Characterization of Peanut Shells for Their Valorization in Earth Brick

Peanut shells from Burkina Faso were characterized using mineralogical, microstructural and chemical methods to perform its possibility to be used as reinforce in adobe bricks. It consists of cellulose (48 wt%), hemicellulose (3 wt%) and lignin (28 wt%). The peanut shells were characterized by high porosity and showed water absorption around 198% at 72 hours. Its chemical composition is essentially composed of silica, iron oxides, alumina and calcium oxide. Its microstructure showed that the peanut shells were a compilation of microfibers with high porous of borders. In watery solution, the peanut shells released polyphenols. Thermal conductivity of peanut at 25 ̊C was 0.155 ± 0.021 W/mK. The physico-chemical characteristics of peanut shells were similar to those found with agricultural by-products used in adobe reinforce.

One of agricultural by-products abundant in Burkina Faso was the peanut shell (PS). Agro-residue of peanut, the shells were mostly abandoned in crop field without a very important issue of valorization. The annual production of peanut in Burkina Faso alone approximatively 334,000 tons [7]. The quantity of shell provides by the peanut corresponds to third part of this annual production.
Many researchers have investigated the use of peanut shells as a carbon source for crop fertilization, as a substrate to remove some impurities of polluted water, as a source of oligosaccharides and as a potential antioxidant and antimicrobial [8] [9]. However, results about peanut shells and their use as reinforce on earth building materials were not available. Many results were available on the use of a large number of fibers (kenaf, fonio, sisal, flax, hemp, bamboo) and wastes (straw, coconut) as reinforce of adobe [2]. Conclusions about mechanisms involved in the enhancement of properties linked to the use of agricultural by-products were sometimes conflicting. The results are closely related to chemistry (cellulose, hemicellulose, lignin, pectin), microstructure (porosity, stiffness) and particle size distribution (filler properties) of the used agricultural by-product. So, the organic compound released by agricultural waste in watery solution participates in the mechanisms. This paper is devoted to analyzing of peanut shells for their physico-chemical, mineralogical, microstructural and thermal conductivity properties to evaluate its suitability as a reinforce of adobe.

Raw Materials
The agricultural waste subject of this work is the peanut shell from Laye, village at 35 km north of Ouagadougou. It is a by-product of a leguminous plant ( Figure 1) called peanut with botanically named Arachis Hypogaea L. Peanut belongs to the subfamily of Papilionaceae in the Fabaceae family. Flowering plant with height around 20 to 90 cm, peanut is grown in warm areas due to its resistance to heat and drought. Peanut is farm mainly for its seeds and oil. It is the sixth largest source of oil production in the world (FAO 2003). Peanut shells were used by local population in the construction of their traditional habitat. The shells were sometimes used in crushed form or powder form to amend adobes.

2) Water absorption of peanut shells
Water absorption of peanut shells was performed according to the method described by Juarez [10] and renew by Magniont [11] for the fibers. The shells were dried an oven at 105˚C until the stabilize mass. Six (06) samples of approximately 1 g were tested each time. They were immersed in distilled water for 5, 15, 30 minutes, 24, 48 and 72 hours. At the end of each immersion period, the shells were superficially dried using absorbent paper to remove the internal water on the surface. The weighing was carried out using 10 −2 g precise scale. Water absorption of the shells is determined by the relation 1. With: -M 1 : dry mass of shells (g); -M 2 : saturated mass of shells after immersion (g).

Characterization of Peanut Shells Powder 1) Physico-chimical analyze
The density of peanut shell powder (Φ < 80 µm) was measured by hydrostatic weighing using garosolve D70 as the immersion liquid. The moisture content J. Minerals and Materials Characterization and Engineering and the loss on ignition of peanut shell powder are evaluated with a Nabertherm C250 oven at 105˚C for 24 hours and 1000˚C for 2 hours, respectively.
The particle size distribution of peanut shells powder (Φ < 80 µm) was performed with laser diffraction using CILAS 1090 Liquide apparatus.
Elementary chemical analysis of peanut shells was performed with X-ray Fluorescence wavelength dispersive technique with a Bruker TIGER S8.

