Characterization of a clay-polymer composite using the infrared

International Conference on Chemical and Environmental Engineering (ICCEE'2013) April 15-16, 2013 Johannesburg (South Africa)
Characterization of a clay-polymer composite
using the infrared spectroscopy
Zuka Maniania B.*, Mbungu Tsumbu J. P. * and Mulaba Bafubiandi A. F**
membranes for the treatment of wastewater. Boulehdid Hanae
[5] has developed a cationic membrane with selectivity for
monovalent cations by chemically modifying an ETFE film
(ethylene-tetra fluoroethylene). He has characterized this
membrane for the use in electrodialysis. In an electrodialysis
unit, the cationic membranes and anionic membranes are
parallel and alternately arranged. Under the action of an
electric field, the cationic membranes block anions and let
cations to go through, while the anionic membranes block
cations and anions can pass through. There is then created
alternating compartments of concentration and dilution.
Solutions are continuously renewed in the compartments by
flowing parallel to membranes.
Many scientists [6, 7, 8, 9, 10, and 11] are interested in
hybrid processes combining membrane filtration and
adsorption / ion exchange. They developed and studied
systems with clays, organic polymers and membranes. We
would like to develop ion exchangers from local clays
collected near Kinshasa in the DRC. Clays are mixed with an
organic polymer to form a composite ion exchanger. The
composite could thus be applied in the treatment of mine
water and hydrometallurgical effluent in Democratic Republic
of Congo.
Abstract— Clay-composite ion exchangers have been used. The
clays used originated from the vicinity of Kinshasa in the Democratic
Republic of Congo while commercial polymers were purchased.
Clays were dispersed into an organic polymer solution to form the
composite material. The clay-polymer composite could be used for
the remediation of mine waters and purification of
hydrometallurgical effluents. The polymer used in this work was the
sodium alginate. X-ray diffraction spectra obtained on the clay
samples show that these clays are mixtures of several clay minerals.
We have studied infrared spectra of clays, infrared spectra of a
polymeric membrane and those of clay-polymer composite. It was
observed that the main infrared vibrations are the same in all the clay
samples. The main vibration bands observed in the polymeric
material are different from those observed in clays. Infrared spectra
of the composite clearly show vibration lines of the polymeric
component hiding those of the clay components. It is concluded that
the polymer component covers completely the surface of the clay
crystallites. Thus, clay particles coated by polymer could prevent the
clay crystallites to form aggregates [1, 2]. The composite material
made of clays and polymer may be used for adsorption properties
from the large specific surface of the clay crystallites and the
presence of exchangeable ions on the surface provided by the
polymer.
Keywords— Clay, polymer organic, ion exchangers, claypolymer composite system.
II. EXPERIMENTAL PROCEDURES
I. INTRODUCTION
We study a clay-polymer composite by infrared
spectroscopy. The clay samples were collected in the DRC
around Kinshasa and have not undergone any purification
treatment. We have applied a sodium alginate gel on a
polished flat surface of glass, and we have obtained a thin
polymeric membrane after drying in open air during 72 hours.
The sodium alginate gel was obtained as follows: 2g Sodium
Alginate was dispersed in 50 ml of water; the suspension was
then stirred for 24 hours at 30 ° C using a magnetic shaker.
The composite system was obtained by simultaneously
dispersing 2g Sodium alginate and 0.5 g of clay (25% of the
amount of sodium alginate) in 50 ml of water. The mixture
was then stirred as for the obtaining the sodium alginate gel. A
thin membrane of composite was obtained in the same manner
as the polymeric membrane.
X-ray diffraction spectra have been measured by using an
Ultima IV/ RIGAKU spectrometer. Table I and Table II show
X-ray diffraction characteristics for clays and the polymeric
membrane.
The study of the samples was carried out by using an
T
HE
accumulation
of
mining
waters
and
hydrometallurgical effluents are a major environmental
problem affecting industrialized countries. Several authors
proposed techniques based on hybrid processes combining
membrane filtration and adsorption / ion exchange for the
treatment of wastewater and secondary effluents. Sarah
Khiarani [3], for example, has focused his work to the
treatment of organic compounds in effluents by coupling a
microfiltration or ultrafiltration membrane with an adsorbent
or an ion exchanger. He has used a resin as an ion exchanger
and as adsorbents a clay (montmorillonite) and a powdered
activated carbon (PAC). Nechad A. [4] has developed a
membrane for water filtration based on low density
polyethylene (LDPE) and Bouzggaïa gypsum. He studied the
proportion of each component to obtain the most efficient
Zuka Maniania B.*, and Mbungu Tsumbu J. P.* are wirh Department of
Physics, Faculty of sciences, University of Kinshasa, D. R. Congo.
