j. Cosmet. sci.

, 58, 45-51 (January/February 2007)

Clay facial masks: Physicochemical stability at different
storage temperatures
VIVIAN ZAGUE, DIEGO de ALMEIDA SILVA,
ANDRI ROLIM BABY, TELMA MARY KANEKO, and
MARIA VALIRIA ROBLES VELASCO, Departme.t of Pharmacy,
School of Pharmaceutical Scie.ces, U.iversity of Sa7o Paulo, 580 Prof.
Li.e Prestes Av., B/-13, 05508-900, Cidade U.iversitdria,
Sa7o PaMo, SP, Brazil
Accepted for publication September 20, 2006.
Synopsis
Clay facial masks--formulations that contain a high percentage of solids dispersed in a liquid vehicle--have
become of special interest due to specific properties presented by clays, such as particle size, cooling index,
high adsorption capacity, and plasticity. Although most of the physicochemical properties of clay dispersions
have been studied, specific aspects concerning the physicochemical stability of clay mask products remain
unclear. This work aimed at investigating the accelerated physicochemical stability of clay mask formula-
tions stored at different temperatures. Formulations were subjected to centrifuge testing and to thermal
treatment for 15 days, during which temperature was varied from -5.0 to 45.0C. The apparent viscosity
and visual aspect (homogeneity) of all formulations were affected by temperature variation, whereas color,
odor, and pH value remained unaltered. These results, besides the estimation of physicochemical stability
under aging, can be useful in determining the best storage conditions for clay-based formulations.
INTRODUCTION
Face mask beauty treatments are among the oldest cosmetic preparations. Current
interest in the development of these formulations is attributed to their warmth, tight-
ening, and cleansing effects. Characteristics such as ease of application and removal,
reduced time for drying and hardening, and dermatological innocuousness are also
required (1-3). One of the most popular face masks is the wash-off type based on clay
raw materials, also known as clay facial masks or the once-fashionable "mud packs" (1).
Cosmetic science and aesthetic medicine have been rekindling interest in clay facial
masks mainly due to clay properties such as particle size, cooling index, high adsorption/
absorption capacity, and plasticity (4-6). Clay facial masks are composed of a high
percentage of solid particles (over 25%) dispersed in a liquid vehicle. The concentration
Address all correspondence to Vivian Zague.
45
46 JOURNAL OF COSMETIC SCIENCE
of these particles depends on the composition of the solids and liquid, and it will
determine the plasticity of the final product (1). Some substances, known as hydrophilic
thickeners, such as gums, can also change plasticity and alter the application character-
istics of the final product. Moreover, such substances may be useful in stabilizing the
dispersion of solids and, consequently, in preventing gradual phase separation, which is
occasionally observed during the shelf storage of clay masks (2). Clay facial masks should
be also formulated so as to prevent a slight or even complete dehydration of the
formulation under aging. Therefore, the inclusion of humectant substances, like glycerin
and propylene glycol, would avoid such dehydration (1).
Clay liquid dispersions involve an assortment of different stages including incorporation,
wetting, the break-down of particle clusters, and flocculation of the disperse particles.
Usually, the stability of the clay dispersion is affected by interactions between liquid and
particles and also by attractive interactions between solid particles (7).
Several authors have studied the effects of size, particle shape, mineralogy, and chemistry
of clays as well as the effects of pH, salt concentration, and mixing conditions on the
final dispersion properties (7-12). To our knowledge this is the first study focusing on
the physicochemical stability of clay mask preparations. Therefore, this study aimed at
predicting the physicochemical stability of clay masks under storage conditions at
different temperatures. This prediction is important in defining the components of
formulation, packing material, cosmetic forms, and preparation techniques (13).
MATERIAL AND METHODS
FORMULATIONS STUDIED
The clay facial mask formulations were developed with grade cosmetic raw materials
selected in agreement with technical and scientific specifications suited in relation to
particle size, microbial load, color, and odor.
The formulations were developed with kaolin (30% w/w) and montimorillonite (15%
w/w) (Alban Muller International, Vincennes, France). Formulations F2 and F3 also
contained magnesium aluminum silicate (5% w/w) (R. T. Vanderbilt Inc, Norwalk,
CT). The hydrophilic thickeners were hydroxypropyl starch phosphate (2.0% w/w)
(National Starch & Chemical Company, NJ) (F1) and xanthan gum (0.2% w/w) (Rhodia
SA, Boulogne-Billancourt, France) (F3). Glycerin (4% w/w) and propylene glycol (4%
w/w) were used as humectants in all formulations.
As the way of preparation has a great influence on the degree of clay dispersity and thus
on the physicochemical stability of the final product, all samples were prepared in the
same way. The clays were weighed and sprinkled into distilled water (at 75-80C)
during continuous stirring for 30 rain using a high-shear mixer (model 252-21, Quimis
Ltda, Sgo Paulo, Brazil) at 8000 rev/min-. The hydroxypropyl starch phosphate gum
was hydrated prior to its addition to the clay dispersion. In the F3 formulation, mag-
nesium aluminum silicate and xanthan gum were blended and then sprinkled into
distilled water in the same manner. The humectants were added in sequence.
