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International Journal of Cosmetic Science , 2011, 33 , 263–268 doi: 10.1111/j.1468-2494.2010.00624.x Design and
International Journal of Cosmetic Science , 2011, 33 , 263–268 doi: 10.1111/j.1468-2494.2010.00624.x Design and
International Journal of Cosmetic Science , 2011, 33 , 263–268 doi: 10.1111/j.1468-2494.2010.00624.x Design and

International Journal of Cosmetic Science , 2011, 33 , 263–268

doi: 10.1111/j.1468-2494.2010.00624.x

Design and application of water-in-oil emulsions for use in lipstick formulations

B. J. D. Le Re´ve´rend, M. S. Taylor and I. T. Norton

Centre for Formulation Engineering, School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.

Received 12 July 2010, Accepted 17 September 2010

Keywords: emulsion, lipsticks, PGPR, span, wax


The addition of water to lipsticks in the form of a water-in-oil emulsion is an attractive opportunity for cosmetics manufacturers to deliver hydrophilic molecules to the consumers, as well as improving the moisturizing properties. In this work, the effect of the emulsifier type and water content on the structural properties of the designed products was investigated. It has been shown that PGPR leads to smaller droplets than the other emulsifiers tested. This was attributed to the ability of PGPR to form elastic interfaces that slow the coalescence between droplets during the process. It was also observed that crystals of wax tend to form structures at the interface upon cooling that prevent coalescence during storage. These structures also prevent leakage of water into the continuous phase. No effect of the water content on the melting properties of the emulsions was observed. Upon addition of more than 10% water, softening of the material was measured, due to the overall decrease in solid content. Addition of crystalline material (hard par- affin) was successfully used to reinstate the material properties.

Re´ sume´

L’utilisation d’eau comme ingre´ dient dans des formulations de rouges a` le` vres sous la forme d’une e´ mulsion repre´ sente l’opportu- nite´ pour l’industrie cosme´ tique de de´ livrer des mole´ cules hydro- philes aux consommateurs, ainsi que d’ame´ liorer leurs proprie´ te´ s humectantes. Au cours de ce travail, l’effet du type de surfactant ainsi que le volume occupe´ par la phase disperse´ e sur la structure de l’e´ mulsion obtenue ont e´ te´ e´ tudie´ s. Nous avons observe´ que les gouttelettes les plus fines furent obtenues avec l’utilisation du surfactant PGPR. Les proprie´ te´ s e´ lastiques des interfaces stabilise´ es par le PGPR permettent de limiter la coalescence entre gouttelettes et donc d’obtenir une taille moyenne plus fine. Nous avons aussi observe´ que les cristaux de cire de la phase continue pouvaient stabiliser l’e´ mulsion via la formation de structures secondaires aux interfaces. Ces structures, semblables a` des coques permettent de limiter la migration d’eau entre la phase disperse´ e et la phase continue. D’un point de vue thermodynamique, l’ajout d’eau n’a pas d’effet sur les proprie´ te´ s de changement de phase de la phase

Correspondence: Benjamin J. D. Le Re´ ve´ rend, Centre for Formulation Engineering, School of Chemical Engineering, University of Birming- ham, Edgbaston, Birmingham B15 2TT, U.K. Tel.:

+44 (0)1214145284; fax: +44 (0)1214145377; e-mail: b.j.d.lerever- end@bham.ac.uk

continue, probablement graˆ ce a` cette barrie` re a` l’interface. Au dela` de 10% de phase disperse´ e, un ramollissement du produit final par rapport a` un e´ chantillon controˆ le a pu eˆ tre mesure´ . Ceci peut eˆ tre corrige´ en modifiant la phase continue par ajout de matie` re cristal- line (paraffine).


