Good
detergency with vegetable oils and fats generally requires
high temperature when using nonionic surfactants or high
salinity when using ionic surfactants [411]. While detergency of oily soils has been studied by several research
groups, very limited information on detergency of semisolid fats or cold water detergency of vegetable oils is
found in the literature [4, 5, 12]. Therefore, the overall goal
of this research is first to investigate the cleaning efficiency
of extended-surfactant-based microemulsion formulations

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on vegetable oils and fats at temperatures above their


melting points, and then to study detergency for these
formulations below the melting point, where microemulsions do not form.
Microemulsion-based formulations have been reported
to enhance the detergency of hydrophobic oily soil from
fabrics [4, 6, 1315], building on the early work of Miller
and Raney [810, 15]. These surfactant formulations can
effectively reduce the interfacial tension (IFT) between the
washing solution and the targeted oily soil to low values
(\0.1 mN/m), thereby lowering the work required to
remove the soil through roll-up and snap-off mechanisms.
Extended surfactants have proven to be the most successful
class of surfactants to produce ultralow IFT and form
alcohol-free microemulsions with vegetable oils at ambient
temperature [1621]. These surfactants have an intermediate polypropylene oxide (PO) and/or polyethylene oxide
(EO) groups inserted between the head and tail of the surfactant molecule. This unique chemical structure allows the
surfactant tail to extend further into the oil phase,
enhancing the surfactant tail-oil interaction without losing
its aqueous solubility [17, 22, 23]. Phan et al. [4] reported
microemulsion formation with canola oil at ambient temperature using a single branched extended surfactant,
C14,158POSO4Na. Very good canola oil detergency was
obtained at relatively low surfactant concentration
(500 ppm). However, the high salinity requirement (NaCl
concentrations of 414 wt%) limited the use of these
extended surfactants in practical applications. The high
salinity requirement was due to the very hydrophilic nature
of the extended surfactant. Minana-Perez et al. [24] reported
on phase behaviors and solubilization in microemulsions
containing mixtures of extended surfactants and conventional non-ionic surfactants. The application of et al. the
mixture of extended surfactants and non-ionic surfactants
has also been reported in the literature [6, 25]. Tanthakit
et al. [13] studied palm oil detergency at 30 C using a
mixture of an extended surfactant (branched C14,153PO
NaSO4) with a nonionic secondary alcohol ethoxylated
surfactant having five ethylene oxide groups. It was reported that the studied anionic/nonionic surfactant mixture at
25/75 weight ratio showed synergism in palm oil detergency performance compared to the use of a single surfactant. Optimum palm oil detergency (84 %) was reported
in the Winsor Type III region at 2,000 ppm surfactant
concentration and 2 wt% NaCl. While good detergency was
achieved, the surfactant and salinity concentrations were
relatively high for the laundry application.
In spite of increasing interest in cold water detergency
for vegetable oils and fats, very limited information on this
topic is published in the literature; therefore, the use of
further optimized extended surfactant mixtures for such an
application is of special interest in this study. The

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J Surfact Deterg (2015) 18:373382

