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regarding the hardness of the final emulsion and (ii) surprisingly ing process was relatively short, no significant water loss was mea-
that increasing water content (5–15%) improved the hardness of sured.
the lipsticks manufactured. The emulsion was then allowed to cool with continuous stirring
In this work, we investigated the use of a range of emulsifiers on (overhead stirrer) to approximately 80C and then transferred to
the droplet microstructure using water contents up to 40% and lipstick moulds. The high moisture content emulsions (30–40%)
showed how the droplets affect the macro-mechanical properties. were transferred with a syringe due to their relatively high
viscosity.
The moulds were then placed in a freezer at )18 to )20C for
Materials and methods
20 min to allow complete crystallization of the waxes present in
the continuous phase.
Formulation of the continuous phase
A model lipstick formulation was used in this study (Table I). These
Pulsed Nuclear Magnetic Resonance – pNMR
are based on the fact that carnauba wax and microcrystalline wax
are the two most abundant waxes in a typical lipstick formulation Droplet sizes were determined by NMR using a low-resolution NMR
whereas hard paraffin was used to harden the emulsions contain- spectrometer, minispec mq20 (Brucker, Coventry, Warwickshire,
ing the highest water content (40 wt. %). U.K.), with a permanent magnetic strength of 0.47 T. NMR offers
the advantage of direct measurement of the sample without pre-
paration or dilution as necessary when using light scattering tech-
Selection of emulsifiers and investigation of their effect on the inter-
niques. The instrument was equipped with a variable temperature
facial tension between the dispersed and the continuous phase
gradient probe head mq-PGU2, with operating range )10 up to
Three emulsifiers were used in this work to produce w/o emul- 70C and a pulse gradient unit corresponding to a field gradient
sions: strength of 2T/m. Calibration was carried out using a 0.5 mM cop-
1 PGPR (ADMUL WOL 1408K; Kerry BioScience, Bristol, UK). per sulphate solution. All samples were placed in glass vials
2 Span 80 (S6760; Sigma-Aldrich, Dorset, UK). (180 · 10 · 0.6 mm thickness), and analyses were carried out at
3 Span 80 (93.5%) and Tween 80 (INCI: Polysorbate 80) (6.5%) temperature 5 to 7.5C via the use of external circulation cooling
(P8074; Sigma-Aldrich), providing an HLB value of 5. unit and cooled with water/ethylene glycol (circulating fluid) to
The interfacial tension between distilled water and the continu- ensure full solidification and accurate measurement of the droplet
ous phase (Formulation 1) was measured using a K100 (Kruss, size. A handheld thermometer was used to verify the probe cham-
Hamburg, Germany) tensiometer. Measurements were carried out ber temperature prior to analysis.
using the Wilhelmy plate (Kruss standard plate – roughened plati-
num, w = 19.9 mm, h = 10 mm and d = 0.2 mm) method with
Texture profile analysis
the temperature maintained at 30.5C using an external circulat-
ing water bath. Sample vessel (121.5 mL with diameter 70 mm) Lipstick hardness is an important determination of the physical
was used for the measurements, with 20.0 g of water and approxi- characteristic properties of the lipstick. Hardness assessment based
mately 45 g of oil. The Wilhelmy plate method was chosen in this on the wax, oil and water composition along with the emulsifier
instance over the du Nouy ring method due to the high viscosity of content is a useful tool in determining objectively the effects of for-
the oil/wax phase. mulation and processing at macro-scale.
The texture profile analysis on the formulated products was con-
ducted using a TaXT+ (Stable Microsystems, Godalming, Surrey,
Emulsion preparation
U.K.) texture analyser. Room temperature was carefully monitored
Emulsions were prepared by first melting all the components of the with all tests being conducted at the same temperature (23± 1C).
continuous phase (waxes, oil and emulsifier) in a beaker placed in The penetration depth of a needle at a constant force was mea-
a water bath at temperature between 95 and 100C. The blend sured to represent the hardness of the emulsion. A standard (SMS
was continuously mixed using a bench-top overhead stirrer. The P/2N) 2-mm needle was selected, using a 5 kg-load cell. All tests
desired amount of distilled water was then added to the continuous were conducted at room temperature (24.5C) using samples mea-
phase and stirred to obtain a coarse pre-emulsion. This emulsion suring 25 mm in height with a standard diameter of 11.80 mm.