CLAY FACIAL MASKS 47
PRELIMINARY STABILITY TEST (PST)
The formulations were left at rest for 24 h before testing to ensure full water adsorption
(11,14). After this period, 5 g of each visually stable formulation (homogeneous visual
aspect) were submitted (three replicas) to centrifuge (model 208N, Fanem Ldta, So
Paulo, Brazil) testing. The formulations were evaluated 1000, 2000, and 3500 rev/min -
rotor speed, during 15 rain at each velocity (15).
The formulations were classified, after centrifuge testing, according to liquid phase
separation volume: 7-10 ml (IM), intensely modified; 4-6 ml (M), modified; 1-3 ml
(SM), slightly modified; and those without phase separation (N). Formulations classified
as normal were submitted to the accelerated stability test.
ACCELERATED STABILITY TEST (AST)
The formulations were submitted to the stress conditions of temperature in a short
storage period. The amount of the formulations submitted to AST was 30 g, considering
that on each day of analysis there was a sample that did not return to storage conditions.
Samples were stored in polyethylene packing material. Temperatures, storage periods,
and days of analysis were (13,15):
(a) 45.0 + 0.5C; 14 days; analysis at the 1 st, 3 rd, 7 th, and 14 th days.
(b) -10.0 _+ 0.5C/24 h and 45.0 + 0.5C/24 h (temperature cycles); -
12 days; analysis at the 6 th and 12 th days.
(c) 5.0 + 0.5C; 14 days; analysis at the 1 s, 3 rd, 7 th, and 14 th days.
The formulations were first acclimatized for at least 1 h at room temperature
(24 + 2.0C) prior to testing, considering the first day of analysis (t) as 24 h after the
preparation of the formulations.
The physicochemical characteristics evaluated, on each day of analysis, were: organo-
leptic characteristics (visual aspect, color, and odor), pH value, and apparent viscosity
(13,15). The formulations were dispersed (1:10) in distilled water in order to measure
pH values. The apparent viscosity of the formulations was determined using a rotational
viscometer (model Visco Star R, Fungilab S.A.). The apparent viscosity measurements
were obtained under the following experimental conditions: 24 + 2.0C, 18 g samples,
TRll spindle, and rotation speed of 100 rpm. Analyses were accomplished in parallel
with a reference sample, stored at a controlled room temperature (22 _+ 2C).
RESULTS AND DISCUSSION
PRELIMINARY STABILITY TEST (PST)
The formulations presented a red color, an earthy characteristic odor, and pH values
ranging from 6.8 to 7.1.
After centrifuge testing, the F2 formulation was intensely modified with a considerable
phase separation. This instability was attributed to an insufficient viscosity of the
fbrmulation to keep a hgh content of solids dispersed. The clay types differed from each
other mainly by their mineral composition, which has an influence on the viscosity and
48 JOURNAL OF COSMETIC SCIENCE
stability of formulations (7). Magnesium aluminum silicate, which was added to the F2
formulation, is widely used as a thickening agent in many cosmetic preparations, due to
its thixotropic and pseudoplastic properties. The colloidal structure of this clay provides
excellent suspension of fine particles in aqueous systems (16); however, it did not offer
the suspension efficiency of other clay particles (kaolin and montmorillonite) in the
formulations studied.
Clays and organic thickeners, such as gums, are often used synergistically in cosmetic
products to provide a balance of suspension stability. The gums' protective colloidal
action improves clay stability in the presence of electrolytes, surfactants, water-solubles,
and even against phase separation (11,17). This fact was also observed in this study, once
hydroxypropyl starch phosphate (F1) and xantham (F3) gums promoted stability in both
formulations after centrifuge testing, preventing phase separation. Therefore, only the
F1 and F3 formulations were classified as normal after PST, and they were submitted to
AST.
ACCELERATED STABILITY TEST (AST)
Formulations F1 and F3 maintained normal color and odor in all storage conditions.
These formulations did not present variation in the initial pH value (7.3), superior to
_+ 1.0%, probably due to the buffer effect of clay that occurs when a suspension is at a pH
very near its natural pH (range of pH close to 6.0 or 7.5-8.0) (18). However, they
presented variations in visual aspect (Table I) and apparent viscosity (Figure 1) in the
same evaluated conditions. These alterations could be associated with temperature and
time influences on the clay hydration process.
The structural framework of clay is composed of thousands of submicroscopic platelets
Table I
Visual Aspects Observed in F1 and F3 Formulations at Different Temperatures in Storage Conditions in
the Accelerated Stability Test
Visual aspect
Temperatures of Days of
storage conditions analysis F 1 F3
5.0 -+ 0.5 C t Homogeneous Homogeneous
3 SM SM
7 SM SM
14 SM SM
22 -+ 2.0C 3 N SM
7 N SM
14 N SM
45.0 -+ 0.5C 3 SM SM
7 SM SM
14 SM N
10.0 _+ 0.5C/24 h 7 SM N
45.0 _+ 0.5C/24 h 14 SM N
t : 24 h after preparation of clay masks.