2) Mineralogical analyze
The mineralogical composition of peanut shell powders was carried out by coupling X-ray diffraction, infrared spectrometry, differential scanning calorimetry and thermogravimetric analysis. X-ray diffraction was carried out with a Brüker D8 Advance apparatus equipped with a monochromator and using Kα radiation To determine lignin content, 2 g (M) of EC were mixed with 30 ml of 72% H 2 SO 4 . The whole is stirred for 2 hours, after diluted 7 times (with 10% sulfuric acid) and the mixture is then heated under reflux in a water bath for 3 hours.
The mixture was filtered and the precipitate was collected and washed extensively with distilled water to neutralize and dry at 110˚C for 20 hours. The mass of obtained product represents the mass P 1 . The calcined residue at 500˚C for 5 hours and weighed corresponds to mineral salts mass P 2 . The residual lignin (RL) is calculated according to relation 2.
With, P 1 , P 2 and M in g.

3) Analyze of extract from peanut shells
The extract of peanut shells was analyzed using UV-visible spectrometry. The extraction was done using two ways. For the first way, the peanut shells were Total polyphenolic content of peanut shells extracts was evaluated using Folin-Ciocalteu reagent and gallic acid according to method described by Singleton et al. [12]. The absorbance value was taken at 760 nm CIBA-CORNING 2800 Spectrascan UV spectrometer. Gallic acid was used as a standard to plot the calibrate curve. The total polyphenolic content of the peanut shell extract was expressed as microgram gallic acid equivalent per gram of shell. Capillary absorption was calculated using Equation (3): where Q is the amount of water absorbed (kg) by the specimen, A is the surface (m 2 ) of specimen in contact with water, t is the contact time(s) and S the sorptivity coefficient of specimen (kg•m −2 •s −1/2 ).

Microstructure of Unground Shells
Microstructure examination is important to predict roughness and porosity of the shells. SEM images of peanut shells at different magnifications are shown by Figure 4. Image of shells border (Figure 4(a)) shows an assembly of spherical particles which presents a great number of cavities. According to these images, peanut shells consist of an important porosity which could influence its thermal conductivity and water absorption. Shells inner (Figure 4(b)) consist of a weave of fine fiber which protects all the interior of shells from any external contact. Image of shells exterior (Figure 4(c)) shows a roughness surface which could well allow the adhesion of the earth matrix during the production of adobes. SEM of the film covering the interior ( Figure 5) shows clearly the nature of this film. EDS analysis ( Figure 5) of the thin film shows that it is composed essentially by CaO (62.44%), K 2 O (24.86%) and of MgO (12.70%).

Water Absorption of Unground Shells
Water absorption of peanut shells is one of determining parameters for future use as reinforce of adobes. Absorption curve ( Figure 6) shown that from 72 hours, the absorbed water around 198 wt% of test mass. This important capacity of peanut shells to absorb water could be an advantage to produce moisture regulating adobes. Water absorption of the peanut shells is greater than that of palm and sisal fibers [2] but similar to that of date fiber and is feebler than water absorption of barley straw and wood aggregates [2].

Physico-Chemical Analyze of Shells Powder
The density of peanut shell powder is (1.46 ± 0.01) g/cm 3 . This value is comparable to those of cotton, flax and sisal fiber which around 1.5 g/cm 3 [2] [13]. It is slightly higher than the density of jute fibers which is 1.37 g/cm 3 [2]. The moisture content of peanut shell powders (6.26 ± 0.12)% is feebler than that of flax and cotton but approximatively equal to hemp moisture content [2]. J. Minerals and Materials Characterization and Engineering  The chemical composition of peanut shells is given in Table 1. Shells are composed mainly of organic matter as indicated by the high rate of loss on

