Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 1 Physico-Chemical and Mineralogical Characterization of some Clays from Coastal Sedimentary Basin of Benin used in CeramicSagbo E., Laibi A., Senou M., Josse R., Mensah J., Borschneck D.5 andNoack Y.Laboratoire de Chimie Inorganique et de l’Environnement (LACIE). Faculté des Sciences et Techniques (FAST), Université d’Abomey-Calavi. 1BP: 526 Cotonou, BENIN Faculté des Sciences Agronomiques (FSA), Université d’Abomey-Calavi. 01BP: 526 Cotonou, BENIN Laboratoire d’Analyse Physico-Chimique et des Environnements Aquatiques, Université d’Abomey-Calavi, 01BP, 526Cotonou, BENIN Laboratoire de Chimie Théorique et de Spectroscopie Moléculaire (LACTHESMO). Faculté des Sciences et Techniques (FAST), Université d’Abomey-Calavi, 03 BP : 3409 Cotonou, BENIN Centre Européen de Recherche et d’Enseignement en Géosciences de l’Environnement (CEREGE), Université d’Aix Marseille III-UMR 6635, FRANCEAvailable online at: www.isca.in, www.isca.me Received 30th Augustr 2015, revised 24th September 2015, accepted 12th November 2015 AbstractThree sites of Benin’s clays from Gbédji-Kotovi, Massi-Sèhouè and Zogbodomey were characterized in this study. Physico-chemical and mineralogical analysis were performed by X-Rays Diffraction, chemical analysis, thermal analyses ATD/ATG, infrared IR, specific surface area and granulometry. Density of clayey particles, capacity of cationic exchange (C.C.E.) and exchangeable bases were also done. It comes out from these analyses that clays of Zogbodomey are essentially kaolinitic while those of Gbédji-kotovi and of Massi-Sèhouè are with smectitic predominance. By its composition the sample of Zogbodomey is constituted by a natural mixture of the elements necessary for the production of ceramic (bricks, tiles, pottery etc). The two others series of samples from Gbédji-kotovi and Massi-Sèhouè will require some kaolinite and sand additions because of their strong proportion in smectite. Thus, they would be more useful in agronomy and environmental protection Keywords: Clay, X-ray, granulometry, mineralogical structure, BENINIntroduction According to their structural compositions and their properties, minerals clays are employed for various applications and specific uses1-6. The clays used in ceramic industry must show certain characteristics specific to each application. For instance, to product good enamel, they must contain a small rate of smectite to guarantee a good rheological stability, and to have a relatively low content of iron and potassium in order to obtain a white color after cooking. Besides, clays for bricks and tiles must answer some criteria of composition in: Mineral clayey ensuring the plasticity and the cohesion of the paste before cooking and the ceramic bonding at high temperature, a kaolinite-illite mixture with a little smectite being most favorable; quartzous sand serving as grease-remover allowing to reduce the drying and cooking withdrawal and to facilitate the water flow of shaping; colouring elements also serving as melting, such as Fe3,TiO MnOIn Benin, minerals clays used in ceramic activities are often taken in the coastal sedimentary basin. The geological reserves of these clays are estimated at 5.157.600 tons in Gbédji-Kotovi, 1.530.000 tons in Massi and 10 000.000 tons in Zogbodomey.The characteristics of these clays were not well study except some rare chemical analyses and x-rays diffraction analysis. This reveals that a good knowledge of these characteristics (compositions and properties) will improve the output and. the quality of the finished products. It is the objective in this study which aims to the determination of the physico- chemical characteristics and mineralogical by four methods (the diffraction of x-rays, chemical analysis and the thermic analyzes ATD/ATG and the infrared IR) supplemented by measurement of the density, of capacity of cationic exchange and of granulometry of these clays. Material and Methods Materials: Located at south-west of Benin between the meridians 1°40' E and 2°45' E and the parallels 6°15' N and 7°30' N, the basin where the samples were took belongs to the basin of Gulf Guinea (figure-1). On the geomorphological level this basin includes two zones (figure-2). A zone of 7 plateau limited by the valleys of the principal rivers (Ouémé, Sô-ava, Couffo