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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb
Coordenao de Qumica, Universidade Estadual Vale do Acara, Av. da Universidade, 850, Campus da Betnia, 62040-370 Sobral-CE, Brazil
Departamento de Qumica, Universidade Estadual de Maring, Av. Colombo, 5790, 87020-900 Maring-PR, Brazil
Departamento de Qumica Orgnica e Inorgnica, Campus do Pici, Universidade Federal do Cear, 60455-760 Fortaleza-CE, Brazil
a r t i c l e
i n f o
Article history:
Received 13 October 2012
Received in revised form 15 February 2013
Accepted 10 March 2013
Available online 22 March 2013
Keywords:
A. Polymermatrix composites (PMCs)
A. Smart materials
D. Thermal analysis
a b s t r a c t
Superabsorbent hydrogel composites based on poly(acrylamide-co-acrylate) and rice husk ash (RHA)
were prepared by free-radical copolymerization in aqueous media, using N,N-methylenebisacrylamide
(MBA), as crosslinker and potassium persulfate (K2S2O8), as initiator. The effect of calcination temperatures (400900 C) for obtaining RHA was evaluated. FTIR, WAXS, SEMEDS and TGA were applied to
characterize a series of hydrogels lled with RHA. The hydrogels composites were formed with constant
amounts of RHA (10 wt.%) and crosslinking agent (0.1 mol-%) in relation to the relative to the total mass
of acrylamide (AAm) and potassium acrylate (KAc) monomers (5050 mol-%). A blank sample of
poly(acrylamide-co-acrylate) hydrogel without RHA was used as control. A superabsorbent hydrogel
composite, with a maximum absorption Weq > 1000 gwater/gabsorbent, was obtained with the RHA calcined
at 900 C. In addition, the hydrogel composite showed to be sensitive to the pH variation and to the presence of salts in the swelling media. From the results, it is possible to infer that the poly(acrylamide-coacrylate)/RHA hydrogel composites presented good characteristics to be applied as soil conditioner for
using in agriculture.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Searching for technologies considered ecologically correct has
become of major concern in recent years. This new paradigm of economic development is directed to provide an improvement in welfare of further generations, incorporating in their conception the
needing of new production methodologies able to reduce the pollution and the environmental impact. The large amounts of materials
that present low degradation rate at ambient conditions have
caused severe environmental, economic, social and juridical issues.
The rice husk ash (RHA) is an agro-industrial residue resulting
from the thermochemical conversion of rice husk, and as a waste,
the majority of RHA generated is discarded, causing pollution. The
physical and chemical properties of RHA are determined according
to the methodology applied to its production (pyrolysis, gasication and/or combustion, for instance) and by some variables, such
as, type of equipment employed, burning temperature and time.
Regardless the process of burning, the resultant ash has silica con-
247
W eq m=m0 1
2.5.2. The effect of the ionic strength and type of metal ions on the salt
The hydrogels were immersed in distinct salt aqueous solutions
at different concentrations (0.001, 0.01, 0.05 and 0.10 M) and the
swelling capabilities of gels were determined through the previously described procedures [17,30]. NaCl and NaHCO3 solutions
were used for studying the anion effect while NaCl and CaCl2 solutions were used for evaluating the cation effect on swelling
properties.
2.5.3. Evaluation of pH effect on swelling capability of gels
The effect of the pH on the swelling was also veried in buffer
solutions (pHs 212). The procedures were the same as described
above. The ionic strength of the buffer solutions was kept constant
(I = 0.1 M).
2.4. Characterization
3. Results and discussion
2.4.1. Fourier transformed infrared spectroscopy (FTIR)
The FTIR spectra were obtained using Shimadzu FTIR-8300
equipment. The dried material was blended with KBr powder
and pressed into tablets before spectrum acquisition.
2.4.2. Wide angle X-ray scattering (WAXS)
The WAXS proles of RHA and hydrogels were obtained through
a powder diffractometer Shimadzu model XRD 6000; with Cu Ka
radiation source at 30 kV and 20 mA.
248
33]. The broad band at 3548 cm1 is assigned to the vicinal silanol
with hydrogen-bonded water. The intensity of band at 621 cm1
can be observed on spectra obtained for RHA calcined at
T P 700 C and intensies as the temperature used for calcinations
is increased. This band is characteristic of crystalline cristobalita
[34,35]. The FTIR spectra of hydrogels formed using the ash obtained at different temperatures are shown in Fig. 1b. These spectra
show the appearance of the bands at 1100, 800 and 471 cm1, assigned to SiO2 and SiAOASi bonds [3133]. Furthermore, a weak
band at 621 cm1 can be observed on FTIR spectra of hydrogel obtained using ashes burnt at T P 700 C. Thus, the presence of crystalline cristobalita [6,34] in hydrogel can be assigned. In addition,
the bands at 1670 cm1 and at 1564 cm1, related to the C@O
stretching and to the NAO stretching, respectively, due to the
formation of copolymers. These results indicate that copolymers
and RHA component coexisted in superabsorbent hydrogels
composites.
