Colloids and Surfaces B: Biointerfaces 102 (2013) 371378

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Colloids and Surfaces B: Biointerfaces

journal homepage: www.elsevier.com/locate/colsurfb

Impact of emollients on the spreading properties of cosmetic products: A combined sensory and instrumental characterization
Graldine Savary, Michel Grisel, Cline Picard
Universit du Havre, URCOM, EA 3221, FR CNRS 3038, 25 rue Philippe Lebon, B.P. 540, 76058 Le Havre cedex, France

a r t i c l e

i n f o

a b s t r a c t
This study deals with the impact of emollients on the spreading properties of cosmetic products using a combined sensory-instrumental approach. To that purpose, three esters and one silicone were selected and incorporated separately into an oil phase. Different cosmetic o/w emulsions were then prepared with these different oil phases. Both of them were analyzed by instrumental techniques and in vivo sensory analyses. A signicant effect of the emollient used was established in emulsions and in oil phases as well. Concerning emulsions, results reveal a clear correlation between in vivo spreading evaluation and friction coefcient parameters measured by texture analyzer, despite a fairly low correlation coefcient (Pearson coefcient = 0.78). Concerning oil phases, characterization of spreading was done by monitoring the contact angle relaxation of a drop of solution after deposition on a at PMMA surface whereas sensory procedure was based on spontaneous spreading of oil phases onto the skin. Finally, good correlations between in vivo sensory analysis and instrumental measurements of both oils and emulsions were found, thus promising the possible development of predictive tools to evaluate spreadability. 2012 Elsevier B.V. All rights reserved.

Article history: Received 15 March 2012 Received in revised form 19 June 2012 Accepted 19 July 2012 Available online 9 August 2012 Keywords: Spreading Cosmetic emulsions Sensory evaluation Contact angle Texture analysis Correlation

1. Introduction Sensory properties in skin care formulations mainly result from ingredients such as emollients, rheology modiers, emulsiers and humectants. Generally speaking, emollients, used at levels between 3 and 20% (w/w) in emulsions, represent the second major ingredient after water [1]. Emollients can be of varied chemical structures including esters and silicones. When incorporated in cosmetic emulsions, esters and silicones are hydrophobic ingredients that compose part of the oil phase. Despite their dubious reputation, cyclic silicones are widely found in skin care products for their specic properties when compared to the other emollients [2]. Esters belong to a large family of compounds used either as emollient or as emulsier in cosmetic emulsions and can be used to replace silicones [3]. Related to their physico-chemical properties, skin-feel effects of these emollients are complex and can be perceived during and/or after application on skin: gliding, sliding, moisturizing, plasticizing, protecting, conditioning, softening, smoothing, etc. [1,4,5]. Concerning the properties during application on the skin, emollients decrease the friction coefcient due to their lubricant properties and modify the spreading performance of the product [6].

Corresponding author. Tel.: +33 232 744394; fax: +33 232 744391. E-mail address: celine.picard@univ-lehavre.fr (C. Picard). 0927-7765/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.colsurfb.2012.07.028

To achieve adequate efcacy and user acceptance of a cosmetic emulsion, spreading is an important property. Descriptive sensory analysis of skin care products usually includes attributes such as difculty of spreading or slipperiness that are evaluated during application of either pure ingredients [7] or creams and lotions [8,9]. For example, Parente et al. [2] characterized eight liquid emollients including esters and silicones (i.e. decyl oleate, isopropyl myristate, dimethicone, cyclomethicone) for both attributes. Authors compared properties of emollients alone but they did not study their characteristics when included in cosmetic emulsions. However, sensory analyses are time-consuming and require an available and well-trained panel of assessors. Therefore, different studies were done in order to establish a relationship between textural attributes and structural or physical characteristics [1012]. In the eld of food sciences, many studies have been carried out to develop an instrumental approach especially using texture prole analysis [1315]. However, nowadays the number of studies on spreading performed in the cosmetic domain remains limited. Kusakari et al. [16] developed a measuring device to evaluate the frictional force as an indicator of the spreading resistance whereas DiMuzio et al. [17] established a correlation between spreadability and rheological parameters obtained from stress sweep and creep tests on o/w emulsions. The rst goal of the present study was to test the potential development of texture analysis to evaluate the spreading