Mineralogical Analysis of Shells Powder
FTIR spectra of peanut shell is reported in Figure 8.  The determined index 28.47% is very low and indicates that shell cellulose is very disordered, which justifies the poor quality of X-ray diffraction pattern.
The DSC-TG curve of peanut shells ( Figure 10) showed an endothermic and exothermic peak corresponding to transformation or pyrolysis of the shell's constituents. The first endothermic peak at 100˚C with mass loss of 6% corresponds to departure of moisture water and could also correspond to the condensation of lignin [25]. The second endothermic peak between 200˚C -300˚C with mass loss of 18% corresponds to the degradation of hemicellulose. The third endothermic peak between 325˚C and 370˚C with a loss mass of 22% is attributable to the decomposition of the cellulose by depolymerization [26] [27] [28]. The first exothermic peak at 370˚C with a loss mass of 4% corresponds to the release of the heat stored in the cellulose and which is restored after rupture of the structure.
The broad exothermic peak centered at 400˚C with a loss mass of 7% corresponds to the degradation of lignin.
Chemical composition (Table 2) showed that peanut shells are richer on cellulose (48 wt%) followed by lignin (28 wt%). Hemicellulose content in peanut shells is feeble comparable to kenaf, jute, flax fibers [2]. Cellulose and lignin content are in the same range for wood fiber. The other compound (21 wt%) are probably proteins, minerals, pectin and tannins.

Analyze of Extract from Peanut Shells
UV-Visible spectrum of extract from peanut shells is given in Figure 11 and has composed of two bands. The first and widest, between 200 and 250 nm correspond to the electronic transitions π ==> π* and is characteristic of the structures of the aromatic cycle of polyphenols (tannin). The second band between 275 and 325 nm corresponds to transition n ==> π* of the same polyphenols (tannins).
Tannin content is deduced from the standard curve. The obtained results for the both ways of extraction (2670 µg/g and 2240 µg/g) are relatively high compare to those found by B. Adhikari et al. [8] for six varieties of peanut from Korea which value is from 428.1 to 739.8 µg/g. However, the extraction using shells ground then dried gives tannin slightly above the second way or the hulls are dried in the shade before being crushed.

Thermal Conductivity of Peanut Shells
Thermal conductivity of specimens made with peanut shells powder, determined at 24˚C, is 0.155 ± 0.021 W•m −1 •K −1 . This value is substantially equal to that found by J. C. Damfeu et al. [29] in 2016 which is 0.09 W•m −1 •K −1 . The low thermal conductivity of peanut shells is an asset for their use in the stabilization of adobes. Indeed, addition of peanut shells to raw earth to produce adobes will  Figure 11. UV-Visible spectrum of peanut shell decoction. J. Minerals and Materials Characterization and Engineering allow, to reduce the thermal conductivity of adobes and thus contribute to provide thermal comfort in houses that will be built.

Capillary Absorption of Peanut Shells-Based Specimen
Absorbed water versus contact time between the specimen and water is given in  strengths of adobes indicates that the size of peanut shells is appropriate for their use as reinforce. So, shells powder is composed of finer particles which could play a filler role in the adobe matrix and reduce considerably its porosity.

Discussion
Microstructure of shells indicates a very porous material that explains its high-water absorption and low thermal conductivity. The examination of shells inner shows that the shells are the compilation of microfiber. Roughness of external surface offers adhesion possibilities to raw earth during the production of brick. Shells are composed mainly of cellulose, hemicellulose and lignin as found in most plant materials.
In solution, peanut shells release polyphenolic macromolecules which are able to react by complexing mechanisms with some ions like iron and participate in the consolidation-densification of adobe.
The water absorption of shells (198% of their mass) is comparable to that of fibers (80% -307%) and agricultural residues (97% -203%). It is lower than the absorption of straw (280% -600%). The significant absorption of water of shells improves their property of humidity regulation inside the houses.

Conclusion
Peanut shells are agricultural waste that has all the properties of plant materials used in the stabilization of earth bricks. They have a low conductivity and a high-water absorption that can validly justify their use in the production of ecological habitats requiring less energy to achieve thermal comfort in the interior.
The release of polyphenol macromolecules from the shells in an aqueous medium is an asset to the stabilization of adobes. In this case, the shells can be used to amend earth bricks.