was then homogenized using a Silverson L4RT (Silverson, Water- The sample cuts were placed centrally under the needle probe, and
side, Buckinghamshire, U.K.) high shear laboratory mixer and the needle adjusted until it was just above the sample (approxi-
mixed continuously at 10 000 g for 5 min. Because the emulsify- mately 1–1.5 mm) and the probe tarred prior to analysis. Once the
trigger force of 5.0 g was attained, the needle penetrated the sam-
ple at 0.50 mm s)1 until a force of 15 g was achieved, at which
point the probe head maintained a 3.0-s hold time prior to extract-
Table I Formulations used for the continuous phase in this study ing the needle at 10 mm s)1.
3 · 2 · 6 mm) was fixed onto the sample holder, the holder hav-
ing a layer of carbon-rich conductive glue (conductive to allow dis-
charge of electrons). The sample was then frozen (cryo-fixed)
rapidly in a bath of boiling liquid nitrogen otherwise known as
nitrogen slush at )196 to )210C for about 2 min. The sample
was then transferred to the high vacuum cryo-unit chamber and
freeze-fractured. Any humidity on the surface was sublimated, and
a thin layer (approximately 10 nm) of gold sputtered on the sur-
face. The sample was then inserted into the observation chamber,
and observations were carried out at 3–5 kV at temperatures
between )100 and )175C.
(a)
Conclusion
The behaviour of w/o emulsions was investigated, and average dro-
plet sizes, melting profiles, microstructures and mechanical proper-
ties of the manufactured products were collected to define the
applicability of such emulsions to be part of lipstick formulations. It
was observed that PGPR gave the smallest droplets and the most
Figure 5 DSC thermograms of emulsions containing formulation 1 (1% stability against coalescence during storage. This was attributed to
PGPR) as the continuous phase (a) and of the individual waxes used (b). its polymeric structure giving elastic properties to the interface,
slowing coalescence during the emulsification process. These inter-
facial properties also allow fat crystals present at the interface to
move and sinter to form at smooth, continuous fat shell. This was
PGPR-containing emulsion. It has already been reported that for a not observed on the emulsions stabilized with Span80 as the inter-
given volume fraction, the decrease in droplets size influences the face formed is more rigid.
visco-elastic properties of the emulsion produced, increasing viscos- The water content of the emulsions did not affect its melting
ity and storage modulus (G’) [18] and also an increase in the yield profile, which correlates with the droplet size measurements and
stress of low-fat margarines [19]. Explanations for this behaviour the SEM micrographs showing that droplet size did not change in
are attributed to (i) the decrease in the mean distance separation the range of water content investigated (10–40%). The SEM micro-
between droplets, thus increasing the hydrodynamic forces between graphs also showed the presence of wax crystals at the interface
droplets and thus viscosity and (ii) the increase in the surface area which could be sintered to form a continuous shell, separating
available for pressure to be applied on, increasing the total force water from the continuous phase.
(stress) necessary to modify the system [20]. Although at high water content, a weakening of the mechanical
An explanation for this general softening of the network upon properties was observed. It was possible to restore the mechanical
addition of water could be that because wax crystals are located at properties to those of a commercial control sample by adding a
the interface of the water droplets, as the water content increases, small fraction of hard paraffin in the continuous phase to restore
the surface to cover increases and therefore fewer crystals to form the overall solid content of the product.
the crystal network in the continuous phase. If this is the case, This study shows that there is great potential in the use of emul-
adding more crystalline material in the continuous phase should sions to produce lipsticks in which water could be used as a carrier
restore the mechanical properties of the material. This was tested for active ingredients.
by the addition of hard paraffin to the continuous phase (formula-
tion 2). As can be seen in Fig. 6, the addition of a small fraction
Acknowledgement
(8.5%) of hard paraffin to the continuous phase has resulted in a
harder final product. The penetration depth measured for formula- The authors thank Boots plc. for providing materials as well as
tion 2 (2.5 mm) is very close to the one measured for the commer- Dr F. Spyropoulos (University of Birmingham) for helpful scientific
cial lipstick used as a control (2 mm), which indicates that as discussions.
interface and correlation with the corre- 14. Wang, T. and Lee, G. The effect of formula-
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