objectives of this research were to (1) develop an extended


surfactant-based formulation with good detergency but
reduced salinity levels from previous research; (2) compare
the experimental microemulsion phase behaviors above the
melting points with the theoretical hydrophiliclipophilic
deviation equation; and (3) study the cold temperature
washing efficiency of mixed extended surfactant and
sodium dioctyl disulfosuccinate (SDOSS) surfactant both
above and below the melting point of select oils. Four oils
were evaluated in this study, including canola, jojoba,
coconut and palm kernel oils. These oils can be characterized into two different groups of high melting temperature oils (coconut and palm kernel oils) and low melting
temperature oils (canola and jojoba oils). They can also be
characterized into two different chemical structure groups,
triglyceride oils (canola, coconut and palm kernel oils) and
waxy oil (jojoba oil) [26]. Selected physical properties and
chemical structures of these oils are shown in Table 1.
The choice of extended surfactant was guided by previous work [18]. When comparing the optimum interfacial
tension (IFT*) values and optimum salinity (S*) among
three types of extended surfactants (linear PO extended
surfactant, branched PO extended surfactants and linear
POEO extended surfactants) with triolein oil, Do et al.
[18] reported that ultralow IFT* could be achieved with
linear POEO extended surfactants, specifically C10
18PO2EONaSO4, at the lowest S*. While the extended
chain of the surfactant lowers IFT values and enhances oil
solubilization, microemulsion formation using extended
surfactant alone took weeks to months to equilibrate due to
the high rigidity of the surfactant membrane [19, 27, 28].
High salinity also caused dehydration of the surfactant
headgroups, leading to close packing of the surfactant
micelles, higher rigidity of the surfactant membrane and a
slow coalescence rate [27, 28]. To overcome this problem,
we propose to use a mixture of C1018PO2EONaSO4
extended surfactant and branched sodium dioctyl disulfosuccinate (SDOSS) surfactant. It has been shown that a
mixture of two branching tail cationic/anionic surfactants
Table 1 Chemical structures and selected physical properties of
studied oils
Oil

Melting point
(C)

Chemical structure

Canola

-10

Triglyceride oil

Coconut

24.4

Palm kernel
Jojoba

28.6
9.7

Wax oila
(Z,Z)-CH3(CH2)7CH=CH(CH2)mCOO
(CH2)nCH=CH(CH2)7CH3 m = 7, 9,
11, 13 and n = 8, 10, 12, 14

Adapted from [17]

J Surfact Deterg (2015) 18:373382

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improved surfactant tail-oil interactions, enhancing limonene oil solubilization [29, 30]. Witthayapayanon et al.
[19] reported that the use of SDOSS surfactant in a mixture
with a branched PO extended surfactant was able to reduce
the coalescence rate to form microemulsions with hexadecane from months to less than an hour while substantially reducing the salinity requirement. While these studies
dealt with microemulsion formation and phase behaviors at
relatively high surfactant concentrations ([4 wt%), our
study here focuses on lower surfactant concentrations for
detergency application.
As stated in the objectives, we are also interested in
correlating the experimental microemulsion phase behaviors with those predicted by the theoretical hydrophilic
lipophilic deviation (HLD) equation. HLD concept was
first introduced and developed by Salager et al. [3133].
An extensive review on the HLD concept was recently
published by Salager et al. [22]. The general HLD equation
for anionic surfactant is described as follows [17, 22, 33
36]:
HLD lnS  K  NC;O  f A Cc  aT DT

where S stands for the salinity concentration in the aqueous


phase (g/100 mL); K is a constant parameter, ranging from
0.1 to 0.16 depending on the surfactant headgroup [32, 34];
NC,O represents the number of carbon atoms in the oil
molecules, also known as alkane carbon number (ACN) for
alkane oils or equivalent alkane carbon number (EACN) of
other oils [17, 22, 34]; f(A) is a function of the co-surfactant
or alcohol; Cc is the characteristic curvature of the surfactant molecule [34] (also referenced to as r which was
defined as a characteristic surfactant parameter in the original work of Salager et al. [33]; aT is the temperature
coefficient and has a value of 0.01 for most ionic surfactants [32, 37]; DT is the temperature difference between the
studied temperature and the reference temperature (25 C).
For co-surfactant and alcohol free microemulsions,
f(A) = 0. The HLD value indicates the deviation of the
microemulsion phase from optimum Winsor Type III microemulsions where the surfactant interactions in the oil
and aqueous phases are balanced [27, 32, 34]. Thus,
HLD = 0 for optimum Winsor Type III microemulsions,
HLD \0 for Winsor Type I microemulsions and HLD [0
for Winsor Type II microemulsions. It is important to note
that the Cc value also reflects the relative hydrophilicity
or hydrophobicity of the surfactant. It has been well
established that the HLD approach is preferred to the
hydrophiliclipophilic balance (HLB) approach for
microemulsion formulation, and that the Cc is preferred to
the HLB number as predicted from the group contribution
number in comparing the relative hydrophobicity/hydrophilicty among surfactants, especially for extended surfactants [32, 38].

