Advances in Environmental Sciences, Development and Chemistry
Differences between structural, textural and rheological properties of two Cameroonian mineral clays used as cosmetic mask Orléans Ngomoa,b*, Joseph Marie Sieliechia, Jean Bosco Tchatchuenga, Richard Kamgaa, Aurel Tabacaruc, Rodica Dinicad , Mirela Praislerd
I. INTRODUCTION
Abstract— This work aims to determine the structural, textural and rheological properties of two clays traditionally used as a beauty mask by women. Clays were sampled at Maroua (M0M) and Douala (D0M) respectively located in the Far North region and Coast of Cameroon. The structure analysis was performed using techniques such as SEM, EDX, FTIR, XRD, and ATG. The determination of the specific surface area was performed by using the adsorption desorption isotherms of nitrogen. The rheological properties were determined using a rheometer. The results show that the Maroua clays consist mainly of montmorillonite, whereas Douala clays consist primarily of kaolinite. Maroua clays have a surface area of 109.48 m2/g and contain in their structure essential elements such as calcium (1.23%) Magnesium (0.95%) and sodium (0.46%); while Douala clays have a surface area of 55.05 m2/g with the presence within their structure of essential elements such as calcium (0.34%) Magnesium (0.51%) and sodium (0.17%). Rheological analyzes show that Maroua clays has the pseudoplastic character typical montmorillonite while Douala clays has the viscoelastic nature characteristic of kaolinite. Both clays can be used as facial mask with more benefits for montmorillonites.
C
lays are alumino-silicate microcrystallines with leaf structure, originating from the alteration of primary minerals of soil [1]. Clay minerals are not only the “most abundant mineral components of the surface world” [2], but also the minerals showing various applications, in cosmetic, environmental protection and in paper, chemical or food industries for the discoloration and stabilization of vegetable oils [3], [4]. During the last decade, clays beneficial to human health have received great interest [5]-[7]. The most frequently encountered clays are kaolinite, montmorillonite, illite, vermiculite and chlorite [8], [9]. The advantages are : a high sorption capacity , high surface area, water solubility , reactivity with acids, a high refractive index , a large capacity of heat retention , opacity , low hardness , high reflectance and good rheological properties [10]. In this study, the analysis of the structural, textural and rheological properties of clay from Maroua and Douala is made. The morphological analyses were performed by scanning electron microscopy (SEM). The chemical composition was determined by X-ray Dispersive Energy Spectroscopy (XDE) and by X Fluorescence (XF). The different crystalline and superficial phases were studied by using X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Thermal Gravimetric Analysis (TGA). Textural properties were analyzed by Nitrogen adsorption-desorption and rheological properties are also determined.
Keywords— kaolinite, montmorillonite, physico-chemical and textural properties, cosmetic masks
This work was supported in part by the scholarship Program "Eugen Ionescu" AUF for granting a fellowship. Orléans Ngomoa Department of Applied Chemistry, National School of Agro-Industrial Sciences, University of Ngaoundere, BP.455 Cameroon. Department of Chemistry, Faculty of Sciences, University of Yaounde I, BP. 812 Cameroon Phone:(0023799614106); e-mail:
[email protected]. Joseph Marie Sieliechia, Department of Applied Chemistry, National School of Agro-Industrial Sciences, University of Ngaoundere, BP.455 Cameroon. email:
[email protected] Jean Bosco Tchatchuenga, Department of Applied Chemistry, National School of Agro-Industrial Sciences, University of Ngaoundere, BP.455 Cameroon. e-mail:
[email protected] Richard Kamgaa Department of Applied Chemistry, National School of Agro-Industrial Sciences, University of Ngaoundere, BP.455 Cameroon. email:
[email protected], Aurel Tabacaruc Department of Chemical Sciences, University degli Stuti of Camerino, Via S. Agostino 1, 62032 Italy. e-mail:
[email protected] Rodica Dinicad . Department of Chemistry, Physics and Environment, Faculty of Sciences and Environment, “Dunarea de Jos” University of Galati, 800008, Romania. e-mail:
[email protected] Mirela Praislerd Department of Chemistry, Physics and Environment, Faculty of Sciences and Environment, “Dunarea de Jos” University of Galati, 800008, Romania. e-mail:
[email protected]
ISBN: 978-1-61804-239-2
II. MATERIAL AND METHODS A. Material The two types of clay analyzed in this study originate from the far north and the littoral of Cameroon, in the areas of Maroua and Douala respectively (fig.1). Clay fractions (99.9995%) that was used for experiments was provided by Alphagaz (Italy). Specific surfaces areas were determined from adsorption data by applying the Brunauer–Emmet–Teller (BET) equation. Micropore volume areas were obtained using the t -plot method. Pore size distributions were calculated based on the desorption branch by using the Barrett–Joyner–Halenda method. The water adsorption capacity was determined using a desiccator and the rheological values are obtained on the Rheological AR 2000 ex with 60mm of stray diameter, by mixing with a ratio water/clay of 3/2 for montmorillonite and 1/1 for kaolinite.