and the Mono) and the depression of Lama. They are the plateau of Aplahoué, Abomey, Zagnanado and Kétou and those of Comé, Allada and Saketé. A zone of low plain constituting a margino-littoral field occupied by marshy depressions, lagoons (lagoon of Porto-Novo, coastal lagoon), sand cords and lakes (Ahémé lake, Nokoué lake). On the geological level, this basin is of cretaceous age to current. It Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 2 contains gritty, sandy, argillaceous and calcareous formations 10,11. The studied materials come from Gbedji-Kotovi (GK), Massi-Sèhouè (MS) and Zogbodomey (ZY). These localities are represented on figure-2. The first prospected site GK is located between 2°00 ' and 2°02' East longitude and 6°40' and 6°42' North latitude. Ten (10) holes of 1m of diameter and 5m of maximum depth are dug there with the mesh of 100m. Overall, the clay are black with by places of the tasks rusts. The second site MS is between 2°13'E and 2°16'E, between 6°57'N and 6°59'N in the depression of Lama. Ten (10) holes to the mesh of 100 m with a maximum depth of 5m for the majority and sometimes 7m were explored there. The clay of this site is in general of beige color. At the 3rd site ZY, it is located between 2°06' E and 2°08' E and between 7°04' N and 7°06' N. 6 holes in bulk, of maximum depth of 7m were done. In general clay appears only after lateritic layer from 2 to 3m. It is initially white with red bands (zone of transition), then white with yellow passages and of the red tasks. The exact geographical coordinates of each hole were raised using a system of positioning by portable satellite of type G.P.S (Global Positioning System). Methods: Before the preliminary analyses, the samples were grinded in a coarse way in agate mortar and sieved through 2mm mesh sieve. The fraction obtained is subjected to a series of physic-chemical analyses, namely the density, cationic exchange capacity, the exchangeable bases, specific surface and granulometry. Then the argillaceous fraction lower than 2 m is obtained by purification and sedimentation. This fine fraction, dried and finely crushed allowed to prepare oriented pastes on natural trial and having undergone specific treatments (Ethylene glycol, Hydrazine, heating during 4 hours at 490°C). Crude clay and these oriented pastes were subjected to x-rays diffraction. The diffractograms were recorded using a Philips diffractometer equipped with a generator PW 1800 with graphite monochromator, using the radiation of cobalt and functioning under 40 kV, 40 mA. They were acquired by data APD and were treated by the software X' PERT and IDENTIFY and X' PERT High Score. The results obtained by DRX (diffraction at X-Ray) are supplemented by the elementary chemical analyses using an atomic spectrophotometer of emission by coupling inductive plasma (I.C.P./AES) Jobin Yvon of the mark Ultima C V5 which makes it possible to have the proportion of chemical elements constitutive of clay material. The curves of DTA (differential thermic analysis) were recorded by differential calorimetry with sweeping of argon with apparatus TG-DTA 92 SETERAM. The reference is calcined alumina. The two powders (sample and reference) are packed in identical platinum crucibles. They are then heated from the ambient temperature to 1100°C at the speed of 10°C/mn. Measurements are made here on the crude or total samples grinded with granulometry 100 µm. Measurements of GTA (Gravimetric thermic analysis) are taken simultaneously with the same apparatus and the same thermal cycle as that of DTA. The granulometry analysis was carried out on the fine particles of diameter lower than 500 m using a laser particle-measurement instrument MALVERN of the type MATERSIZER. Specific surfaces were given starting from the analysis of the isotherm of adsorption of a gas by the solid by using the method of Brunauer, Emmett and Teller (B.E.T.) Moreover for the infra-red spectroscopy, after a mixture (2% in mass approximately) with of KBr (average IR) or polyethylene (remote IR), the samples, (fine fraction 2µm) are put in pastilles of diameter of 13 mm and thickness of about 0,4mm. Measurements were carried out in the field of the average infra-red between 400 and 4000 cm-1 using a spectrometer with Fourier transform of the type PERKIN ELMER (model 1760X), provided