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properties of cosmetic emulsions. The second target of this study was to establish an instrumental measurement to characterize the spreading attributes of the various oil phases used to formulate the o/w emulsions. In their study, Gorcea and Laura [1] assessed the physicochemical properties of four cosmetic emollient esters in vitro to correlate with in vivo sensory attributes. Spreading properties were characterized by spreading values on Vitro-Skin , surface tension, contact angle and viscosity measurements. Indeed, surface wetting and absorption dynamics are two key phenomena that govern the spreading of a uid on a given surface [18]. Wettability phenomena can be evaluated by studying the contact angle formed at the air/solid/liquid contact point when a drop of liquid is deposited on the solid surface [19]. When a liquid drop is placed in contact with a at, horizontal substrate, capillary forces drive the interface spontaneously towards equilibrium. As the drop spreads, the contact angle changes from its initial maximum value at the very rst instant of contact, towards its nal equilibrium angle 0 in the case of partial wetting, or 0 if the liquid completely spreads and wets the solid. The results more or less t a master curve showing relationships between contact angle versus time [20]. Several parameters affect wettability [1922]: chemical characteristics of the liquid and substrate, roughness and heterogeneity of the solid, viscosity, surface tension, density and volume of the drop of the liquid and its potential evaporation. In the present study, three esters and one silicone ingredients chosen as major emollients used in the cosmetic industry were studied as components of the oil phase of the given emulsions. The impact of emollients on the spreading properties of the oil phases and of the o/w emulsions formulated with these oil mixtures was studied by a combined sensory-instrumental approach. Spreading of emulsions was rst investigated by in vivo tests and in vitro methods including texture analysis. Then spreading and penetration of the oil phases were characterized using sensory evaluations and contact angle measurements. Results were then analyzed and compared, and a correlation matrix was drawn up to establish the relationships between both sensory and instrumental measurements.

2. Those whose oil phase is a good solvent to solubilize the different emollients chosen. Thus, at room temperature, a liquid oil phase with or without emollient is obtained, making it easier to characterize. For the standard emulsion (200 g), the oil phase (A) was rst prepared by mixing the ingredients as listed in Table 2 and by heating the mixture to 75 C under stirring. In the meantime, the aqueous phase (B) was prepared using puried water (type 1). The mix of water and glycerine was slowly sprinkled with carbomer powder and left 20 min without stirring. Then the aqueous phase was heated to 75 C. When both phases were at 75 C, the water loss due to evaporation was compensated by adding water to the aqueous phase and the oil phase was then gently added to Phase B under stirring for 3 min with a D7801 homogenizer (Ystral GMBH, Germany). The emulsion was then continuously stirred at 300 rpm using a Turbotest motor generator with a 65 mm turbine (VMI, France) until it cooled down to 50 C. Sufcient amount of 1 M aqueous NaOH solution (CarloErba, Italy) was then added to yield a nal pH between 6.2 and 6.5 in the preparation. The stirring rate was then increased to 500 rpm. Finally, the preservative (Phase C) was added at 40 C and the emulsion was kept under stirring for an additional period of 5 min until its temperature dropped to ambient temperature. For the test emulsions with ester, the preparation was exactly the same except for the composition of the oil phase (Table 2). For the test emulsion with silicone, the emollient was added with the preservative at 40 C in order to avoid its evaporation. Samples were stored at 4 C during three months at the most. 2.2. Instrumental spreading characterization 2.2.1. Contact angle measurements Spreading of emollients solubilized in the oil phase was investigated by the sessile drop method (Digidrop GBX goniometer). To this purpose, a drop of product is formed at the end of a syringe until it gently falls under its own weight on the solid support, and then spreads onto it. A high speed camera (25 images/s) recorded the evolution of the contact angle just after deposition and during the entire spreading process. The solid support chosen for these experiments was polymethyl methacrylate (PMMA) plates (Helioplate HD2, Helioscreen, France). This support is commonly used in cosmetics for the in vitro determination of SPF and offers several advantages for our concerns, as compared to articial skin: it is less expensive, easier to handle in terms of surface preparation and cleaning, it is reproducible in terms of surface chemistry and roughness and it is reusable. For each ingredient, both the right and the left contact angles were measured using the Windrop++ software, and the corresponding average contact angle was followed over a period of time until stabilization. The nal results correspond to the mean of three reproducible kinetic experiments. All measurements were realized at room temperature. 2.2.2. Texture analysis Spreading of cosmetic creams was measured on a TA.XT plus Texture Analyzer (Stable Microsystems, United Kingdom), equipped with the A/FR Friction rig module at room temperature. The principle of the test consists in displacing at a constant speed of 3 mm s1 a PMMA plate (Helioplate HD6) surmounted by a square weight (207.9 g, 6.2 cm length), on a static plate covered with a polypropylene sheet. Prior to experiment, using a pipette designed for creamy products (Microman , Gilson, France), 4 drops of cream of 40 L each were deposited on the under-side of the weight in order to design a 2 2 cm2 . The force required to move the weight over a length of 6 cm was monitored over time. Textural data related to friction and spreading of creams were calculated from a graph obtained during experiments (Fig. 1). The positive