ISBN: 978-1-61804-239-2
a
b
Fig.2. SEM of Maroua (a) and Douala (b) clay samples, size 1000µm.
a
b
Fig.3. Elemental analysis of Maroua (a) and Douala (b) clay.
Table1. Chemical composition (major elements) of Maroua and Douala clays determined by XDE. 426
Advances in Environmental Sciences, Development and Chemistry
Elements % weight MOM
Si
Al
Fe
Cl
26,377
15,575
6,948
0,284
0,464
DOM
20,469
18,195
2,570
0,286
0,167
d(A°)
Na
Elements % weight MOM
K
Mg
Ti
Ca
1,651
0,949
1,285
1,233
57,658
DOM
1,039
0,513
1,500
0,341
57,388
Elements d(A°)
O
Fe
Co
Zn
Pb
Rb
Sr
Zr
Mo
MOM
12844
478
37
13
63
53
66
18
DOM
4747
222
146
30
43
44
150
13
M0M D0M
4.26, 3.35, 4.26 4.26 Fe Oxyde 2.57 2.57
Ti Oxyde 3.58 3.58
7.20 7.20 Montmorillonite 15.78 /
The important number of peak characteristic of quartz on clay from Maroua shows a more amorphous structure. When the Greene–Kelly test is used on Maroua sample reexpand partly upon contact with glycerol vapor, there is no peak at 19.8 Å, Montmorillonite is the smectite of this mineral clay (not represented here). The infrared spectra of Maroua and Douala clays are shown in Fig.5. The band interpretation is given in Table 4. The adsorption bands of the two types of samples are similar; many superficial groups have Si and Al, as indicated previously by the EDX observations. The Douala clay shows thinner bands and the band of smectite (around 3400 cm-1) is missing from its spectrum.
Table2. Composition in trace elements of Maroua and Douala clays determined by XF
Elements (ppm)
M0M D0M
a
B. Structure and superficial phases The nature of different phases is identified by XRD, as shown in Fig4 for the Maroua and Douala clays. The different elements that were identified are listed in Table 3. a
b
b
Fig.5. Infrared spectra of Maroua (a) and Douala clays (b) Fig.4. XRD diffractogramms of Maroua (a) and Douala (b) clays Table4. Attribution of the infrared spectra bands of Maroua and Douala clays
Table3. Diffraction results obtained by XRD
Elements
Silice (quartz)
ISBN: 978-1-61804-239-2
kaolinite 427
Advances in Environmental Sciences, Development and Chemistry
Wavenumber (cm-1) M0M D0M
Vibration type
3695
36933650
γOH, mainly Al-OH-Al of kaolinite
Nguetkam et al [12], [14]
3621
3621
γOH of kaolinite and montmorillonite, AlAlOH coupled to AlMgOH
Nguetkam et al [12], Christidis et al [4]
3406
/
γOH of water and hydroxyde groups involved in the hydrogen links (smectite)
Nguetkam et al [14], Christidis et al [4]
1634
1639
Deformation vibration γOH of water or Si-O, Si-O-Al
/
1115
Peak characteristic to kaolinite
Unuabonah et al[15] ,Nguetnk am et al[12], [14] Nguetkam et al[14]
987
995
Si-O of orthosilicates
Nguetnkam et al[12], [14]
909
908
Deformation vibration γOH of Al-OH-Al (smectite / kaolinite)
Wang et al[16] Nguetnkam et al[12], [14]
Deformation vibration Si-O of Quartz
Unuabonah et al[15], Nguetka m et al[12], [14] Nguetkam et al[12] Nguetkam et al[12], [14]
797
792
747
748
679
668
Deformation vibration γOH of kaolinite Si-O-Al (kaolinite and smectite)
The thermoponderal curves of Maroua and Douala clays are presented in Fig.6. We observe on the curve of Maroua clay two loss of weight of about similar importance. The first on 100°C corresponds to absorbed water. The strong slope on the curve indicates that water is absorbed between the leaf like observations on 2/1 clays (swelling clays). The second loss of weight shows between 250-550°C, corresponds to the dehydroxylation of clay. The loss of weight of Douala clays takes place in two steps also. However, the first one less important at 100°C (loss of absorbed water). The weak slope on the curve means that water is on the surface of clay material, meaning that we have 1/1 clay (not swelling clay). The second one is more important occurs between 250-600°C, corresponding to the dehydroxylation of water. Table5. illustrates these losses of weight.