Applying the linear mixing rule for microemulsions


systems containing binary mixture of anionic surfactants,
the HLD equation can be written as [34]:
HLDmix X1 HLD1 X2 HLD2

where X1 and X2 are the molar fractions of surfactants 1 and


2. Correlations between the experimental and predicted
microemulsions phase behaviors are discussed in this paper.

Experimental Procedures
Materials
The linear extended surfactant C1018PO2EOSO4Na
(22.55 %) was donated by Hunstman Chemical Co.
(Houston TX, USA), and the branched surfactant dioctyl
sodium sulfosuccinate (SDOSS, ?99 % anhydrous) was
purchased from Fisher Scientific. Sodium chloride (NaCl,
?99 %) and oil-soluble dye Oil-red-O were purchased
from Sigma-Aldrich (St. Louis, MO, USA).
Crisco pure canola oil (The J. M. Smucker Company,
Orrville, OH, USA) was purchased from a local market.
Pure jojoba oil was purchased from NOW Foods. Palm
kernel and coconut oils were purchased from Mountain
Rose Herbs (Eugene, OR). All materials were used without
further purification.
The fabric used in the detergency test was a white 65/35
polyester/cotton blend and was purchased from a local
market. A commercial detergent (Tide Liquid Laundry
Detergent, Clean Breeze) was also purchased from a local
market and was used for comparison purpose.
Methods
EACN Determination of Studied Oils
The use of an optimum formulation correlation method or
HLD method for determining the EACN or NC,O value of
an unknown oil has been well documented in the literature
[18, 32, 34]. The EACN and NC,O terms are used interchangeably in this paper. EACN values of studied oils were
determined using the surfactant C1018PO2EONaSO4 at
25 C. The HLD equation for C1018PO2EONaSO4 in
the absence of alcohol and at 25 C is [18]:
HLDC10 18PO2EONaSO4 lnS  0:1042  NC;O
 0:0314

Semi-solid coconut and palm kernel oils were mixed


with canola oil at a 1:1 weight ratio to form liquid oil
mixtures at 25 C in order to find their EACN values. The
EACN value of unknown oil can be calculated from a
mixture using the formula below [34]:

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EACNmix X1 EACN1 X2 EACN2

J Surfact Deterg (2015) 18:373382

where X1 and X2 are the mole fractions of each oil in the


mixture and EACNmix was found from the optimum
salinity for a given oil and Eq. (3).
HLD Calculations of Mixed Ionic Surfactants
Equation (2) was used to calculate HLDmix for binary
anionic surfactant mixtures of C1018PO2EONaSO4 and
SDOSS. The HLD equation for SDOSS in co-surfactant
free systems and at 25 C was reported in the literature as
the following [34, 38]:
HLDSDOSS lnS  0:17  NC;O 2:50

Dynamic Interfacial Tension (IFTDyn)


Dynamic interfacial tension experiments were performed
using a spinning drop tensiometer (University of Texas,
Model 500). First, 13 lL of oil was injected into a 300-lL
capillary tube containing the aqueous surfactant solution.
Each IFTDyn sample was repeated in triplicate and recorded
at 20 min.
Microemulsion Phase Behavior Experiments
Phase behavior experiments were carried out by fixing the
total surfactant concentration at 1 w/v % and varying the
salinity concentration. For low melting point oils (canola and
jojoba oils), equal volumes of aqueous phase and oil at 5 mL
(or water to oil ratio, abbreviated as WOR at 1) were put into
a 15-mL glass vial. For high melting point oils (coconut and
palm kernel oils), due to the difficulty in mixing the semisolid fat with the aqueous surfactant solution, (i.e., the semisolid fat adhered strongly to the vial wall and did not suspend
into the aqueous surfactant solution at high WOR), a WOR of
4:1 (4 mL of water and 1 g of semi-solid fats) was used. The
solutions were shaken three times a day for three days and
left for two weeks to ensure equilibrium.
Detergency
Detergency testing was conducted following the procedures documented in the literature [4, 5] and summarized
here. The 65/35 polyester/cotton blend fabric was prewashed in deionized water [39]. The fabric was then ironed
flat and cut into a 3 9 4 inch swatches in the warp and weft
direction. Studied oils were mixed with chloroform at 20
vol%. Coconut and palm kernel oils were heated above
their melting points prior to mixing with chloroform. The
swatches were completely submerged in the oil/chloroform
mixture for one minute. The soiled fabrics were then hung
to dry and allowed to equilibrate overnight prior to use.