The WAXS patterns of RHA calcined at different temperatures
for 2 h and cooled to room temperature (within the mufe for
24 h) are shown in Fig. 1c. Such proles provide information relative to the main mineral constituint and structural parameters of
RHA. It can be noticed from WAXS proles that RHA calcined at different temperatures presented different structures corroborating
the FTIR data. The ashes obtained at T < 700 C showed no dened
diffraction peaks, but rather an amorphous halo that appears at ca.
2h = 22, which indicates the absence of crystalline domains, being
Fig. 1. (a) FTIR spectra of the RHA calcined in different temperatures; (b) FTIR spectra of the hydrogels composites; (c) WAXS patterns of the RHA calcined in different
temperatures and (d) WAXS patterns of the hydrogels composite.
249
Fig. 2. Proposed model for the structure of hydrogel composite network (particle size 644 lm).
t=W A Bt
where
and
1
ks w2t
1
wt
250
Fig. 3. SEM and EDS diffractograms of (a) RHAG400, (b) RHAG600, and (c) RHAG900 hydrogels composites.
ACRYL network greatly improved the equilibrium water absorbency, the necessary time to reach the equilibrium was higher
leading to a slower swelling rate. The relationship between water
uptake capability and the temperature applied for obtaining the
RHA is shown in Fig. 6.
According to the swelling assays it is veried the RHAG900 presented highest water uptake because RHA900 has virtually no residue. RHA900 showed high crystallinity degree and the preferable
intra-interactions among its silanol groups set free new sites on
the hydrogel matrix that could interact to water increasing their
water uptake capacity.
Fig. 4. (a) TGA and (b) DTG curves of PAMACRYL and hydrogels composites (RHAG
400,
251
Fig. 5. (a) Degree of swelling and (b) plot of t/W versus t as a function of immersion time.
Table 1
Effect of temperature of obtaining the RHA swelling kinetics of hydrogels composites
formed.
a
b
c
d
Hydrogel
Weqa
Wtb
teqc
ksd
PAMACRYL
RHAG400
RHAG500
RHAG600
RHAG700
RHAG800
RHAG900
645 21
781 27
773 25
802 19
939 24
1031 26
1077 32
649
791
789
800
952
1056
1124
24 3
12 2
13 4
10 1
24 4
29 5
35 4
6.54 104
1.15 103
1.91 103
1.42 103
2.49 104
1.19 104
7.40 105
Fig. 6. Effect of temperature for obtaining the RHA in the maximum swelling value
(Weq) of hydrogels composites.
252
Table 2
Weq (gwater/gabsorbent) as function of the ionic force for the hydrogels.
Hydrogel
RHAG400
RHAG600
RHAG900
PAMACRYL
H2O
NaCl (0.001 M)
NaCl (0.01 M)
NaCl (0.05 M)
NaCl (0.1 M)
Weq
Weq
Weq
Weq
Weq
781 27
802 19
1077 32
645 21
445 6
459 4
638 7
361 4
0.43
0.43
0.41
0.44
249 3
253 2
345 4
195 2
0.68
0.68
0.68
0.70
118 2
123 2
169 3
85 1
0.85
0.85
0.84
0.87
84 1
87 1
114 2
63 1
0.89
0.89
0.89
0.91
f 1
W saline
W water
Table 3
Weq (gwater/gabsorbent) as function of the type of anion and cation.
Hydrogel
RHAG400
RHAG600
RHAG900
PAMACRYL
H2O
NaCl
Weq
Weq
Weq
NaHCO3
f
Weq
781 27
802 19
1077 32
645 21
85 1
87 2
114 3
63 1
0.89
0.89
0.89
0.91
83 2
79 2
117 2
69 1
0.89
0.90
0.89
0.89
26 1
24 1
38 2
17 1
0.97
0.97
0.96
0.97
CaCl2
Acknowledgements
The authors would like to thank the nancial support by FUNCAP (BPI 0280-106/08 and PIL 139.01.00/09), by CNPq (Proc.
507308/2010-7) and to COMCAP-UEM.
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