ISBN: 978-1-61804-239-2
a
References
428
b
Fig.6. Thermoponderal curves of Maroua (a) and Douala (b) clay Table5. Relative proportions of weight loss between 30-200°C and 200-600°C as determined by TGA
Temperature variations (°C) Weight loss (%)
30-200
200-600
MOM
39,4
60,6
DOM
19,4
80,6
The different analyses of structure and superficial phase indicate that the Maroua clay is a mixture of kaolinite (type1/1) and montmorillonite (type2/1), while the Douala clay is mainly kaolinite (type1/1). C. Textural properties of clays The objective of this part is to define the interstitial spaces between clay platelets and the vacant sites. a
Advances in Environmental Sciences, Development and Chemistry
The water adsorption evaluation (Fig.8) confirms the results of thermoponderal analysis, which shows that the Maroua clays is swelling (type 2/1) and adsorbs too much water, contrary to Douala clays that shows no swelling (type 1/1) property.
b
D. Rheological properties of clays The main rheological parameters of suspensions are viscosity, shear rate, yield stress, thixotropy. Fig.9 shows a linear relationship between shear stress and shear rate, and fig. 10 illustrates the relationship between viscosity and shear rate. Fig.7. Adsorption/desorption isotherms for Maroua (a) and Douala (b) clay
1400
1200
shear stress (Pa)
The nitrogen adsorption–desorption isotherms obtained for the Maroua and Douala clays display very similar shapes (Fig.7). All the isotherms are close in shape to type IV because hysteresis occurs during the desorption branches, according to the IUPAC (International Union of Applied Chemistry) classification. This behavior can be attributed to mesoporous structures [17-19]. However, there are noticeable differences in the shape of their hysteresis loops (Table 6). The specific surface area of Maroua clays is twice that of Douala clay.
0
0,228
109,48
55,05
Weight water absorb (g)
0,4
M0M D0M
0,0 20
40
60
80
100
120
140
160
180
time (hours)
Fig.8. Water adsorption isotherms of Maroua and Douala clay
ISBN: 978-1-61804-239-2
60
80
100
120
180 160 140 120 100 80 60 40 20 0 0
20
40
60
80
100
120
Shear rate (1/s)
Fig.10. Effect of shear rate on viscosity on clay from Maroua (●) and Douala (○).
According to the graphs below, the two clays behave as viscoplastic suspensions, meaning that, below a certain critical value of stress ( the yield point corresponding to the elastic limit defined as a static yield, it marks the beginning of the solid - liquid transition [20], the material behaves as a solid , but flows like a viscous liquid when this stress exceeds. Viscosity depends on the applied stress and decreases with increasing shear rate. We note that the Maroua clay have yield point lowest (about 300Pa) while, Douala clay have greater levels of shear (about 400Pa) (Fig.9). This difference can be explained by the fact that Maroua clay is a swelling clay 2: 1 and adsorb more water, have a high fluidity and low viscosity. It is noted that the evolution of the viscosity versus shear rate is the same for both clays, but it is less important for clays Maroua (fig. 10); this might be due to the more important Calcium quantity [21]. However, the two suspensions formed are thixotropic.
0,6
0
40
Fig.9. Effect of shear stress on shear rate on clay from Maroua (●) and Douala (○).
0,8
0,2
20
shear rate (1/s)
D0M Pore Percenta volume ge (%) (ml/g) 0,014 6,2 0,008 3,5 0,009 3,9 0,012 5,1 0,021 9,0 0,020 8,8 0,130 57,3 0,015 6,3
0,130
600
200
Viscosity (Pa.s)
M0M Pore Percenta volume ge (%) (ml/g) 0,048 37,2 0,015 11,7 0,011 8,3 0,008 6,2 0,007 5,6 0,006 4,2 0,025 19,5 0,010 7,3
800
400
Table6. Pore size distribution and specific surface of clays
Pores size distribution (nm) 80 Total volume(ml/g) Specific surface (m2/g)
1000
429
Advances in Environmental Sciences, Development and Chemistry
The oxillation dynamic tests are also significant tools to reveal the microscopic structure of viscoelastic materials. In general, the material can respond to this type of deformation through two mechanisms: conventional storage energy and viscous dissipation energy. Quantitatively, these responses can be represented as storage modulus (G') or stored energy per volume unit, and loss modulus (G'') or energy dissipated per unit strain rate per volume unit. The storage modulus is proportional to the extent of the elastic behavior of the system and the loss modulus is proportional to the extent of the viscous behavior of the system. Fig. 11 presents the evolution of the elastic and viscous depending on the frequency modules.