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The initial oil content in percentage of the soiled swatch


was determined gravimetrically by dividing the amount of
oil soiled on the swatch to the mass of pre-soiled swatch
times 100. The resulting swatches had an average oil
content to fabric mass of 25.5 1.7 % jojoba oil,
24.4 2.3 % canola oil, 25.1 1.3 % coconut oil and
24.2 1.6 % palm kernel oil.
Detergency experiments were conducted using a TergO-Tometer (Model 7243; USA Testing Co., Inc., Hoboken,
NF). Three soiled swatches (triplicate samples) were
washed for 20 min in 1 L of surfactant washing solution.
The swatches were then rinsed twice with 1 L of deionized
water for 3 and 2 min, respectively (i.e., two rinse cycles).
All washing and rinsing cycles were conducted at 120 rpm
agitation speed. The treated swatches were hung to dry
overnight using laundry wooden hanging clips with the
temperature in the laboratory ranging from 21 to 24 C
prior to evaluating the detergency performance. It is
important to note that under high humidity condition, the
fabric could take up moisture from the air causing error in
detergency performance analysis; this was not found to be
an issue in our work as the humidity in the laboratory was
relatively low and consistent (ranged from 35 to 55 %).
Preliminary tests were conducted to determine if the oil
soluble dye Oil-red-O was suitable for evaluating the
detergency performance. According to Goel [7], a suitable
dye should be soluble in tested oils, but not soluble in fresh
surfactant solution. However, it was found that the O-reddye was partially soluble in the fresh C1018PO2EO
NaSO4 and C1018PO2EONaSO4/SDOSS surfactant
solutions. Thus, the use of O-red-dye was deemed unsuitable in this case [7]. Also from [7], it was found the
detergency performance on 65/35 polyester/cotton blend
fabrics evaluated gravimetrically gave consistent and valid
results. We also found that the fabric weight loss due to
washing was less than 0.4 %. Therefore, we decided to use
the gravity method to evaluate the detergency performance
in this study. The detergency performance was determined
gravimetrically by weighing the pre-soiled, soiled and
treated fabrics directly on the mass scale. The fraction of
oil removed in percentage was determined by dividing the
amount of oil removed by the initial amount of oil and
multiplying by 100. It is important to note that, to further
examine whether the use of Oil-red-O dye is suitable for
evaluating the detergency performance, one can test for the
preferentially solubilization in micelles by adding an
excess amount of an oildye mixture into a micellar solution and evaluate if the concentration of the dye in the
excess oil phase changes. If it changes, the dye is indeed
not suitable for evaluating the detergency performance.
However, if the concentration of the dye in the oil after
solubilization is the same as the initial concentration, then
the use of Oil-red-O dye is still a valid method.

J Surfact Deterg (2015) 18:373382

Results and Discussion


EACN Determination
Figure 1 presents optimum salinity values (Table 2) for the
test oils as well as the HLD correlation for our surfactant
systems (lnS* vs. EACN developed using oils of known
EACN [18]). The EACN of the studied oils can be estimated from the information using the Do et al. [18] correlation as a calibration curve. The interfacial properties
(IFT values) and predicted EACN values of jojoba, canola,
coconut and palm kernel oils are summarized in Table 2. It
can be seen that ultralow IFT (\0.01 mN/m) were achieved
using the C1018PO2EONaSO4 extended surfactant. The
vegetable oils studied in this work had varying EACN
values, from a medium hydrophobic oil (jojoba,
EACN = 11) to a highly hydrophobic oil (canola,
EACN = 17). The hydrophobicity of the studied oils is in
the order of jojoba \ coconut \ palm kernel \ canola.