with a software of automatic processing data. In the remote infra-red (between 50 and 400 cm-1), the spectra IR were recorded with a spectrometer BONEM D.A. 8 with Fourier transform. As for the calculation of the density it was carried out by pycnometry with the hexachlorure of methane. The principle is based to the measure of the mass of the unit volume of material. The cationic exchange capacity measurements was done on the total rock using the method of Aubert12. Results and DiscussionPhysico-Chemical and Granulometric Analysis: On the average, the values of density, those of the capacity of cationic exchange and those of specific surface area are gathered in table-1. These values are similar for GK and MS. The figures-3a, 3b and 3c show the curves of particles distribution of some samples of the three sites. The curves are bimodal for samples GK, a big mode and a small one between 0,1 and 100µm and trimodal between 000,1et 200µm for samples ZY as in case of the kaolinitic compounds13. While with samples MS, its curves are trimodal successively a big mode a small and a smaller one beyond 100µm14.. The particles of these samples are divided into four, even five great classes as shown it tables 4 Clays (diameter 2m) are on average, in a decreasing way, 44,8; 33,1 and 30,4% respectively for samples GK, MS and ZY. The fine silts (2-20µm) are more numerous in samples MS (59,1 %), than samples GK (52,7 %) and ZY (43,6 %). The coarse silts (20-50µm) are more significant in samples ZY (14,5%), than samples MS (3,5%) and GK (1,9%). Fine sands (50-200µm) are in an increasing way 0,6; 4,1 and 11,5% respectively for samples GK, MS and ZY. Finely, only samples MS present a small quantity (0,3 % on average) of coarse sands (0,2-0,5mm) per place. Table-1 Cationic Exchange Capacity (CEC), Specific Surface area and Density of samples (GK), (MS) and ZY on averageSamples CEC in meq/100g Density Specific Surface (m²/g) GK 34,84 2,37 105,41 MS 37,18 2,36 100,59 ZY 4,16 2,61 69,2 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 3 Figure-1 Card of geographical situation of Benin (IHETA et al, 1983) Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 4 Figure-2 Geological Card of the coastal basin of the Benin (Slansky, 1962) Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 5 Figure-3a Particles size distribution in samples MS Figure-3b Particles size distribution in samples GK Figure-3c Particles size distribution in samples ZY Mineralogical and Chemical Analysis: The figures-4a, 4b and 4c show the diffractograms from the crude or total fractions of the samples. On these diffractograms, it is observed that the major crystalline phases contained in all the samples are kaolinite (k)(7,14Å; 3,56Å), quartz (q) (3,33Å; 1,81Å; 4,26Å), smectite ((S): (Ca, Mg) (Al, Fe)2 (Si, Al)O10 (OH) (14-15 Å) and some traces of anatase phase (A) (3,52Å; 1,89Å). Feldspar traces are also noted ((Na, K, Ca) (Al, Fe, Si)4 8 (3,18-3,33Å; 0 1 2 3 4 5 0,01 0,1 110 100 1000 ZP0 ZPI1 ZPII1 ZPII2 ZTI2 ZTII2 Diameter of the Particles (µm) ZPIII2 0 1 2 34 5 0,01 0,1 1 10 100 1000 Diameter of the Particles (µm) GS1 GS2 GO1 GO2 GN1 GNE1 GNE2 -1 0 1 2 34 5 6 7 0,01 0,1110100 1000 Diameter of the Particles (µm) MNO2 MO2 MSO 1 MSO2 MSSO ME1 MNE MNE2 MO1 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 6 4,02-4,25Å) for the samples GK and goethite (G) -FeOOH (4,18 Å; 2,49Å) for the samples ZY. The samples resulting from the same site present same minerals thus showing the homogeneity of each site. The figures-5a, 5b and 5c give the results of the diffractograms of the fine fractions from representative samples of each site after various specific treatments (normal, Ethylène-glycol, Hydrazine, heating at 490°C during 4h). These treatments make it possible to put forward detected minerals. The results of the chemical analysis are gathered in tables 3.a, 3.b and 3c. Quantitatively the samples contain all mainly oxides SiO2 (45,4-63,8%) and Al3 (13,9-23,1%), followed by small quantity of Fe3 (6-11%), TiO2 (0,9-1,5%) and according to each site of NaO, of P5 of MgO de CaO and KO in variable quantity. Other components (Sr, Ba, Pb, Zn, V, Cu, Ni, Cr) also appear in traces. Thermic and Infrared Analyses²: The thermograms of samples GK, MS and ZY are represented respectively in figures 6a, 6b and 6c. The figures-7a, 7b and 7c show