Mulaba Bafubiandi A. F** is with Department of Metallurgy, Faculty of
Engineering and the Built Environment, University of Johannesburg, South
Africa, [email protected]
10
International Conference on Chemical and Environmental Engineering (ICCEE'2013) April 15-16, 2013 Johannesburg (South Africa)
infrared Fourier transform spectrometer NICOLET
IS10/THERMO SCIENTIFIC. Infrared spectra were measured
at room temperature. Fig. 1 shows the spectra obtained for
different clay samples, while Fig. 2 shows spectra for the
polymeric membrane and clay-polymer composites.
III. RESULTS AND DISCUSSION
The X-ray diffraction spectra show several clay minerals in
the samples (Table I). We observe structures of Keatite,
Quartz, orthoclase, Nacrite, Sodalite, Birnessite, Carnegieite,
Kaolinite, Clinohypersthene, and of Alumino-phosphate.
TABLE I
RESULTS OF X-RAY DIFFRACTION ANALYSES FOR CLAYS
Samples
clay minerals
N°
1
A1
Keatite,
80% ; Quartz SiO 2 11% Orthoclase,
K(AlSi 3 O 8 ), 9%
2
A2
Orthoclase, K(AlSi 3 O 8 ), 62%; Quartz, SiO 2 , 32%
3
A3
Nacrite, Al 2 Si 2 O 5 (OH) 4 , 65% ; Quartz, SiO 2 , 35 %
4
A4
Sodalite, Na 8 (Al 6 Si 6 O 24 ), 84% Quartz, SiO 2 , 9,4%;
Birnessite, KO 48 Mn 1,94 O 5,18 , 2,38%; Carnegieite,
NaAlSiO 4 , 3,8%
5
A5
Kaolinite, Al 2 (Si 2 O 5 °(OH 4 ), 75% ; Quartz, SiO 2 ,
25%
6
A6
Clinohypersthene, Mg 0,31 Fe 0,87 , 80%; Aluminophosphate, Al(PO 4 ), 8,9% Quartz, SiO 2 , 11,1%
Fig. 1 Infrared spectra for clay samples
Infrared spectra of clays show a large amplitude vibration
around 1000 cm-1. They also show vibrations between 675 cm1
and 784 cm-1, around 909 cm-1, 1634 cm-1, 3386 cm-1 and
3678 cm-1. In agreement with the previous results obtained for
kaolinitic clays [8], we can assign the vibrations around 1000
cm-1 and those between 675 cm-1 and 784 cm-1 to vibration of
valence bands Si-O-Si and Si-O-Al, and vibration of
deformation bands Si-O-Al. We can also assign vibration at
909 cm-1 to vibration of deformation bands Al-OH, while
those at 3678 cm-1 can be attributed to the vibrations of
valence bands Al-OH. According to the same study, the
deformation band at 1634 cm-1 and the large absorption
around 3386 cm-1 are characteristic of OH vibrations of water
of clay hydration.
The infrared spectra of the polymeric membrane and those
of clay-polymer composite indicate the same vibration lines
(Fig. 2) but with different intensities. These spectra are
characterized by vibration bands of great intensity between
950 cm-1 and 1200 cm-1, between 1200 cm-1 and 1500 cm-1,
between 1500 cm-1 and 1600 cm-1, and a broad vibration band
between 2500 cm-1 and 3700 cm-1. The observed band around
1000 cm-1 is shifted to higher values , while the similar band
observed in clays is shifted towards lower values. The bands
between 1200 cm-1 and 1500 cm-1 and between 1500 cm-1 and
1600 cm-1 do not nearly exist in clays. The broad band
between 2500 cm-1 and 3700 cm-1 is very intense and covers
all the vibrations observed in clays. Infrared spectra for
composite show the vibration lines of the polymeric
membrane while masking those for clays. Other authors such
Benchabane Adel et al. [1] Jörn Dau et al. [2] who worked
with clay-polymer composites have also found the same
results. Despite clays are hidden, there is an interaction
between the clay and polymer. It is necessary that we study
this interaction in next section.