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and IFT reduction is expected for longer chain length


surfactants [17], using an extended surfactant alone also
makes the surfactant membrane highly rigid, causing the
formation of undesirable phases like gel or liquid crystals
[28, 38]. Adding a shorter tail branched surfactant into such
a system helps the surfactant membrane to be more flexible
[28, 29], thereby enhancing the surfactant interaction with
the oil phase. Mixtures of a linear or branching cationic
surfactant and a branched anionic surfactant has been
reported to avoid liquid crystal or gel formation [29, 30].
Using mixed anionic surfactant formulations in this study,
more than 90 % detergency of canola oil could be achieved
at relatively low salinity (2 %) without encountering this
aqueous solubility problem. Thus, in subsequent experiments, the C1018PO2EONaSO4 to SDOSS mole fraction was fixed at 0.260.74.
Table 2 Interfacial properties at optimum conditions and predicted
EACN values of studied oils with C1018PO2EONaSO4 at 0.15
w/v% at 25 C
MWa (g/
mol)

S* (w/
v%)

IFT*
(mN/m)

EACN

Jojoba

NA

3.00

0.00052

11

Canola

880

6.00

0.0057

17

50 vol% Coconut/canola
mixture

NA

4.50

0.0024

14

50 vol% Palm kernel/


canola mixture

NA

5.35

0.0026

16

Coconut

646

NA

NA

12

Palm kernel

756

NA

NA

15

DetergencySingle Versus Mixed Surfactant Systems

Oil

Figure 2 shows canola oil detergency as a function of C10


18PO2EONaSO4 mole fractions in the mixture with
SDOSS using optimum salinity (S*) conditions predicted
by the HLD method (HLDmix 0) at 25 C. The S* values
predicted from HLDmix 0 are also shown in Fig. 2. It can
be seen that mixture of these anionic surfactants showed
synergism in detergency performance compared to using a
single surfactant which is consistent with the literature
[40]. More than 90 % canola oil detergency efficiency
could be achieved using surfactant mixtures as compared to
68 % using SDOSS alone or 85 % using C1018PO2EO
NaSO4 alone. The detergency performance using an
extended surfactant alone (mole fraction of 1) was comparable to values reported in the literature using other
extended surfactants [4, 6]. While better oil solubilization

Fig. 1 EACN values of studied oils and their mixtures predicted


from the optimum formulation correlation for C1018PO2EO
NaSO4 at 25 8C. The optimum formulation correlation was adapted
from [18]

EACN for pure coconut and palm kernel oils were predicted from
Eq. (4)
NA not available
a

Adapted from [13]

Fig. 2 Effect of C1018PO2EONaSO4 mole fraction in mixture


with SDOSS on detergency of canola oil at 25 8C at their optimum
salinity concentration predicted from HLDmix and compared to a
commercial detergent. All surfactant concentrations were at 1000
ppm. Agitation was at 120 rpm. Full procedure test consisted of 20
min wash-cycle, 3 min rinse-1 and 2 min rinse-2

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Fig. 3 Correlations between


experimental microemulsion
phase behaviors and theoretical
HLD prediction for a coconut
oil and b palm kernel oil versus
NaCl scan. Phase behavior
experiments were conducted at
25 8C using 1 w/v% of total
surfactant concentration
consisting of C1018PO2EO
NaSO4 and SDOSS at 0.26/0.74
mole fraction