2. Material and methods 2.1. Preparation of the emulsions Table 1 reports the name and physico-chemical properties of the cosmetic grade esters and the silicone selected for this study. Esters 1 and 2 are ester or diester from penta- or dipentaerythrityl alcohol respectively. They exhibit a star-shaped structure and a relatively high molar mass, so they are generally selected for the consistency and texture they bring to the formulations. Ester 3 is a linear ester with a low molar mass. It exhibits properties very close to those of silicone: improvement of spreading on skin, silky after-feel sensation on skin. Silicone belongs to the so-called group of cyclic volatile dimethylsiloxanes or cyclomethicones. It is wellknown in cosmetics for producing a silky after-feel sensation and improving spreading on skin. Esters 1, 2 and 3 were kindly given by Starinerie Dubois (France) and silicone was obtained from Evonik Goldschmidt (Germany). A standard emulsion and four test emulsions were prepared by varying the composition of the oil phase in order to analyze the effect of each emollient by itself (Table 2). Ingredients were chosen in order to respect two main criteria:

1. Those that produce a stable emulsion close to an industrial cosmetic one in terms of complexity and number of ingredients

G. Savary et al. / Colloids and Surfaces B: Biointerfaces 102 (2013) 371378 Table 1 Names and physico-chemical properties of the emollients used. Code INCI name Structure Mw

373

log Pa

Ester 1

Pentaerythrityl tetraethylhexanoate

640.9

11.3

Ester 2

Dipentaerythrityl pentaisononanoate

(content > 97%)

949.0

12.0

Ester 3

Propanediol dicaprylate

328.5

6.4

Silicone

Cyclopentasiloxane, cyclohexasiloxane

(content > 95%)

370.8

5.2

log P values were obtained or calculated from http://pubchem.ncbi.nlm.nih.gov.

area between 0 and 14 s was determined for each cream and the mean value of 3 reproducible experiments was reported and considered as an instrumental parameter characterizing the spreading of creams (TEM ).

2.2.3. Physico-chemical characterization of ingredients, oil phases and creams Density of pure ingredients and oil phases containing one ingredient was characterized with a portable densimeter (Mettler Toledo, France).
Table 2 Composition of the standard and test emulsions. Phase Ingredients (INCI name)

Surface tension of pure ingredients and ingredients in the oil phase was determined by the pendant drop method (Digidrop GBX goniometer). Surface tension value was the mean value obtained when measuring ten drops of the same volume. Both measurements were done at room temperature. Rheological properties in ow mode of pure ingredients, oil phases and creams were measured on a AR 2000 rheometer (TA Instruments, USA) at 25 C. Cone-and-plate measuring system geometries were used for these characterizations, and chosen depending on the viscosity range, respectively: 60 mm diameter aluminium coneplate with an angle of 0 19 57 , 60 mm diameter

Suppliers

Weight (%, w/w) Standard emulsion Test emulsions 8 3 5 11 61.7 5 0.3 1

Coco caprylate/caprate Isohexadecane Cetyl alcohol (and) glyceryl stearate (and) PEG-75 (and) ceteth-20 (and) steareth-20 Emollient Aqua Glycerine Carbomer Propylene glycol (and) methylpropanediol (and) potassium sorbate (and) methylisothiazolinone

Starinerie Dubois (France) Croda (England) Starinerie Dubois (France) See Table 1 CarloErba (Italy) Lubrizol (Belgium) Biophil (Italy)