The cosmetics industry has a total revenue of 60 billions in Europe and of this about 4.2 billions is attributed to the sales of lipstick products. The continuous phase of a conventional lipstick formulation is hydrophobic and contains a number of ingredients such as carnauba wax (INCI: Copernicia Cerifera), microcrystalline wax (INCI: Cera Microcristallina), beeswax (INCI: Beeswax), hard paraffin (INCI: Paraffin), berry wax (INCI: Rhus Verniciflua), perfor- malene 400 (INCI: Polyethylene ) and castor oil (INCI: Ricinus Com- munis). In addition, suspended solid particles of pigments and lipophilic materials in the oil phase such as fragrances are added to provide their cosmetic dimension to these products. Water-in-oil emulsions are commonly found in the food industry where milk fats [1, 2], vegetable oils [3–5] and more recently cocoa butter [6] have been used to produce such emulsions. To stabilize these emulsions with sufficient water content, there is a need for an emulsifier to reduce the interfacial tension between the two phases. These can be of different natures (i) monomeric like Span80 (INCI: Sorbitan monooleate) [7], (ii) polymeric such as PGPR (INCI: Polyglyceryl-3 Polyricinoleate) [8] and (iii) crystalline mono-, di- or tri-glycerides (such as triolein or tristearin) [9, 10]. The latter essentially act as Pickering particles as the crystals and sit at the w/o interface blocking the back reaction (coalescence) during the emulsification process [3]. The processing conditions that are tem- perature and shear can be used to control the behaviour of these crystals at the interface. Under certain conditions, one can sinter these crystals and form an intact crystalline shell of fats around each droplet that can be used to isolate the internal water from water-soluble components dispersed in the fat phase [11]. The addition of water in the form of droplets of various sizes (1–100 lm) depending on formulation and processing provides benefits such as spreadability, texture and taste to the fat phase [12]. The addition of water droplets in lipsticks has been reported previously to deliver: water-soluble molecules to the consumer, as well as improving their moisturizing properties [13]; however, in this study, only examples containing up to 20% water droplets are mentioned. Wang and Lee [14] investigated emulsion-based lip- sticks and concluded that (i) the emulsifier type was not important

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ICS ª 2011 Society of Cosmetic Scientists and the Socie´ te´ Franc¸aise de Cosme´ tologie


Water-in-oil emulsion lipstick technology

B. J. D. Le Re´ ve´ rend et al.

regarding the hardness of the final emulsion and (ii) surprisingly that increasing water content (5–15%) improved the hardness of the lipsticks manufactured. In this work, we investigated the use of a range of emulsifiers on the droplet microstructure using water contents up to 40% and showed how the droplets affect the macro-mechanical properties.

Materials and methods

Formulation of the continuous phase

A model lipstick formulation was used in this study (Table I). These

are based on the fact that carnauba wax and microcrystalline wax are the two most abundant waxes in a typical lipstick formulation whereas hard paraffin was used to harden the emulsions contain- ing the highest water content (40 wt. %).

Selection of emulsifiers and investigation of their effect on the inter- facial tension between the dispersed and the continuous phase

Three emulsifiers were used in this work to produce w/o emul-


1 PGPR (ADMUL WOL 1408K; Kerry BioScience, Bristol, UK).

2 Span 80 (S6760; Sigma-Aldrich, Dorset, UK).

3 Span 80 (93.5%) and Tween 80 (INCI: Polysorbate 80 ) (6.5%) (P8074; Sigma-Aldrich), providing an HLB value of 5. The interfacial tension between distilled water and the continu- ous phase (Formulation 1) was measured using a K100 (Kruss, Hamburg, Germany) tensiometer. Measurements were carried out

using the Wilhelmy plate (Kruss standard plate – roughened plati-

w = 19.9 mm, h = 10 mm and d = 0.2 mm) method with

the temperature maintained at 30.5 C using an external circulat- ing water bath. Sample vessel (121.5 mL with diameter 70 mm) was used for the measurements, with 20.0 g of water and approxi- mately 45 g of oil. The Wilhelmy plate method was chosen in this instance over the du Nouy ring method due to the high viscosity of the oil/wax phase.


Emulsion preparation

Emulsions were prepared by first melting all the components of the continuous phase (waxes, oil and emulsifier) in a beaker placed in

a water bath at temperature between 95 and 100 C. The blend

was continuously mixed using a bench-top overhead stirrer. The desired amount of distilled water was then added to the continuous phase and stirred to obtain a coarse pre-emulsion. This emulsion was then homogenized using a Silverson L4RT (Silverson, Water- side, Buckinghamshire, U.K.) high shear laboratory mixer and mixed continuously at 10 000 g for 5 min. Because the emulsify-

Table I Formulations used for the continuous phase in this study


Formulation 1

Formulation 2

Carnauba wax



Microcrystalline wax



Hard paraffin



Castor oil






ing process was relatively short, no significant water loss was mea- sured. The emulsion was then allowed to cool with continuous stirring (overhead stirrer) to approximately 80 C and then transferred to lipstick moulds. The high moisture content emulsions (30–40%) were transferred with a syringe due to their relatively high viscosity. The moulds were then placed in a freezer at )18 to )20 C for 20 min to allow complete crystallization of the waxes present in the continuous phase.