50
a
Delta (degrés)
40
30
20
10
0 0
25
20
40
60
80
100
120
80
100
120
fréquence (Hz)
a 20
b 50
10
Delta (Degrés)
G',G" (KPa)
60 15
5
0 0
20
40
60
80
100
120
40
30
20
frequence (Hz) 10 80
b
0 0
G',G" (KPa)
60
20
40
60
Fréquence (Hz)
Fig.12. Effect of phase shift between the imposed stress and displacement, and frequency Maroua a) and Douala b)
40
20
Gels clays show the characteristics intermediate between liquids and solids with flows generally plastics and high viscosities [23] and hysteresis [24. This thixotropic behavior is typical to cosmetic products [25]. The paste of clay mineral 2: 1 are typically pseudoplastic with a large usual properties: thixotropy and yield stress (resistance to breaking of the structure) improved stability of the paste [26]. With a high concentration in solids, kaolinites dispersions exhibit a viscoelastic behaviour. This rheological behavior is attributed to pockets closed of deflocculated particles clay, which during shear results of interaction contact and interparticle [27]. The morphology (spherical plane or tubular) greatly affects the viscosity of paste of kaolinite.
0 0
20
40
60
80
100
120
Fréquence (Hz)
Fig.11. Variation of elastic modulus G’(●) and viscous modulous G’’(○) according to fréquence a)M0M et b) D0M.
We see that Maroua clay is more elastic than viscous, with the storage module most important about 20000 Pa and 25000 Pa for Douala clay, the viscous modulus is 10000 Pa and about 15000 Pa for Douala clay (figure11). Otherwise, the storages and losses modules are comparable, leaving the phase angle delta (phase shift between the imposed stress and displacement, in degrees) around 25 degrees for Maroua clay and 35 degrees for Douala clay (fig.12). This lower angle delta clay Maroua value confirms its greater elasticity compared to Douala. However, the values of the storage and loss modules and phase angle of the two clays are typical for systems of low elasticity [22].
ISBN: 978-1-61804-239-2
IV. CONCLUSION We have identified notable differences between the Maroua and Douala clays by analyzing their SEM/XDE images, as well as their XF, XRD and FTIR patterns, nitrogen adsorption–desorption isotherms, water adsorption and rheological behavior. We may conclude that the Maroua clay is mainly montmorillonite, few kaolinite and is pseudoplastic. On the other hand, Douala clay is essentially kaolinite and is pseudoplastic. Both of them can be used for cosmetic 430
Advances in Environmental Sciences, Development and Chemistry
application like facial masks, as they are a good support to the skin, ensure expansion of pores and contribute to its moisturizing. Kaolinite has few minerals; it is neutral, sweet and cover very well. montmorillonite absorbs very well and is the best for in-depth cleaning with best thixotropy.
[21]
[22]
REFERENCES [1]
[2] [3]
[4]
[5] [6]
[7] [8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18] [19]
[20]
H Chamayou and J.P Legros.,. Les argiles. Les bases physiques, chimiques et minéralogiques de la science du sol, Presses universitaires de France (1989). B. Velde,. Origin and Mineralogy of Clays: Clays and the Environment. 1995 (Springer, Berlin). Vicente Rodríguez, M.A., López González, J.D., Bañares Muñoz, M.A., Casado Linarejos, J.,. Acid activation of a Spanish sepiolite: II. Consideration of kinetics and physicochemical modifications generated. Clay Minerals (1995) 30, 315–323. G.E, Christidis, P.W. Scott, A.C.Dunham . Acid activation and bleaching capacity of bentonites from the islands of Milos and Chios, Aegean, Greece. Applied Clay Science (1997) 12, 329–347. Isabel M. Carretero Clay minerals and their beneficial effects upon human health. A review. Applied Clay Science. (2002) 21 155– 163 I. M. Carretero, C. S. F. Gomes Tateo F.,. Clays and human health. In Bergaya, F., Theng, B.K.G., and G. Lagaly, (Eds.), Handbook of Clay Science, Developments in Clay Science, , (2006) vol. 1 pp. 717–741. E. Gamiz, J. Linares, R. Delgado,. Assessment of two Spanish bentonites for