the thermogravimetric curves of these same samples. The shape of the curves obtained are those of argillaceous minerals detected by x-rays and their resemblance in each site confirm well their homogeneity. The curves IR are gathered on the figures 8a; 8b; 8c and 8d. The spectra (medium IR) characterize clayey minerals like the thermic curves, and to be alike of a site another.. What led us to make the remote infra-red only on one representative sample of each site to knowing GNE1 MNO1 and ZTI2 3-4 Quantitative Semi-Composition of the total samples: By combination of results of the analysis with the X-ray, the chemical analysis15 and in addition to the results of CEC by the method QuantArg216 one obtains the quantitative semi- composition of the table-4.Discussion: The definition of clay starting from the particle which has a diameter lower than 2µm must be taken with reserve. Indeed, certain clayey particles have a size higher than 2µm while certain mineral particles associated to clays (feldspar, quartz, goethite etc.) have a size lower than 2µm. This is why it is thought that the argillaceous minerals start to be present starting from the fine siltsThe samples of the three sites contain essentially clay and silt (more than 70%) with more clay for GK (44,8%) more fine silt for MS 59,1% and a enough balanced texture for ZY with apart clay and fine silt, has 14,5% of coarse silts and 11,5% fine sand (table-2). On the figures-5a, 5b, 5c, it is noticed that the smectite, under the normal conditions of moisture is presented at the basal distance d (001) at 14-15Å (to saturation Ca or Mg) (samples GNE1N, MNO1N, ZTI2N) whereas it inflate and is to 17-18 Å (GNE1G, MNO1G, ZTI2G) with glycol saturation. After heating at 490°C the smectite becomes anhydrous and its basal distance is approximately of 10 Å (GNE1C, MNOC, ZTI2C)17. The basal distance (d001) of kaolinite is approximately 7,15Å (GNE1N, MNO1N, ZTI2N). Treated with hydrazine, the peak of kaolinite moves to 10Å (GNE1H, MNO1H, ZTI2H). In addition, kaolinite is destroyed by heating at 490°C (GNE1C, MNO1C, ZTI2C) and does not inflate with saturation with ethylene glycol (GNE1G, MNO1G, ZTI2G). It is necessary to note the presence of illite traces in samples GNE1 and ZTI2 at 10 Å. These results confirm well the presence of minerals identified in the total samples and the normal fractions of these samples. The chemical analysis translates the results of the analysis by X-rays diffraction. They show that the samples contain all, a quantity of (SiO2 + Al3 ranging between 67 and 81%. They are thus primarily silico-aluminous minerals with prevalence of SiO. The relatively significant rate of SiO2 is probably due to the presence of a significant quantity of free silica (quartz, amorphous silica) detected with the X-ray, especially in the materials of ZY which totalize 39% of quartz on average. All the samples count too, small quantities of TiO2 indicating the presence of anatase on average of 1,30 % also detected by X-rays diffraction. Only the samples GK totalize an appreciable quantity of (KO + NaO) equalizes to 1,5%, suggesting the presence of fedspar detectable too by X-ray diffraction. The average content of (MgO + CaO) is 2,8 % of samples GK and MS, and show the probable presence of smectites saturated to Mg and Ca. This saturation is checked with DTA. In addition, the content of Fe of GK (8%) of MS (6,7%) and ZY (8,7%) on average suggests the presence of goethite found in samples ZY or structural iron in the smectites of the three sites. Furthermore, the thermograms analysis of the total part of the samples GK (Figure-6a) showed that the curves are almost the same. This certifies the homogeneity attested by the X-ray. It was observed four phenomena characterizing generally clays of the smectite type17-19. Three endothermic peaks follow-ups of an exothermic peak. A first intense accident which are spread out between 0 and 200°C to 300°C correspond at the departure of water slightly linked (water of hydratation and zeolithic water). This peak presents an splitting between 170 and 200°C which confirms the presence of the Mg2+ ions and Ca2+ contained in the smectite losing its water of hydration20. A second endothermic effect which appears towards 500-550°C, indicates the loss of the radicals structural hydroxyls (dehydroxylation) in the form of composition water18. This departure of the OH at this low temperature is allotted to minerals of tetrahedral substitutions of beidellite type, nontronite and mixed beidellite21 whereas true montmorillonites are characterized by a thermal accident between 600 and 700°C18,19,22,23. Besides it should be necessairy to signalize that the observed temperature of this endothermy in the majority of clays is a data which characterizes them. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 7 Another endothermic accident very widened (right before the exothermic peak) towards 845-860 °C approximately, sometimes non-existent in the case of a beidellite or nontronite like here on our curves, corresponds to the loss of the last hydroxyl traces18,19,24. Finally, the exothermic reaction, which is towards 850 -950°C has a round form. Moreover, these samples present an exothermic hump around 384°C and an endothermic derivative towards 428°C which respectively announce the presence of the organic matter and of kaolinite contained in these materials25. Organic matter no detectable by the X-ray but detected by hydrogen peroxide 30% and the kaolinite 17% detected by X-ray. For samples MS (Figure 6-b), the thermograms obtained are identical between them (those of MNO1 and MN1 are practically confused) and almost comparable with those of GK. With the only difference that the exothermic hump relating to the organic matter towards 356°C here, is less marked than the cases of GK as well as the drift around 428°C for kaolinite, safe for MEI towards 424°C which is the richest in kaolinite. At last a small hook towards (579-582°C) corresponds to the transition from phase of quartz according to the following reaction27: -quartz -quartz. Figure-6c is relative to the curves of ZY. Three fundamental phenomena are also detected there but with the following nuances: Compared to the curves of the preceding sites, the intensity of the first endothermic peak (77-94°C) stripped to the profit of the 2nd peak which has increased and is in the neighbourhoods of 529°C. When with the 3rd exothermic accident, it is acuter and is at a temperature higher (955-970°C). All this show the prevalent nature of kaolinite in these samples. If the accident always corresponds at the beginning of hygroscopic or zeolithic water and cannot appear in certain kaolinites. The 2nd the departure ofstructural hydroxyls following by the decomposition of the octahedral layer announces here28. Kaolinite loses then its water of composition to form the metakaolinite according to the diagram: AlSi (OH))        AlSi + 2HO Kaolinite Métakaolinite The 3rd indicates the transformation of the metakaolinite into a spinel aluminium-silicon and following amorphous silica: 2AlSi¾®960 SiAl12 SiO Al-SiSpinelle silice In addition to these traditional accidents, two other endothermic peaks appear in the neighbourhoods of 300 et 580°C allotted to the deshydroxylation of the goethite detected by the X-ray which changes into hematite according to: -FeOOH           -Fe3 + O and with the allotropic transformation of quartz into quartz like previously notified19,27. When one analyzes the thermogravimetric curves of the samples of GK Figure-7a it is noticed that they are curves with two inflections characteristic of the smectites. Between 20 and 200°C a first hygroscopic and significant zeolithic water departure of about 6 to 9% in loss of mass is followed of a soft slope instead of a stage. This slope, approximately 1,5% of loss of mass, is due to the combustion of the amorphous substances in occurrence of the organic matter. Finally a last reduction in mass of order 4 to 7 % approximately, occurring between 400 with 650°C and follow-up of a stage, correspond at the departure of water of composition. All these losses of mass correspond to accidents of the differential thermal analysis. On the whole the reduction is about 11,5 with 18,5%. These results confirms the phenomena obtained with DTA and shows that the exothermic transformation announced towards 900°C occurs without variation of mass. Figure 14 relating to site MS presents thermogravimetric curves similar to those of GK.The thermogravimetric curves obtained for samples ZY are represented on Figure-15. From 0 to 250°C a loss of mass of 1,5-2,5% announced the departure of the adsorbed water followed