Pulsed Nuclear Magnetic Resonance – pNMR

Droplet sizes were determined by NMR using a low-resolution NMR spectrometer, minispec mq20 (Brucker, Coventry, Warwickshire, 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- niques. The instrument was equipped with a variable temperature gradient probe head mq-PGU2, with operating range )10 up to 70 C and a pulse gradient unit corresponding to a field gradient strength of 2T/m. Calibration was carried out using a 0.5 mM cop- per sulphate solution. All samples were placed in glass vials (180 · 10 · 0.6 mm thickness), and analyses were carried out at temperature 5 to 7.5 C via the use of external circulation cooling unit and cooled with water/ethylene glycol (circulating fluid) to ensure full solidification and accurate measurement of the droplet size. A handheld thermometer was used to verify the probe cham- ber temperature prior to analysis.

Texture profile analysis

Lipstick hardness is an important determination of the physical characteristic properties of the lipstick. Hardness assessment based on the wax, oil and water composition along with the emulsifier content is a useful tool in determining objectively the effects of for- mulation and processing at macro-scale. The texture profile analysis on the formulated products was con- ducted using a TaXT+ (Stable Microsystems, Godalming, Surrey, U.K.) texture analyser. Room temperature was carefully monitored with all tests being conducted at the same temperature (23± 1 C). The penetration depth of a needle at a constant force was mea- sured to represent the hardness of the emulsion. A standard (SMS P/2N) 2-mm needle was selected, using a 5 kg-load cell. All tests were conducted at room temperature (24.5 C) using samples mea- suring 25 mm in height with a standard diameter of 11.80 mm. The sample cuts were placed centrally under the needle probe, and the needle adjusted until it was just above the sample (approxi- 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- ing the needle at 10 mm s ) 1 .


Cryo-scanning electron microscopy was used to observe, evaluate and classify the size of the droplet particle individually. A XL-30ESEM (Philips, Eindhoven, The Netherlands) cryo-scanning electron microscope was used for the analysis. Cryogenic tempera- tures were used to preserve the structure of the sample in its original state. A small amount of the sample (approximately


ª 2011 The Authors

ICS ª 2011 Society of Cosmetic Scientists and the Socie´ te´ Franc¸aise de Cosme´ tologie

International Journal of Cosmetic Science , 33 , 263–268

Water-in-oil emulsion lipstick technology

B. J. D. Le Re´ ve´ rend et al.

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 )210 C 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 )175 C.

Differential scanning calorimetry

The emulsions melting profile were analysed using a DSC 7 (Perkin Elmer, Seergreen, U.K.) fitted with an Intra-cooler 3 heat sink. Samples were enclosed in 40 lL-aluminium pans and heat at a constant rate of 5 C min ) 1 . Results were post-processed using the pyris software (Perkin Elmer). Calibration was carried out before the evaluation of samples using Indium and Zinc as suggested by the manufacturer.

Results and discussion

The interfacial tension between the two phases was measured as a function of emulsifier type and concentration. As can be seen in Fig. 1, the surfactant that lowered the interfacial tension the most was a combination of Span 80 and Tween 80. This can be explained by the fact that Span80 is more lipophilic whereas Tween80 is more hydrophilic; thus, interfacial tension is greatly reduced by the presence of surfactant on both sides of the interface. Span80 and PGPR were shown to have similar efficiencies in redu- cing the interfacial tension, which is considerably less than that of the Span80 + Tween80 combination because it requires 8% PGPR or Span80 to achieve the same interfacial tension as the one mea- sured with 1% of the Span80 + Tween80 combination. This result tells us that from a thermodynamic perspective, dro- plets in the Span80 + Tween80–stabilized system should be more stable as the interfacial tension is further decreased using this sur- factant. Emulsions were produced using the different emulsifiers and emulsifier mixtures shown in Fig. 1. As can be seen in Fig. 2,

mixtures shown in Fig. 1. As can be seen in Fig. 2, Figure 1 Interfacial tension

Figure 1 Interfacial tension between water and oil phases depending on the type and concentration of surfactant dispersed in the oil phase.

and concentration of surfactant dispersed in the oil phase. Figure 2 Average droplet size D 3

Figure 2 Average droplet size D 3,3 measured by NMR depending on the mass fraction of water in the w/o emulsion.

emulsions made using 1% of the investigated emulsifiers and 10% water have similar average droplet size (D 3,3 approximately 5 lm). As the water content is increased up to 40%, the droplet size mea- sured for the Span80 + Tween80 or Span80 is much higher than that of systems using PGPR as the emulsifier. The droplet sizes measured by the pulsed NMR device correlate with those observed on the cryo-SEM photographs such as the ones presented in Fig. 4.