Phase Behavior, Optimum Salinity and HLD

Canola Detergency Versus Salinity and Rinse/No Rinse

Figure 3 presents salinity (NaCl) scans for microemulsion


phase behaviors of coconut (Fig. 3a) and palm kernel oils
(Fig. 3b) at 25 C (above both their melting points). The
lower portion of the figure visually shows the phase
behavior versus NaCl concentration. The upper region of
the figure shows microemulsion phases versus NaCl concentration as predicted by the HLD equation. It can be seen
that the HLD equation correlates very well with the
experimental microemulsion phase behaviors; e.g., at low
NaCl the phase behavior and HLD both show Winsor Type
I systems while at higher NaCl both show Winsor Type II
systems. It is interesting to observe the microemulsion
formation consisted of an excess semi-solid phase with
normal micellar microemulsions in the Type I region and a
middle phase microemulsion in equilibrium with excess
semi-solid phase and the aqueous phase in the Type III
region. A middle phase microemulsion of coconut oil was
experimentally obtained at 1 % NaCl, which agreed very
well with that predicted by the HLD method. Similarly, a
middle phase microemulsion for palm kernel oil was
observed at 1.5 % NaCl experimentally versus 1.56 %
NaCl predicted by the HLD method. Similar agreement
was likewise observed for canola and jojoba oils (data not
shown). Thus, the HLD concept proved to be very useful in
predicting the microemulsion phase behaviors of vegetable
oils using the studied surfactant systems.

Figure 4 shows the effect of NaCl concentrations (or microemulsion type) and washing cycles on the detergency
performance of canola oil at 25 C with C1018PO2EO
NaSO4/SDOSS mixture at 0.24/0.76 mole fraction. The
total surfactant concentration was 1,000 ppm. All studied
formulations had IFT values with canola oil well below 1
mN/m. Using NaCl concentrations from 0.05 to 1 % produced Winsor Type I behavior and from 4 to 5 % produced
Winsor Type II systems with 2.5 % corresponding to
Winsor Type III microemulsions. Considering the detergency performance from 20 min wash only cycle (no rinse)
with the surfactant formulation, it can be seen that the
highest oil detergency performance was achieved in the
Type I region approaching the Type III region. The trend in
increasing detergency efficiency as the microemulsion
phase approached the Type III region has also been
observed by other researchers [4, 14]. As the microemulsion phase approaches the Type III region, the IFT
decreases and the oil solubilized increases, thereby
enhancing the detergency performance [5, 14]. About 90 %
detergency was achieved in the Type I region at 0.5 %
NaCl. The detergency performance in the wash only (no
rinse) was slightly reduced in the Type III region and
dramatically reduced to about 45 % in the Type II region.
This trend is similar to what was observed before by Phan
et al. [4] using a single extended surfactant formulation.

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Fig. 4 Effect of microemulsion types and washing cycles on canola


oil detergency at 25 8C, 120 rpm agitation speed and 1000 ppm of
total surfactant concentration. Surfactant mixture consisted of C10
18PO2EONaSO4 and SDOSS at 0.26:0.74 mole fractions

The dramatic detergency reduction in Type II region was


attributed to the hydrophobicity of the surfactant system
leading to the tendency to form reverse micellar microemulsions. Thus the surfactants are more oil soluble and
tend to partition into the oil phase.
Considering the detergency performance of the full
washing cycle (20 min wash, 3 min for rinse 1 and 2 min
for rinse 2), also shown in Fig. 4, it can be seen that in the
Type I region, a slight increase in oil removal is realized
during the rinsing steps compared to the washing step
(wash ? rinse results are slightly higher than wash only in
Type I region, NaCl B1 %). However, in the Type II
region, the detergency increased substantially with the
rinse steps added, achieving more than 95 % oil removal,
surprisingly exceeding the detergency performance in both
Type I and III regions. Similar results have been observed
in previous research when using an extended surfactant
alone system; however, for such system, the NaCl
requirement was substantially higher (14 %) compared to
our formulation (4 %) [4]. One possible explanation for
good detergency performance in the Type II region is the
gradient effect in the rinsing step. In the washing step, the
Type II system favored surfactant partition into the oil on
the fabrics. Once the fabric was rinsed with deionized
water, the system presumably underwent phase transition
from Type II to Type I and in between transition to an
optimum Type III [4], thereby producing excellent
detergency.
Effect of Temperature on Detergency
Figure 5 presents the effect of washing temperature
(1030 C) on detergency of the four studied oils. The right
y-axis in Fig. 5c and d is the solid fat index defined as the
solid to liquid ratio in fat. The SFI data was adapted from