by a 2nd light loss approximately of 0,8% correspondent to the deshydroxylation of the goethite transformation into hematite appears. To finish a significant reduction in mass of order 4 to 7 % approximately, ranging between 400 with 650°C following the elimination of the structural hydroxides, the whole followed by a stage. All these results go in the same direction as those observed with DTA. Here also the exothermic reaction occurs towards 900°C without variation of mass. The results of the physic-chemical analysis (table-1) come to confirm those of the mineralogical analysis. It is noticed whereas clays of the three sites have overall average cationic exchange capacities lower than those their majority clay components. 34,85 meq/100g for the GK ; 37,18 for MS et 4,17 for the ZY against 80-150 for the smectites and 5-15 for kaolinites12. These low values would be explained by the fact that in the method used, measurements are done on the total samples which contains in our case a considerable quantity of quartz unable to exchange cations29. 27% on average for the GK, 36% for the MS and up to 71% for the ZY. In addition, kaolinites are not very exchanging cations what explain the low value of 4,17 meq/100g of samples ZY which contain more kaolinite than GK and MS. The density gives an idea of the prevalent species in samples. Thus the samples GK (density =2,36) and MS (density = 2,37) are smectitic (2,08 - 2 ,35) whereas those of ZY (dmoy=2,61) are kaolinitic (d=2,40 - 2,64) and /or quartzous (d=2,65). It is noticed too that GNE1 and MNO1, which are more smectitic than ZTI2 have a greater specific surface (100,59 against 69,20 m2/g for ZTI2). Moreever ZTI2 contains more kaolinite, a little smectite and a little goethite which has raised his specific surface (69,2 m2/g) than a normal kaolinite (10-30 m2/g)15,28 ¾®580 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 8 Table-2 Granulometric compositions of different samples GK, ZY and MSNature Samples Clay (2µm) Fine silts (2-20µm) Coarse silts (20-50µm) Fine sand (50-200µm) Coarse sand (0,2-0,5mm) Total GS1 36,4 58,0 4,8 0,8 0,0 100,0 GS2 45,4 51,7 2,2 0,7 0,0 100,0 GO1 47,3 51,8 0,6 0,3 0,0 100,0 GO2 38,5 60,0 1,3 0,3 0,0 100,0 GN1 36,9 58,3 3,8 1,0 0,0 100,0 GNE1 48,9 48,2 1,9 1,0 0,0 100,0 GNE2 44,8 54,1 0,7 0,5 0,0 100,0 GN2 45,1 53,9 0,7 0,4 0,0 100,0 GC1 43,8 56,2 0,0 0,0 0,0 100,0 GNN1 48,4 48,9 2,4 0,4 0,0 100,0 GNN2 52,0 44,5 2,7 0,8 0,0 100,0 GNO2 50,4 46,7 2,3 0,6 0,0 100,0 GSO1 26,3 57,7 12,0 3,9 0,0 100,0 GSO2 26,4 65,4 7,9 0,2 0,0 100,0 Average 44,8 52,7 1,9 0,6 0,0 100,0 MNO2 26,6 51,7 8,8 11,8 1,0 100,0 MO2 35,7 50,0 5,3 8,3 0,8 100,0 MSO1 35,5 54,6 5,4 4,4 0,0 100,0 MSO2 41,7 55,8 1,2 1,3 0,0 100,0 MSSO 23,0 68,2 3,7 4,7 0,4 100,0 ME1 40,4 55,2 1,4 2,7 0,2 100,0 MNE1 37,8 54,8 3,5 3,8 0,0 100,0 MNE2 33,6 62,4 1,6 1,9 0,5 100,0 MNOI 31,4 64,8 3,2 0,7 0,0 100,0 MO1 25,1 73,0 1,1 0,8 0,0 100,0 Average 33,1 59,1 3,5 4,0 0,3 100,0 ZP0 36,6 47,6 9,8 5,8 0,0 99,9 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 9 Nature Samples Clay (2µm) Fine silts (2-20µm) Coarse silts (20-50µm) Fine sand (50-200µm) Coarse sand (0,2-0,5mm) Total ZPI2 27,6 56,0 10,5 5,9 0,0 100,0 ZPI1 31,7 44,0 13,1 11,2 0,0 100,3 ZPII1 27,6 30,6 23,4 18,5 0,0 100,0 ZPII2 33,9 42,4 12,8 10,8 0,0 100,0 ZPIII2 31,2 42,6 9,6 16,3 0,0 99,7 ZTI2 31,1 46,1 13,8 9,0 0,0 100,0 ZTII2 23,4 39,0 22,9 14,6 0,0 100,0 Average 30,4 43,6 14,5 11,5 0,0 100,0 Figure-4a Diffractograms of samples GK Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 10 Figure-4b Diffractograms of samples MS Figure-4c Diffractograms of samples ZK Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 11 Figure-5a Diffractograms of samples GK after treatment. GNE1N: normal; GNE1C: heated at 490°C; GNE1G: With glycol; GNE1H: with hydrazine Figure-5b Diffractograms of samples MS after treatment MNO1N : normal ; MNO1C : heated heated at 490°C ; MNO1G : with glycol ; MNO1H : with hydrazine Figure-5c Diffractograms of ZY after treatment ZTI12N : normal ; ZTI12C : heated at 490°C ; ZTI12G : with glycol ; ZTI12H : with hydrazine Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 12 Table-3a Chemical composition of samples of ZogbodomeyOxyde Sample Si0(%) TiO (%) Al (%) Fe (%) MgO (%) CaO (%) Na (%) (%) (%) O+ (%) 0- (%) Sr (ppm) Ba (ppm) Pb (ppm) Z n (ppm) V (ppm) Cu (ppm) ZP0 62,35 