SM = slightly modified.
N = normal.
CLAY FACIAL MASKS 49
(a)
. 5.0_+0.5C '- 22_+2C . ,45.0+0,5C--o---10. O+0.5C/24h45.0+0,5C/24h
5000
4000
3000
2000
1000
0
5.0 + 0.5
1 3 7 14
Days of analyses
=- 222oc _ .- '45.0 :t: 0.5 C -- -10.0 :t: 0.5 C/-24-h 45.0 :t: 0.5 C/-24 h
5000
8
4000
>%
3000
2000
o. 1000
0
1 3 7 14
Days of analyses
Figure 1. Apparent viscosity as a function of days of analysis at different temperatures in storage conditions
(a = F1 formulation; b = F3 formulation).
stacked in sandwich fashion. The faces of these platelets carry a negative charge, while
their edges have a slightly positive charge. The net negative charge of the platelet is
mostly balanced by inorganic cations. These charge-balancing ions are associated with
platelet faces and are termed "exchangeable" since they can be readily substituted by
other cations (17,18). When the clay is dispersed in water, the latter penetrates into the
platelets, forcing them further apart. As this happens, the exchangeable ions begin to
diffuse away from the platelet faces. Further penetration of water between the platelets
then proceeds until complete separation (17,19). Generally, the speed with which plate-
let separation occurs is directly related to the amount of mechanical and thermal energies
introduced during hydralion (7). Therefore, the technological conditions of clay masks'
preparation were concisely controlled in this study to achieve reproducible results (see
Formulations Studied, above).
Once the clay is hydrated, the weakly positive charges are attracted to negatively charged
platelet faces. The resulung three-dimensional structure builds rapidly at first, giving a
quick increase in viscosity. As time passes, the remaining free platelets take a longer
50 JOURNAL OF COSMETIC SCIENCE
time to find an available site in the structure, and so viscosity increases at a progressively
slower rate (18). This was observed in the F1 and F3 formulations (Figure la and b,
respectively) which present a progressive increase of apparent viscosity in the days of
analysis at room temperature (22 + 2C). Apparent viscosity as a function of the days
of analysis at different temperatures in storage conditions is illustrated in Figure 1. In
both formulations, at 5.0 + 0.5C and temperature cycles, apparent viscosity decreased
in relation to room temperature. Moreover, these formulations presented a slight visual
aspect modification with cluster formations. Lower temperatures possibly decrease the
clay hydration speed, promoting particle agglomerates. In contrast, the F1 and F3
formulations at high temperature (45.0 + 0.5C) presented a viscosity increase in re-
lation to room temperature (as shown in Figure 1), which was perceived visually. This
fact could be attributed to clay-accelerated hydration caused by high temperature, which
accelerates the fitting of free platelets in the structure. Jefferson and Rogers (14) ob-
served that thermally induced structural rearrangements, which are shown by slight
swelling, occur when clay suspensions are stored at higher temperatures. Formulations
F1 and F3 also presented notable drying due to water loss at high temperature, which
could also explain the increase in apparent viscosity in this storage condition. These
results indicate that the amount or kind of humectants in the formulations was not
enough to retain water.
The association between clays and gums is indicated to obtain stable clay dispersions at
different temperatures since most gums, in contrast to clays, have a chemical structure
without the tendency of association (11). Thus, studies have been developed with dif-
ferent concentrations and kinds of gums, as well as with other humectant concentrations,
in order to stabilize these formulations in light-and-temperature storage conditions.
In most clay mask formulations, clays are used in aqueous suspensions, and they present
gelification under certain conditions of pH values, electrolytes, clay concentration, and
temperature (14,18-20). The results obtained in this study indicate the behavior of these
formulations at different temperatures in storage conditions. These results are of a great
importance and can determine in which conditions the clay can be used, since formu-
lators are more concerned with the behavior of clay in the presence of the other ingre-
dients, rather than in water alone. Understanding the mechanism of gel structure
formation has important implications for its optimization in order to control the settling
of clay suspensions, although this is beyond the scope of this paper and needs further
study.
CONCLUSIONS
This study provides useful results to estimate physicochemical stability under the aging
of clay-based formulations. Magnesium aluminum silicate did not improve the physico-
chemical stability of formulation F2 in the preliminary stability test, while gums
stabilized formulations F1 and F3 in the same test. Formulations F1 and F3 were
unstable in the accelerated stability test, presenting variations in visual aspect and
apparent viscosity in storage conditions at different temperatures. Moreover, humectants
added to the formulations did not retain water under the same conditions, promoting
slight drying at a temperature of 45.0 + 0.5C.
ACKNOWLEDGMENTS
This work was supported by the National Council for Scientific and Technological
CLAY FACIAL MASKS 51
Development (CNPq), a foundation linked to the Ministry of Science and Technology
(MCT) to support Brazilian research, and CAPES.
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