379

[3]. The NaCl was fixed at 0.5 % for these tests, corresponding to Winsor Type I for all systems. In all systems, it
can be seen that the detergency performance of our formulation is superior to that of the commercial detergent,
especially at low temperature. For all systems, at temperature above the melting points of the studied oils, our
formulation achieved more than 90 % detergency performance at relatively low NaCl concentration of 0.5 %
(much lower NaCl levels than previous research with
extended surfactants [4, 6]). At temperatures below the
melting points of the coconut (Fig. 5c) and palm kernel
(Fig. 5d) oils, detergency performance using our formulation gradually reduced, but still exceeded the performance
of the commercial detergent. When using our formulation
at temperatures well below the melting point of coconut
and palm kernel oils, the detergency performance gradually
increased as the temperature increased or SFI decreased
(the amount of solid fraction decreased with increasing
temperature). This trend was not observed when using the
commercial detergent. These results are thus quite
encouraging as they suggest that an extended surfactant
based system can show superior performance in cold water
detergency of triglyceride oils and fats; this should be
further explored in the future research.
We speculated that below the melting points, the IFT
reduction of our formulations for the liquid fraction of the
oil was sufficient to enhance the semi-solid fat (mixture of
liquid and solid) detergency. Another possible explanation
is based on the microemulsion phase behavior study of
palm kernel oil shown in Fig. 6. In Fig. 6, three surfactant
systems were investigated including commercial detergent
with no NaCl added (Fig. 6a), C1018PO2EONaSO4 at
0.5 % NaCl (Fig. 6b) and C1018PO2EONaSO4-/
SDOSS mixture at 0.5 % NaCl. It can be seen that Type I
bluish microemulsion phases were formed when using
extended surfactant alone or in mixture with SDOSS
(Fig. 6b, c, respectively), whereas no appreciable oil was
solubilized by the commercial detergent solution (Fig. 6a).
To our knowledge, we have not seen reported phase
behavior study with semi-solid fat in the literature.
Regarding the effect of temperature on the HLD value,
the HLD value of ionic microemulsions with conventional
surfactants (non-ethoxylated or propoxylated) is expected
to increase as the temperature decreases. In other words,
the conventional ionic surfactant systems become relatively more hydrophobic as the temperature decreases.
However, the change in temperature will not have a significant effect on the hydrophiliclipophilic balance of the
ionic surfactant system as the temperature coefficient has a
small value of 0.01. Thus, for a 10 C decrease in temperature, the HLD would only be expected to shift 0.1 and
thus have a negligible impact on performance. For surfactants with ethylene oxide groups [4144], and,

123

380

J Surfact Deterg (2015) 18:373382

Fig. 5 Effect of temperature on


detergency of a canola,
b jojoba, c coconut and d palm
kernel oils. 1000 ppm total
surfactant concentration,
consisting of C1018PO2EO
NaSO4 and SDOSS at 0.26:0.74
mole fractions. NaCl was fixed
at 0.5 w/v% (Type I). Solid fat
index (SFI) was adapted from
the literature [3]

Fig. 6 Phase behaviors of palm kernel oil with different surfactant


systems: a commercial detergent, b C1018PO2EONaSO4 and
c C1018PO2EONaSO4/SDOSS at 0.24/0.76 mole fraction, 0.5
w/v% NaCl and 25 8C. Total surfactant concentration was at 1 w/v%

somewhat surprisingly, for extended surfactants with propylene oxide (PO) groups [42], the temperature effect has
been shown to be the oppositeas the temperature decreases these surfactants become more hydrophilic. For