1,42 17,64 7,47 0,38 0,19 0,02 0,34 0,09 8,13 1,17 108 74 67 17 194 184 ZPI1 56,6 1,37 23,1 6,99 0,40 0,15 0,01 0,33 0,11 9,28 1,51 145 96 58 15 211 148 ZPII1 63,84 1,31 16,84 8,53 0,26 0,12 0,01 0,19 0,11 7,67 0,71 128 88 43 17 196 178 ZPII2 62,58 1,5 17,36 9,03 0,26 0,12 0,01 0,14 0,11 7,9 0,65 127 79 41 16 184 187 ZTI2 52,67 1,46 21,07 11,25 0,45 0,3 0,06 0,27 0,05 10,02 1,42 105 80 59 17 201 423 Table 3b Chemical composition of samples of GBEDJI- KOTOVIGO1 47,31 1,24 21,94 8,34 1,64 1,16 0,23 0,71 0,11 12,32 4,9 590 95 91 44 205 109 GO2 52,45 1,35 18,79 7,68 1,69 1,18 0,39 1,17 0,12 10,15 4,05 933 84 97 43 190 111 GSO1 57,24 1,2 16,53 7,45 1,45 1,31 0,46 1,14 0,18 9,48 3,19 774 72 77 29 163 96 GSO2 59,1 1,25 16,14 6,86 1,36 1,41 0,79 1,49 0,12 7,95 3,33 730 78 71 30 154 106 GN1 45,41 1,16 21,17 8,13 1,6 1,31 0,08 0,61 0,13 14,07 5,55 450 93 99 43 198 107 GC1 48,59 1,38 20,06 8,44 1,69 0,96 0,32 1,13 0,17 10,82 5,09 589 88 99 42 200 115 GNE1 45,58 1,34 21,13 9,61 1,72 0,87 0,48 1,34 0,2 14,31 5 ,48 533 90 84 40 121 144 Table-3c Chemical composition of samples of MASSI-SEHOUEMNO1 54,84 1,09 16,75 7,11 1,51 1,1 0,01 0,01 0,07 9,57 6,84 107 81 73 11 196 177 MNO2 54,91 1,06 16,6 6,81 1,75 1,19 0,05 0,04 0,07 9,68 6,78 309 79 82 11 204 167 MO1 56,12 0,89 13,86 5,92 1,68 3,75 0,25 0,08 0,06 9,85 6,14 229 64 70 12 182 132 MO2 56,92 1,12 15,3 7,1 1,49 1,13 0,01 0,07 0,07 9,82 5,76 137 78 81 13 198 172 MN1 56,49 1,01 15,24 6,54 1,45 0,98 0,07 0,03 0,06 9,27 5,42 387 82 72 11 192 154 MS 57,33 0,99 14,46 6,8 1,48 1,11 0,06 0,05 0,08 8,55 6,33 63 76 74 10 204 158 MNE1 54,25 1,03 18,36 7,2 1,51 0,78 0,09 0,02 0,08 11,9 5,25 251 91 63 9 115 333 MNE2 53,37 1,07 18,83 6,78 1,68 0,9 0,17 0,07 0,06 10,75 5,17 226 91 71 10 110 208 ME1 56,87 1,33 17,45 6,71 1,3 0,68 0,31 0,1 0,08 10,49 3,72 166 94 66 18 166 223 ME2 60,27 1,06 14,76 6,5 1,7 1,06 0,21 0,03 0,06 9,26 4,28 289 85 69 17 112 187 MT2 55,64 0,95 14,87 6,24 1,59 1,18 0,05 0,02 0,06 9,28 6,19 208 75 73 14 138 162 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 13 Temperature (°C) Figure-6a Thermograms of samples GK Temperature (°C) Figure-6b Thermograms of samples MS 356°C917°C118°C582°C189°C920°C108°C354°C580°C508°C928°C112°C579°C521°C357°C424°C188°C020040060080010001200 T(°C) ATD MNOI MNI MCI MEIMNOIMNIMCIMEI Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 14 Figure-6c Thermograms of samples ZY Loss of Mass Figure-7a Thermogravimetric curves of samples GK Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 15 Loss of Mass (%) Figure-7b Thermogravimetric curves of samples MS Loss of Mass (%) Figure-7c Thermogravimetric curves of samples ZY 511°CMNOI108°CMCI503°C519°C110°CMEIMNI119°C516°C80828486889092949698 100 322324326328321032T EMPERATURE (°C) 536°C94°C93°C C 526°C77°C512°C9293949596979899100101020040060080010001200TEMPERATURE (°C) PERTE DE MASSE EN % ZTI2ZPII1ZPIII Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 16 Figure-8a Spectra Infra-red of samples GK Wavelength (cm-1) Figure-8b Spectra Infra-red of samples MS MCI871 930 1157 3694 426 467 536 692 748 779 797 912 1007 1087 1032 MEII 3661 MNI 3221 3649 3618 3410 1628 MSI 1415 2326 2355 MNOI0,20,40,60,81,21,41,605001000150020002500300035004000 3414 3696 3638 3620 1622 3202 871 928 870 629 743 2356 23301082 467 534 424 691 777 797 910 1011 1030 1159 0 0,2 0,4 0,6 0,8 1 1 ,2 1,4 1,6 300 800 1800 2300 2800 3300 3800 Wavelength (cm - 1 ) GNI1 GNE1 GTA1 GC1 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 17 Wavelength (cm-1) Figure-8c Spectra Infra-red of samples ZY Figure-8d Spectra Infra-red of samples GNE1N, MNO1N and ZTI2N between 50 and 450Cm-1 467 3694 3649 3620 748 689 426 534 910 1030 1111 1007 3660 935 787 0,40,60,81,21,41,61,8 ZP0 ZPI1 ZTI2 ZPII1 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 18 Table-4 Quantitative semi- composition of samples GK, ZY and MSSamples Smectite Kaolinite Illite Quartz Goethite Albite Orthoclase Anathase ZY 5 40 4 39 10 - - 2 GK 53 17 11 13 _ 2 3 1 MS 59 12 - 28 - - - 1 Conclusion The combination of several methods of physico-chemical and mineralogical analysis have shown that the clays of the three sites contain mainly kaolinite, smectite and quartz in variable proportion. They are primarily silty-argillaceous (more than clay 70% + silt). Taking into consideration results of analysis and above mentioned criterion, clays