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DOI 10.1007/s11743-014-1659-1
ORIGINAL ARTICLE
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
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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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
375
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
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
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376
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377
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
NA
5.35
0.0026
16
Coconut
646
NA
NA
12
Palm kernel
756
NA
NA
15
Oil
EACN for pure coconut and palm kernel oils were predicted from
Eq. (4)
NA not available
a
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378
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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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,
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380
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
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