14 8 5 0 61.7 5 0.3 1

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35 30 25

Force (g)

20 15 10 5 0 0 2 4 6 8 10 12 14

2.3.2. Evaluation of spreading for oil phases Spreading of the oil phases was dened as the surface of skin covered by the sample in one minute [23]. The larger the covered surface, the easier the sample spreads. The assessors were asked to put down 10 L (10 L syringe, SGE, Australia) of sample at 6 cm from the arm bend and to keep the forearm horizontal, without moving, for one minute. According to the anatomy of assessors forearms, circular or ellipsoidal forms were covered by the oils. Outlines of the form covered by the spread substance were then drawn with a pen for skin and the lengths of the semi-major and semiminor axes of the ellipse were measured. The spreading of each oil phase was then calculated according to the following equation: SOP = ab VS tS

Time (s)
Fig. 1. Texture prole obtained with the standard emulsion.

where a and b are the lengths of the semi-major and semi-minor axes respectively (in mm), VS is the volume of sample (in L) and tS , the time (in min). 2.3.3. Evaluation of the oil phase penetration Penetration of the oil phases was dened as the time necessary to observe the total disappearance of the sample put down on skin. 0.5 L of sample was put down at 6 cm from the arm bend. The assessor started the chronometer and kept her forearm still under lighting. The assessor was asked to observe the deposit and indicated when she could not observe the product any more on the skin as the consequence of its absorption into the skin. The time for total penetration was recorded and the penetration rate was then calculated according to the equation: POP = tP VP

acrylic coneplate with an angle of 2 01 53 and 40 mm diameter steel coneplate with an angle of 0 59 . Flow curves were recorded with a continuous ramp test in shear rate (0.0117,000 s1 ) during 5 min. Viscosity values for pure ingredients and oil phases (VOP ) were selected in the Newtonian region, while for the cosmetic emulsions, viscosity values (VEM ) at a shear rate of 1000 s1 were chosen. 2.3. Sensory analyses Sensory analyses were carried out to evaluate spreading of the ve emulsions (SEM ) on the one hand, and spreading and penetration of the ve corresponding oil phases (SOP and POP respectively) on the other hand. Each of these three attributes was evaluated separately. The sensory panel consisted of ten female volunteers from 20 to 40 years old. The assessors were trained in two training sessions followed by two test sessions in which samples were evaluated twice. Samples were labelled with three-digit random numbers and were randomly presented at room temperature in 5 mL opaque vials. Sensory attributes were assessed on the internal side of the forearm according to well-dened procedures as described below. Tests were carried out successively on the left and right arms. Prior to and between each sample test, the assessors cleaned the skin of their forearm with skin cleanser, then water and nally dried it carefully. Testing took place at the sensory facilities of the University of Le Havre, France. Analysis conditions were controlled before sessions, in particular the lighting in sensory booths. Because ingredients and emulsions possess quite different physicochemical properties, three different evaluation procedures were dened, all with strict protocols as described below. 2.3.1. Evaluation of spreading for emulsions Spreadability was dened as the ease of moving the cosmetic emulsion over a given distance. The distance dened on the skin was of 6 cm. The assessor put down 50 L of the sample at 6 cm from the arm bend with a M250 positive displacement pipette (Microman , Gilson, France). With the index nger, the sample is spread only once towards the hand for a xed distance of 6 cm. The assessor evaluated the force while applying the sample onto the skin surface and indicated the score for each sample on a scale from 0 to 9 with 0.5 increments and verbal anchor points. To quantify this attribute, assessors were trained to the response scale with internal referent samples (scores 1 and 8). During the test sessions, assessors were authorized to re-test either samples or references several times.

where tP is the time for penetration (in min) and VP , the volume of sample (in L). 2.4. Data analysis Analyses of variance (ANOVA) were conducted to check differences between properties of each emollient. One-way ANOVAs were performed on each instrumental measurement and two-way ANOVAs were computed on each sensory attribute with samples and assessors as variables. In case of signicant difference at 95%, Tukeys HSD post hoc comparisons were then carried out to investigate the sample effect. The correlation matrix of the mean values was used in order to establish and interpret the relationship between sensory and instrumental measurements. All mathematical and statistical analyses were performed using XLSTAT software. 3. Results and discussion 3.1. Sensory spreading of emulsions Spreading of a cosmetic cream is a determinant textural attribute that governs the performances of the product during its application on the skin. In order to evaluate the impact of the emollient on this attribute, a sensory analysis was carried out on the ve creams formulated as described above, by a trained panel. The precise protocol of testing was established with physical references to distinguish and evaluate specically this textural attribute. Spreading of emulsions (SEM ) scored between 0 and 9 is indicated in Table 3. We observed that all emulsions were evaluated to be signicantly different on this attribute with scores ranging from 2.50 to 8.05. Spreading was higher with Ester 1 and