A range of hypotheses can be formulated to explain the better

emulsification properties of PGPR:

1 PGPR is well known for its ability to reduce the viscosity of fat- continuous systems such as chocolate [15]. Decreasing the visc- osity of the continuous phase creates a more turbulent flow (higher Reynolds number), which encourages droplet break-up and leads to smaller droplets. 2 PGPR is a polymeric emulsifier that results in a thick elastic interface that acts as a kinetic barrier slowing down coalescence


the process [3], resulting in smaller droplets.


is of particular interest to have small droplets in systems car-

rying active or functional ingredients, as it tends to accelerate

release rates by increase the available surface area to transfer

material from the droplets to the recipient side. For example, in our case, the reduction from 15 lm (Span80 or Span80 + Tween80) down to 5 l m (PGPR) leads to an increase in the total interfacial area by a factor of 3. The stability of the droplets over a 3-months period at room temperature (23± 1 C) was investigated. The data obtained at 1% emulsifier are shown in Fig. 3. As can be seen, the emulsions made with PGPR did not show any increase in droplet size over the per- iod of the study (3 months). However, the emulsions made with Span80 alone showed a small increase in droplet size whereas the samples made with a mixture of Span80 and Tween80 showed an

17 ± 1 lm. These differ-

ences again can be explained by considering the nature of the interfacial layer. With PGPR, a thick and elastic interface is pro- duced (dilatational elasticity measurements report E 0 between 2.5 and 11 mN m ) 1 [16]) that slows down the coalescence kinetics both during the emulsification process and on storage. With the other emulsifier systems studied, the interface does not have these elastic properties (dilatational elasticity measurements report E 0 around 1 mN m ) 1 [7]); droplets are thus more prone to coales- cence or ripening, which explains the increase in droplet size dur- ing storage. However, it is likely that in the presence of wax crystals, the microstructure is more complicated. As has been

increase in droplet size from 14 ± 1 to

ª 2011 The Authors

ICS ª 2011 Society of Cosmetic Scientists and the Socie´ te´ Franc¸aise de Cosme´ tologie

International Journal of Cosmetic Science , 33 , 263–268


Water-in-oil emulsion lipstick technology

B. J. D. Le Re´ ve´ rend et al.

lipstick technology B. J. D. Le Re´ ve´ rend et al. Figure 3 Evolution of the

Figure 3 Evolution of the average droplet size D 3,3 measured by NMR dur- ing storage of 40 wt. % w/o emulsions.

previously described [3, 6, 10], a combination of emulsifier and crystalline material can result in crystals being present in the inter- face resulting in Pickering stabilization. Emulsions stabilized in this way have been shown to be highly stable against coalescence on storage. To check the nature of the emulsions produced in this study, we carried out a microstructure analysis of the water dro- plets (Fig. 4). As can be seen, wax crystals are present at the inter- face between the oil continuous phase and the dispersed water


Figure 4 SEM micrographs of water droplets in the surrounding hydropho- bic continuous phase (a) formulation 1 – 1% PGPR – 10% water, (b) formu- lation 2 – 1% Span80 – 40% water.

phase. These crystals provide Pickering stabilization to the emul- sions, which explains the high stability of the emulsion against coalescence. By careful investigation of the EM pictures, differences between the nature of the crystals at the interface when the differ- ent surfactant systems were used can be identified. In Fig. 4a, a smooth crystalline shell is present at the interface when PGPR is used. These shells are similar to those already described in the lit- erature [6]. However, as can be seen in Fig. 4b, the wax crystals present at the interface are rough and look as if total sintering has not occurred. It would therefore be expected that the crystal shells with PGPR would result in slower ripening of the structure. The difference in shell structure may well be a consequence of the different surfactants used. We have already discussed the properties of PGPR, making elastic interfaces and reducing viscosity. These properties could allow the crystals to be more mobile at the inter- face and increase their chances to sinter with each other. When a mixture of Span80 + Tween80 was used, the crystals have less freedom to move at the interface leading to an accumulation of individual crystals with no linkage between them which explains the rougher surface of the structures. As crystals present at the interface stabilize the emulsion, two questions have to be answered: (i) At what temperature does the emulsion become unstable and how does this relate to the melting of the crystals? (ii) How does the presence of droplets influence the material properties of the wax crystal network used to impart the desired textural properties of a lipstick? The melting behaviour of the waxes in the emulsions was mea- sured for all the emulsifiers used and at all water contents using DSC. Figure 5(a) shows the effect of the dispersed phase fraction on the melting curve of the emulsions (formulation 1 with 1% PGPR). As expected, the melting of the waxes is not affected by the pre- sence of the water. Similar results were obtained for cocoa butter emulsions made using a similar processing route [6]. Comparable results were obtained with the other emulsifiers investigated (data not shown). A softening point around 32 C is observed, which can be attributed to the onset of melting of the microcrystalline wax, as shown in Fig. 5b. Similarly, the high melting peak (70 C) of the carnauba wax that can be observed in Fig. 5b can also be seen in the thermograms of the emulsions in Fig. 5a. This tells us that if the crystals at the droplets interface are not carefully selected through processing, there is a chance that the droplets would be too stable to allow any significant release on the lips. The optimal formulation engineering of an emulsion designed to release active ingredients on the lips would be made so that the crystals at the interface of the droplets would be microcrystalline wax crystals (or another wax with a low melting point), so that these crystals melt at body temperature. The emulsion would then be locally destabilized allowing the release of the actives. The mechanical properties of the emulsion-based lipstick formu- lation were investigated using a penetration technique. Figure 6 shows the results of the penetrometry tests carried out on the var- ious samples as well as on a commercial lipstick used as a refer- ence. A gradual softening effect is observed between 10% and 30% water phase whilst the softening is more pronounced at 40% water. These results do not agree with previously reported data on lipsticks [14] that showed an increase in hardness with increasing water content; however, the data obtained here are consistent with previous studies on food emulsions, all of which showed a decrease in hardness as the phase volume of water is increased in a fat-con- tinuous system (references) and which is expected as the number of included soft filler particles is increased [17]. There is more soft- ening for the Span80 and Span80 + Tween80 systems than for the