pharmaceutical uses. Appl. Clay Sci. (19926), 359– 368. V. Chatain, karacterisation of potential mobilisation of arsenic and others inorganic component in soil from aurifer minin site. Doctorat Ph.D. these of chemical Lyon school. (2004) 189p. Vivian Zague, Diego De Almeida Silva, Andri Rolim Baby, Telma Mary Kaneko, And Mariav Ali Riar Oblevse Lasc. Clay facial masks:P hysicochemicaslt abilitya t different storage temperatures j. Cosmest.c i., (2007) 58, 45-51 Isabel M. Carretero, Manuel Pozo. Clay and non-clay minerals in the pharmaceutical and cosmetic industries Part II. Active ingredients Applied Clay Science (2010) 47, 171–181. Green-Kelly,R.,. The montmorillonite minerals. In: MacKenzie, R.C.(Ed.), The differential thermal investigation of clays. Mineralogical Society, London, (1957) pp. 140-164. J. P. Nguetnkam, R. Kamga, F. Villiéras, G.E. Ekodeck, A. Razafitianamaharavo, J.Yvon. Assessment of the surface areas of silica and clay in acid-leached clay materials using concepts of adsorption on heterogeneous surfaces. J. of Colloid and Interface Science (2005) 289, 104–115. Gomes Figueredo Celso de Sousa et Silva Pereira Joao Baptista. Minerals and clay minerals in medical geology. (2007) Appl. Clay Sc. 36, 4-21. J. P. Nguetnkam., R. Kamga, F.Villiéras, G.E. Ekodeck, J. Yvon. Assessing the bleaching capacity of some Cameroonian clays on vegetable oils. (2008) Appl. Clay Sci. 39 113–121. Emmanuel I. Unuabonaha, Kayode O. Adebowale, Folasegun A. Dawodu Equilibrium, kinetic and sorber design studies on the adsorption of Aniline blue dye by sodium tetraborate-modified Kaolinite clay adsorbent Journal of Hazardous Materials 157 (2008) 397–409. Tsing-Hai Wang, Tsung-Ying Liu, Ding-ChiangWu, Ming-Hsu Li , Jiann-Ruey Chen, Shi-Ping Teng, Performance of phosphoric acid activated montmorillonite as buffer materials for radioactive waste repository. Journal of Hazardous Materials 173 (2010) 335–342 Qian Zhongzhong, Hu Guangjun, Zhang Shimin, Yang Mingshu; Preparation and characterization of montmorillonite– silica nanocomposites: A sol– gel approach to modifying clay surfaces. Physica B (2008) 403 3231– 3238. Srasra E. , Trabelsi-Ayedi M. Textural properties of acid activated glauconite. Appl. Clay Sci. (2000). 17, 71–84. Kumar P., Jasra R.V., Bhat T.S.G.,. Evolution of porosity and surface acidity in montmorillonite clay on acid activation, Ind. Eng. Chem. Res. (1995)34, 1440–1448. Uhlherr, P.H.T., J. Guo, C. Tiu, X.-M. Zhang, J.Z.-Q. Zhou and T.-N. Fang, , The shear-induced solid-liquid transition in yield stress materials
ISBN: 978-1-61804-239-2
[23]
[24] [25]
[26] [27]
431
with chemically different structures, J. Non-Newt. Fluid Mech. (2005) 125, 101-119. S. Paumier, P. Monnet and A. Pantet. Etude des propriétés viscoélastiques de suspensions de smectite homoioniques à bi-ioniques (Ca2+, Na+): influence de la concentration (2-100 g/l). 18ème Congrès Français de Mécanique Grenoble, 27-31 août 2007. Sabine Kempe, Metz Hendrik, Bastrop Martin, Hvilsom Annette, Vidor Contri Renata, Mader Karsten. Karacterization of thermosensitive chitosan-based hydrogels by rheology and electron paramagnetic resonance spectroscopy. European Journal of Pharmaceutics and Biopharmaceutics (2008) 68; 26–33 J. Mewis, , C.W. Macosko. Suspension rheology. In: Macosko, C.W. (Ed.), Rheology: principles, measurements and applications. VCH Pub, New York, (1994) pp. 425–474. Cl.Thirriot , Th.Karalis. Quelques experiences sur la rhéologie des argiles sèches et humides. Rheologica acta. (1980) 19, 124-132. Peter Herh, Tkachuk Jullian, Wu Spencer, Bernzen Monica and Rudolph Bruce. The rheology of pharmaceutical and cosmetic semisolids. Application Note, American Laboratory, (1998)12-14. P.F. Lukham, , S.Rossi, , The colloidal and rheological properties of bentonite suspensions. Adv. Colloid Interface Sci. (1999). 82, 43–92. C.Viseras, C.Aguzzi, P.Cerezo, A.Lopez-Galindo. Uses of clay minerals in semisolid health care and therapeutic products Applied Clay Science (2007) 36. 37–50