G. Savary et al. / Colloids and Surfaces B: Biointerfaces 102 (2013) 371378 Table 3 Sensory properties and instrumental measurements for the different emollients incorporated either in the oil phase (OP) or in the emulsion (EM). Standard Sensory properties Oil phase penetration POP (min/L) Oil phase spreading SOP (mm2 /min/L) Emulsion spreading SEM (score from 0 to 9) Instrumental measurements Oil phase viscosity VOP (Pa s) Contact angle at 0 s A0s ( ) Contact angle at 4 s A4s ( ) Emulsion viscosity VEM (Pa s) Texture of emulsion TEM (g s) 5.36c 49.9b 3.55d 0.0058c 38.3bc 12.3ab 0.08c 242c Ester 1 10.1b 29.0c 8.05a 0.0152b 45.5b 16.2a 0.16bc 112e Ester 2 14.3a 18.6d 2.50e 0.0344a 55.6a 17.1a 0.61a 416a Ester 3 5.85c 43.0b 6.05b 0.0063c 39.2bc 8.97b 0.11c 324b

375

Silicone 5.83c 78.4a 4.95c 0.0046c 32.0c 5.70b 0.24b 180d

Different letters in the same row indicate a signicant difference between samples at p < 0.05.

Table 4 Correlation matrix of the mean sensory and instrumental measurements across the samples. POP Sensory properties Oil phase penetration (POP ) Oil phase spreading (SOP ) Emulsion spreading (SEM ) Instrumental measurements Oil phase viscosity (VOP ) Contact angle at 0 s (A0s ) Contact angle at 4 s (A4s ) Emulsion viscosity (VEM ) Texture of emulsion (TEM )
* ** ***

SOP 1.00 0.03 0.79* 0.93** 0.92** 0.46 0.43

SEM 1.00 0.40 0.26 0.08 0.58 0.78*

VOP 1.00 0.96** 0.78* 0.91** 0.57

A0s 1.00 0.90** 0.75* 0.54

A4s 1.00 0.46 0.21

VEM 1.00 0.63

TEM 1.00

1.00 0.79* 0.23 0.98*** 0.94** 0.81* 0.86* 0.42

Signicance at p < 0.05. Signicance at p < 0.01. Signicance at p < 0.001.

Ester 3 and then with silicone. The cream with Ester 2 as emollient had the lowest performance in terms of spreading, even lower than the property with the standard oil phase. For these sensory analysis results, the ANOVA revealed that assessors were not a signicant source of variation (p = 0.22). As a consequence, the composition of the oil phase had a signicant effect on the spreading of emulsions. 3.2. Instrumental characterization of emulsions Additionally, rheological measurements and texture analyses were performed on the emulsions. Flow properties were measured in order to characterize the behaviour of emulsions when subjected to a shear, this corresponding to the physical phenomenon when a cosmetic emulsion is spread on skin. Rheological behaviours of the ve creams exhibited the same prole with a zero-shear viscosity, a shear-thinning region and an innite shear viscosity that t the Cross Model. Here we only focused on shear-rate viscosities at 1000 s1 which can be representative of a spreading process on skin [24]. Corresponding values for the viscosity (VEM ) for each emulsion are reported in Table 3; results indicate that the emulsion with Ester 2 showed the highest viscosity (VEM = 0.61 Pa s) whereas the other emulsions are less viscous, especially the ones formulated with the standard oil phase and with Esters 1 and 3. At this range of shear rate, emulsions actually experience loss of structure followed by breakdown as evidenced on rheograms showing a sharp decrease in viscosity. Furthermore, a characterization using a TA.XTplus Texture Analyser was also carried out to physically evaluate spreading of the ve emulsions. Spreading was estimated as the work required for a weight rst to provoke its motion and then to move it a distance of 6 cm at a constant rate of displacement. Resulting proles, as shown in Fig. 1, were obtained in triplicate for each cream. The area under the curve was calculated, thus interpreted as the difculty