ª 2011 The Authors

ICS ª 2011 Society of Cosmetic Scientists and the Socie´ te´ Franc¸aise de Cosme´ tologie

International Journal of Cosmetic Science , 33 , 263–268

Water-in-oil emulsion lipstick technology

B. J. D. Le Re´ ve´ rend et al.


Figure 5 DSC thermograms of emulsions containing formulation 1 (1% PGPR) as the continuous phase (a) and of the individual waxes used (b).

PGPR-containing emulsion. It has already been reported that for a given volume fraction, the decrease in droplets size influences the visco-elastic properties of the emulsion produced, increasing viscos- ity and storage modulus (G’) [18] and also an increase in the yield stress of low-fat margarines [19]. Explanations for this behaviour are attributed to (i) the decrease in the mean distance separation between droplets, thus increasing the hydrodynamic forces between droplets and thus viscosity and (ii) the increase in the surface area available for pressure to be applied on, increasing the total force (stress) necessary to modify the system [20]. An explanation for this general softening of the network upon addition of water could be that because wax crystals are located at the interface of the water droplets, as the water content increases, the surface to cover increases and therefore fewer crystals to form the crystal network in the continuous phase. If this is the case, adding more crystalline material in the continuous phase should restore the mechanical properties of the material. This was tested 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 (8.5%) of hard paraffin to the continuous phase has resulted in a harder final product. The penetration depth measured for formula- tion 2 (2.5 mm) is very close to the one measured for the commer- cial lipstick used as a control (2 mm), which indicates that as

lipstick used as a control (2 mm), which indicates that as Figure 6 Penetration depth recorded

Figure 6 Penetration depth recorded for different emulsion-based lipstick samples. Softening occurs upon addition of water above 10% (formulation 1), which can be compensated by adding hard paraffin to the continuous phase (formulation 2).

expected, the general mechanical properties are dependant on both the dispersed and the continuous phase properties.


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 stability against coalescence during storage. This was attributed to 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 not observed on the emulsions stabilized with Span80 as the inter- face formed is more rigid. The water content of the emulsions did not affect its melting profile, which correlates with the droplet size measurements and the SEM micrographs showing that droplet size did not change in the range of water content investigated (10–40%). The SEM micro- graphs also showed the presence of wax crystals at the interface which could be sintered to form a continuous shell, separating water from the continuous phase. Although at high water content, a weakening of the mechanical properties was observed. It was possible to restore the mechanical properties to those of a commercial control sample by adding a small fraction of hard paraffin in the continuous phase to restore the overall solid content of the product. This study shows that there is great potential in the use of emul- sions to produce lipsticks in which water could be used as a carrier for active ingredients.


The authors thank Boots plc. for providing materials as well as Dr F. Spyropoulos (University of Birmingham) for helpful scientific discussions.

ª 2011 The Authors

ICS ª 2011 Society of Cosmetic Scientists and the Socie´ te´ Franc¸aise de Cosme´ tologie

International Journal of Cosmetic Science , 33 , 263–268


Water-in-oil emulsion lipstick technology

B. J. D. Le Re´ ve´ rend et al.


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ª 2011 The Authors ICS ª 2011 Society of Cosmetic Scientists and the Socie´ te´ Franc¸aise de Cosme´ tologie International Journal of Cosmetic Science , 33 , 263–268