TABLE II
RESULTS OF X-RAY DIFFRACTION ANALYSES FOR THE POLYMERIC
MEMBRANE
N°
Molecules
content
(%)
1
Iron Oxide
Fe 2 O 3
3.215.517
Disodium tetraoxotellurate
Sodium Gadolinium
Chloride
Na 2 Te O 4
0.986687
NaGdCl 4
1.073.843
Sodium Iron. Oxide
Na 2.4 Fe 10.99 O 16.03
1.055.926
Cerium Zinc
Ce 3 Zn 22
1.368.081
Magnetite
Fe 3 O 4
14.203.568
Sodium Chloride Oxide
NaClO 4
33.127.117
Sodium Iron Oxide
Na 0.5 FeO 2
0.503730
Sodium chlorate(VII)
NaClO 4
41.322.292
Zinc Chloride
ZnCl 2
1.867.677
Zinc Telluride
ZnTe
1.275.562
2
3
4
5
6
7
8
9
10
11
Infrared spectra for clays show characteristics of particular
vibrations (Fig. 1). These are vibrations of bands between 500
cm-1 and 1300 cm-1, 1300 cm-1 and 1800 cm-1, and between
3000 cm-1 and 3800 cm-1.
11
International Conference on Chemical and Environmental Engineering (ICCEE'2013) April 15-16, 2013 Johannesburg (South Africa)
leur réutilisation, thèse de doctorat, Institut national des Sciences
Appliquées de Toulouse (2007).
[4] Nechad A., Elaboration d’une membrane de filtration d’eau à base de
polyéthylène basse densité et de gypse de Bouzggaïa, mémoire de
maitrise, Université Hassiba Benouali de Chlef, 2009.
[5] Boulehdid Hanae, Elaboration et caractérisation d’une membrane
cationique monosélective par modification chimique d’un film ETFE,
Thèse de doctorat, Université libre de Bruxelles, 2008.
[6] Dumsile W. Nyembe, Natural clinoptilolite for the removal of Cobalt
and Copper from aqueous solution, mémoire de maitrise, Université de
Johannesburg.
[7] Soumaya Bouguerra Neji, Mahmoud Trabelsi*, Mohamed Hedi Frikha,
activation d’une argile smectite tunisienne à l’acide sulfurique : rôle
catalytique de l’acide adsorbé par l’argile, Journal de la Société
Chimique de Tunisie, 2009,11, 191-203.
[8] H. Elfil, E. Srasra et Dogguy, Caractérisation physico-chimique de
certaines argiles utilisées dans l’industrie céramique, Journal of Thermal
Analysis, 1995, 44, 663-683.
[9] Mustapha Chikhi, Etude de la complexation des cations métalliques en
vue de leur séparation par un procédé membranaire, Thèse de Doctorat,
Université Mentouri Constantine, Alger, 2008.
[10] S. Benbrahim, S. Taha, J. Cabon et G. Dorange : Elimination des
cations métalliques divalents : complexation par l’alginate de sodium et
ultrafiltration, Revue des sciences de l’eau, Rev. Sci. Eau 4(1998) 497516.
[11] Emilie Vincent, les alginates et leur utilisation en pharmacie et en
ingénierie (application à la construction d’un biomatériau, Thèse de
doctorat, Université Henri Poincaré Nancy 1, 2010.
Fig. 2 Infrared spectra for (M) polymeric membrane, and
various composites.
IV. CONCLUSION
A clay-polymeric membrane composite was fabricated for
its potential use as ion exchanger. FTIR vibrations for the
original polymer and those of the composite material covered
those of clays. It was noticed that the signals attributive to
clays were masked by those of the polymer component in the
composite. It was also obsreved that the infrared spectrum of
the composite clays-polymer differs from that of clays. The
infrared spectrum of the composite resembles that of the
polymer in all the vibration domains, but differs in the
intensities. It is therefore concluded that the clays interact
physico-chemically with the polymer to form the composite.
This is in agreement with the findings of many other scientists
[3, 4, and 5]. The mechanisms of such interactions will be
elucidated in a separate work.
ACKNOWLEDGMENT
The authors thank the University Commission for
Development (CUD) for funding the doctoral fellowship of
ZM and scientific equipment obtained under the project CUD
/ CIUF KIN04. The running costs of the experiments carried
out by ZM at the University of Johannesburg have been
supported by the University Research Committee (URC). The
assistance received from Ms. Nomasa Baloyi and Dr. Rajinee
Kanth is appreciated.
REFERENCES
[1]
[2]
[3]
Adel Benchabane, Karim Bekkour, Etude de l’effet d’un polymère
anionique sur
le comportement rhéologique de suspensions de
bentonite, "39ème Colloque annuel du Groupe Français de Rhéologie,
Mulhouse : France (2004)".
Jörn Dau and Gerhard Lagaly, Surface Modification of Bentonite. II.
Modification of Montmorillonite with Cationic Poly (ethylene oxides),
CCACAA71 (4) 983-1004 (1998),
Khiarani Sarah, Procédés hybrides associant la filtration membranaire et
l’adsorption/échange ionique pour le traitement des eaux usées en vue de
12