of spreading: the smaller the area, the easier the spreading. Mean areas for the creams are presented in Table 3 (TEM ). Values differed signicantly among emulsions, with Ester 1 and silicone containing emulsions being the easiest to spread, followed by standard, then Ester 3 and nally Ester 2 based emulsions. The aim of this study was also to determine how instrumental measurements could replace sensory analyses. For that purpose, the correlation matrix of the mean sensory and instrumental values was computed as reported in Table 4. One can observe that the sensory data obtained through spreading of the test emulsions appears to be signicantly correlated with the spreading of emulsion as evaluated by instrumental measurements (Pearson coefcient = 0.78). The negative correlation coefcient observed is the consequence of opposite scales: the scale used by assessors was graduated from 0 for poor to 9 for high spreadability whereas the instrumental spreading was measured as a force that is proportional to the difculty to spread the product. Thus, a correlation between sensory and instrumental analyses was clearly established here. It is thus possible to implement texture analysis of in vivo tests to evaluate the spreading properties of emulsions. It is worthwhile to note that the PMMA and polypropylene surfaces chosen in this study were of practical relevance and do not mimic either the chemical composition or the surface energy of the stratum corneum. These surfaces made it possible to have appropriate friction conditions to measure the spreading of cosmetic creams and are easily found everywhere. The correlation coefcient was lower than expected in spite of cautiously dened experimental parameters adopted to achieve this correlation: the distance of spreading in both experiments was identical, assessors were trained to evaluate the force while applying the sample onto the skin, physical references were freely available for the assessors at each session. A better correlation might be obtained by studying the effect of other parameters such as, for example, the speed to move the nger on the skin or the weights applied in sensory and instrumental

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Table 5 Physico-chemical properties of ingredients either pure or dispersed in the oil phase. Density Pure ingredients 0.963 Ester 1 Ester 2 0.976 Ester 3 0.932 Silicone 0.957 Oil phases Ester 1 Ester 2 Ester 3 Silicone Standard 0.894 0.900 0.880 0.894 0.827 Surface tension (mN/m) 28.09 0.59 Nd 20.16 0.09 17.37 0.07 26.36 0.59 25.55 0.91 27.96 1.19 19.65 0.34 25.03 0.91 Viscosity (Pa s) at 10 s1 124 103 3630 103 10 103 4 103 15 103 34 103 6 103 5 103 6 103

experiments, respectively, that could be different and induce different deformations of the products. 3.3. Characterization of the oil phases To establish correlations between instrumental techniques and in vivo sensory analysis in the case of the oil phases, some experiments were carried out on the oil mixtures alone. Various characterizations were performed including sensory spreading and penetration evaluations, viscosity, and contact angle measurements. A previous preliminary study [25] has shown that the spreading of pure ingredients, characterized by sensory and instrumental analyses, was mainly inuenced by the physical state of the ingredients. Thus, surface tension and dynamic contact angle were not measurable for highly viscous ingredients like Ester 2 and sensory evaluation became particularly difcult as products could be liquid as well as close to solid state. Table 5 sums up the interest of studying the emollients solubilized in the oil phase (Phase A, Table 2). Incorporation of esters or silicone into the oil phase both increases the oil phase density and leads to a lower density difference between the different emollients. Due to solubilization, and taking into account standard deviation values, surface tensions of esters alone and oil phases fell into the same range. Surface tension of silicone remained the lowest, nevertheless gaps between emollients were strongly reduced. Lastly, all emollients, either pure or included in the oil solution, showed a Newtonian behaviour (curves not shown here). Compared to pure ingredients, solubilization in the oil phase shifted viscosity values (VOP ) of Esters 1 and 2 to much lower values. They still remained signicantly higher than that of Ester 3. 3.3.1. Sensory characterization of oil phases Spreading of the ve different oil phases (SOP ) was evaluated by the assessors according to a different procedure from the one used for spreading evaluation of the emulsions. When deposited on the skin surface, the oil phases exhibited different behaviours from the emulsions as the consequence of the effect of consistency. Emulsions formed a mound that assessors spread on the skin, whereas the oil phases spread spontaneously without requiring any action for the assessors. Therefore, oil phases promptly formed an oval stain when deposited on the skin. Each sample was characterized by a shiny appearance. The assessors were then able to visually evaluate the surface of skin covered by the product by measuring the corresponding area one minute after deposition. During this time, dermal penetration of emollients may happen. As a result, we decided to ask the panellists to assess also skin penetration of the ve oil phases (POP ). This property was evaluated as the time necessary to observe the total disappearance of the shiny stain formed by the sample deposited on the skin. In