of the three sites are appropriate for the discounted use. By its composition the samples of Zogbodomey constitutes a natural mixture of the necessary elements with the condition to remove slightly iron.. The two other sectors, because of their strong proportion of smectite, will require some kaolinite and sand grease-remover. Tests laboratories and geotechnics tests will confirm that these clays are ready to provide raw materials of quality for production of bricks, tiles, confined, hollow block. Elsewhere, the layers of Gbédji-kotovi and Massi-Sèhouè because of their strong proportion in smectite would be more useful in agronomy and environmental protection. References 1.Caillère S., Hénin S., Ratureau M., Minéralogie des Argiles, Tomes I, II, 2ème édition.Masson et Cie, (1982)2.Cases JM., Liétard O., Yvon J. and Delon JF., Etude des propriétés cristallochimiques,morphologiques, superficielles des kaolinites désordonnées. Bulletin de Minéralogie, 105, 439–455 (1982) 3.Holtzapffel T., Les Minéraux argileux: préparation, analyse diffractiométrique et détermination, Société Géologique du Nord 12. (1985) 4.Singh B. and Gilkes R.J., Properties of soil kaolinites from South-Western Australia, Journal of Soil Science, 43, 654–667 (1992) 5.Decarreau A., Structures, Propriétés et Applications.Société Française de Minéralogie et de Cristallographie, (1994) 6.Sigg J., Les Produits de Terre cuite. Septima Editeur Paris, (1995) 7.Alliprandi G., Matériaux Réfractaires et Céramiques Techniques-I Eléments de Céramurgie et de Technologie, Editions Septima Paris, 132 (1996) 8.Jouenne C.A., Traite de Céramiques et Matériaux Minéraux, Editions Septima Paris, (1990)9.Iheta B., Kirov M., Tsawlassou G. et and Houessou A., Rapport sur les recherches géologiques d’argiles dans la zone du bassin côtier: Secteur Gbédji Kotovi, Massi, Zogbodomè, (1983) 10.Slansky M., Contribution à l’étude géologique du bassin sédimentaire côtier du Dahomey et du Togo (1962)11.IRB, Etude de la cartographie en géologique et prospection de reconnaissance au Sud du 9ème parallèle (1989)12.Aubert G., Méthodes d’Analyses des Sols, Centre régional de Documentation Pédagogique de Marseille (191) 2ème trimestre (1978) 13.Sei J., Etude de matériaux de dimensionnalité réduite: Relation structure-propriété dans des kaolinites naturelles de Côte d’Ivoire. Thèse, Univ. Montpellier, France (1998) 14.Robert M. and Tessier D., Annales Agronomiques 26, nº6, 859 (1974) 15.Njopwouo D., Minéralogie et physicochimie des argiles de Bomkoul et de Balengou (Cameroun), Utilisation dans lapolymérisation du styrène et dans le renforcement du caoutchouc naturel. Thèse de Doctorat d’Etat, YAOUNDE, 300, (1984) 16.Lahlou M., Badraoui M., Tessier D. and Elsass F., Quant Arg2: Un modèle linéaire de quantification des minéraux argileux des sols Partie1: Présentation du modèle Revue H.T.E. N, 126 (2003) 17.Lucas J.T., Etude du comportement à haute température, Bull .Serv. Carte géol. Lorr.,18, 217-2428 (1965) 18.Van Olphen H., Clay Colloïd Chermistry, Second Edition, A Wiley-Interscience-Publication, John Wiley and Sons (1964) 19.Bouaziz R. and Rollet AP., l'analyse thermique tome 1: les changements de phase, Editions GAUTHIER-VILLARS, 410-411 (1972)20.Mackenzie et Bishui, Clay Minéral, Bulletin, 3, 276 (1958) Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 1-19, December (2015) Res. J. Chem. Sci. International Science Congress Association 19 21.Medard T., (Groupe Français des Argiles), Les argiles plastiques du bassin de Paris, Livret guide (1991) 22.Grenne Kelly R., The montmorrillonite minérals. The différential thermal investigation of clays. in Mackenzie R.C., Minéral Soc, London, chap. V, 140-164 (1957) 23.Chantret F., Desprairies A., Douillet P., Jacob C., Steinberg M. and Trauth N., Revison critique de l’utilisation des méthodes thermiques en sédimentologie: cas des montmorillonites Bull Gr, Fr. Argile, 23, 141-172 (1957)24.Weir A.H. et, Grenne-Kelly R., Beïdellite, Amer, Min, 37, 137-146 (1962) 25.Keith et Tuttle, Am. J. Sci., Bowen, Pt., 1, 203 (1952)26.Schulze D.G., Schwertmann U., The influence of aluminium on iron oxides: X. Properties of Al-substituted goethite, Clay Minerals, 19, 521–539 (1984)27.Liétard O., Contribution à l’étude des propriétés physico-chimiques, cristallographiques et morphologiques des kaolins, These Nancy(1997)