123

extended surfactants with PO groups this temperature


effect has been attributed to the first several PO groups
(first 23) being near the interface and thus somehow
hydrated (as for EO groups); with decreasing temperature
the hydration increases thus making the surfactant slightly
more hydrophilic [42]. Interestingly, for extended surfactants temperature changes will have opposing effects on the
ionic head group and the EO/PO intermediate groups,
further minimizing the anticipated effect of a 10 C temperature decrease on the system HLD.
In summary, cold temperature detergency of semi-solid
fats is a complicated process. While this paper reports on a
very promising surfactant mixture for cold temperature
detergency application at relatively low salinity concentration (0.5 % NaCl) which is competitive with or better
than commercial detergents, additional research needs to
be conducted to obtain good detergency at lower salinity
concentrations and gain fundamental understanding of the
detergency of solid to semi-solid fats. Ongoing research
work is evaluating the model methyl palmitate oil of high
melting point (30 C) to gain more fundamental insights
into the detergency mechanism of semi-solid fats. Future
research should also study the detergency performance as a
function of the surfactant concentration. A surfactant

J Surfact Deterg (2015) 18:373382

concentration as low as 125 ppm would be more desirable


for practical applications. Finally, to our knowledge, select
extended surfactants are commercially available and can be
used to formulate in personal care and consumer products,
making this work of practical interest.
Acknowledgments The authors would like to thank George Smith
from Huntsman Corporation (The Woodlands, TX) for providing the
extended surfactant sample. Funding for this work was provided by
industrial sponsors of the Institute for Applied Surfactant Research at
the University of Oklahoma: CESI Chemical, Church & Dwight,
Clorox, Conoco Phillips, Ecolab, GlaxoSmithKline, Haliburton Services, Huntsman, InVia Westvaco, Novus, Procter and Gamble,
Phillips 66, Sasol, SC Johnson and Shell Chemicals.

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Linh D. Do received her B.Sc. (2004) and Ph.D. (2010) from the
University of Oklahoma, all in chemical engineering. She is currently
a Principal Chemist at Nalco ChampionAn Ecolab Company. Her
research interests include surfactant properties and their applications
in microemulsions, consumer products, oilseed extraction, biofuels
and enhanced oil recovery. Her research now focuses on developing
hydraulic fracturing fluid systems for unconventional oil and gas
reservoirs.
Chodchanok Attaphong received her B.Eng. (2005) and M.Sc.
(2007) from Chulalongkorn University, Thailand and her Ph.D.
(2014) from the University of Oklahoma. She is currently a
postdoctoral researcher at the University of Oklahoma. Her research
interests include surfactant properties, surfactant adsorption, and their
applications in vegetable oil-based microemulsions (i.e., biofuels and
consumer products). Her research now focuses on formulating
microemulsions for detergent applications at low temperature and
surfactant characteristics of bio-surfactants for oil spill cleanup in
seawater.
John F. Scamehorn is Emeritus Director of the Institute for Applied
Surfactant Research at the University of Oklahoma where he is Asha
Glass Chair Emeritus in Chemical Engineering. He received his B.Sc.
and M.Sc. at the University of Nebraska and his Ph.D. at the
University of Texas, all in chemical engineering. Dr. Scamehorn has
worked for Shell, Conoco, and DuPont. His research interests include
surfactant properties important in consumer production formulation
and thermodynamics of surfactant aggregation processes.
David A. Sabatini is David Ross Boyd Professor and Sun Oil
Company Endowed Chair of Civil Engineering and Environmental
Science, is Associate Director of the Institute for Applied Surfactant
Research and Director of the WaTER Center at the University of
Oklahoma. He received his B.Sc. from the University of Illinois
(1981), his M.Sc. from Memphis State University (1985) and his
Ph.D. from Iowa State University (1989). His research focuses on
surfactant-based environmental technologies, surfactant-based formulations for vegetable oil extraction and biofuel production and
cleaning systems, and sustainable technologies for drinking water
treatment in developing countries.