this study, we assume that there was no difference in terms of volatility between samples. This supposition was made since the emollient represented only 11% (w/w) of the composition of the oil phase. Among ingredients, silicone was the most volatile with a vapour pressure of 0.2 mmHg at 25 C and a boiling temperature of 210 C against for instance, Ester 3, 5.93 106 mmHg and 352 C, respectively. Measurements of skin penetration POP in Table 3 indicate times above 5.36 min. As a consequence, we assumed that the duration of the spreading evaluation (1 min) was short enough to consider that there was no signicant penetration occurrence of samples into the stratum corneum. Generally, the penetration ability of the emollients into the lipophilic stratum corneum depends on both the polarity and the molecular size of the compound [26]. This is conrmed here, penetration variation among oil phases is mainly related to both the polarity and the molecular size of ingredients (Table 1); the higher the values of log P and Mw , the longer the time needed to penetrate into the stratum corneum as illustrated for Esters 1 and 2. Concerning spreading, results reveal a large effect of the composition of the oil phase (SOP in Table 3). Values ranged from 18.6 to 78.4 mm2 /min/L, for Ester 2 and silicone respectively. The standard oil phase displays an intermediary spreading of 49.9 mm2 /min/L. As discussed by other authors [5], the ingredients with higher molecular weight exhibit lower spreading values, as observed among esters (Table 1). 3.3.2. Instrumental characterization of oil phases spreading Contact angle measurements for standard or emollient-oil mixtures were performed from initial time, as the drop of liquid was deposited on PMMA surface, until it reached a measurable constant value. At t = 0, initial contact angle values are respectively: Ester 2 (55.6 3.9), Ester 1 (45.5 2.4), Ester 3 (39.2 1.7), standard (38.3 1.9), silicone (32.0 0.3). This emphasizes different afnity of ingredients with the support. The curves of contact angle versus time then exhibit a rapid exponential decrease, corresponding to the rapid spontaneous spreading of each solution on the support, until an asymptotic contact angle value is reached (after 4 s for silicone (approx. 6 ) and Ester 3 (approx. 9 ), after 14 s for Ester 2, Ester 1 (approx. 12 ) and standard (approx. 11 )). Selection of the data for contact angles were thus restricted to the shortest time period necessary to obtain one of these asymptotic values, that is 4 s in the case of silicone. Fig. 2 shows the relaxation of the contact angle, over a time period of 4 s, for each emollientoil mixture as well as the prole for the corresponding drop of the ve systems at t = 0 s (immediately after deposition) and t = 4 s. Table 3 also displays the values for the contact angle just after deposition (A0s ) and at t = 4 s (A4s ). Study of spontaneous spreading of a liquid on a solid surface involves different key parameters that are: surface tension, viscosity and density of liquid, surface free energy, roughness and heterogeneity of solid support [19]. Due to solubilization of the emollients in the oil phase, the impact of density, viscosity and surface tension on spreading is actually reduced. When considering these last parameters for the different mixtures tested, only differences in terms of surface tension and viscosity may explain the contact angle results. Therefore, surface tension and volatility differences between silicone and Ester 3 can explain the different spreading that is observed. In the case of the ester molecules dispersed in oil and also oil phase, the main parameter governing the different spreading behaviour is undoubtedly the viscosity. It is also necessary to keep in mind that a droplet can evaporate somewhat, depending on the wetting behaviour and the hydrophobicity/hydrophilicity of the substrate [21]. In all cases, evaporation phenomena remain negligible during the time of experiments [21,22]. This appears evident as Orejon et al. [21] have demonstrated that a typical evaporation time for ethanol droplets was

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Fig. 2. Contact angle evolution of oil phases deposited on PMMA surface.

between 90 s and 300 s for hydrophilic and hydrophobic substrates respectively. Initial and equilibrium contact angles values show an almost complete wetting of the liquids on the PMMA substrate, this being in good agreement with the roughness of PMMA plates (2 m) on the one hand, and surface free energy of the substrate on the other hand. Alterai and Sasa [22] reported a critical surface tension of 39 mN/m for a smooth PMMA surface, which is characteristic of intermediary properties (between PTFE around 20 mN/m and soda-lime glass 70 mN/m). This is also in good agreement with the relatively low polarity of the oily liquids tested in the present study. These measurements appear particularly relevant to anticipate the spreading ability of a sample, as evidenced by the correlation coefcients between SOP and A0s or A4s (Table 4). All these coefcients are negative since the contact angle was inversely proportional to the surface of PMMA covered by the product. Thanks to this correlation, it is possible to envisage predicting the spreading of different oil phases using an instrumental method instead of sensory evaluation. Moreover, present contact angle measurements were conducted with a PMMA surface, a fairly reproducible, easy-to-use and low cost material when compared to real as well as synthetic skin. At this step, it is possible to compare surface properties of PMMA and skin surface, in terms of surface tension and chemical composition, thanks to data from the literature. A surface free energy is reported for human skin varying from about 27 to 38.2 mJ m2 in the dorsal region of skin index [27] but also on the volar forearm or forehead skin [28]. Lowest values are obtained for a dry skin submitted to a cleaning with delipidizing solvent and highest ones were obtained on skin washed with soap and rinsed thoroughly under tap water or unwashed skin during 16 h. Concerning PMMA surfaces, values are similar or higher than skin, data in the literature ranged from 39 to 48 mJ m2 depending on methods used and cleaning of the surface [22,27,29]. Taylor et al. [30] reported even values ranging from 46 to 54 mJ m2 related to roughness and treatment of PMMA surfaces. Both types of surface exhibit also a high dispersive component close to total surface free energy, an acidic component close to zero, a basic component varying from about 5 to 20 mJ m2 for PMMA and from about 0 to 28 for human skin. This can be related to a similar chemical surface composition: epidermal lipids on the one hand and ester methyl groups [31] on the other hand for PMMA surface. Even if PMMA surface does not mimic stratum corneum in terms of chemical composition and porosity, contact angle measurement is a pertinent method to measure pure

spreading properties of oils. However, it is important to take into account that such physical characterizations are not easy or possible with any kind of sample as for example with highly viscous liquids or the cosmetic emulsions of the present study. 3.4. Relationships between oil phase and emulsion properties When formulating a cosmetic product, a major point is to know how the properties of the end product can be governed by the intrinsic characteristics of ingredients. Our study shows that the relationship between the properties of emollients and the corresponding emulsions is not necessarily obvious. Concerning the viscosity of emulsions (VEM ), we observed a signicant correlation with VOP (Table 4). In this case, it is possible to anticipate the viscosity of the cream according to the composition of the oil phase. As an example, Ester 2 induced the highest viscosity for both the oil phase and the corresponding emulsion. However, concerning spreading, there is no linear correlation between SEM and SOP (Table 4) as an oil phase characterized by a high spreading performance does not necessarily generate a cosmetic emulsion with the same performance; this is illustrated with the silicone ingredient. Emulsions are complex structures that exhibit original behaviours inuenced by many parameters including composition and proportion of the dispersed and continuous phases, droplet size, emulsier type, composition and structure of the interface, and interactions between ingredients [32]. Concerning spreading of emulsion, our experiments should be completed with other data to develop a predictive model with multiple parameters to be considered. 3.5. Relationship between sensory and instrumental measurements In conclusion, as shown in Table 4, penetration of the oil phase (POP ) was best correlated with viscosity of the oil phase (VOP ) followed by contact angle at 0 s (A0s ). Spreading of the oil phase was correlated with both A0s and A4s contact angles among the instrumental measurements. The sensory spreading of emulsion correlated best with the spreading of emulsion instrumentally measured in terms of work required to move a weight on a surface. Consequently, all these results made it possible to implement physical measurements of sensory evaluations of either oil phases or emulsions to avoid time-consuming in vivo methods.

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Acknowledgements The authors thank different contributors. Authors sincerely acknowledge Clmentine Lachaud for instrumental measurements and Nathalie Loubat-Bouleuc (Starinerie Dubois, France) for helpful discussions. References
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