Di bandingkan dengan jurnal Synthesis, characterization, and fertilizer release study

of the salt and pH-sensitive NaAlg-g-poly(AA-co-AAm)/RHA superabsorbent

nanocomposite

The superabsorbent nanocomposite was synthesized by graft copolymerization of AA and AAm monomers onto
alginate chains in an aqueous medium containing cross-linking agent (MBA), initiator (APS), and RHA. Figure
1 illustrates the proposed reaction mechanism. As can be clearly seen from Fig. 1, initially, APS molecules are
dissociated under heating to generate sulfate anion radicals. These free radicals attack the alginate chains and
pick up hydrogen atoms from their hydroxyl groups, resulting in the formation of alginate macro radicals. These
active macro radicals that were produced in this way transfer their own free radicals onto the nearest AA and
AAm monomers which are amenable to free-radical polymerization. Therefore, free-radical graft
copolymerization reactions start by transferring radicalactive centers onto neighboring acrylate monomers. As
the chain propagation process proceeds, two end vinyl groups of MBA molecules react with the radical
centers of the copolymer chains to create cross-linked structure. Eventually, a final hydrogel network is formed
in the presence of RHA. The hydroxyl groups of silica nanoparticles can make strong hydrogen bonds with the
functional groups of hydrogel components which act as physical cross-linking points.

The percentage of polymer that has been grafted onto stock polymer is defined as GE. The amount of GE for
hydrogel sample without RHA was about 684%, while in the presence of RHA its value was increased to 820%.
This enhancement in GE for Hyd/RHA sample may be assigned to the interaction of OH groups in RHA with
the AA and AAm monomers, which in turn can also improve the hydrogel polymer network. GC of a hydrogel
defines its insoluble ratio in deionized water. The GC of the Hyd sample was about 96.2%, while in the case of
the Hyd/RHA sample its value was decreased to 85%. The reduced GC of the Hyd/RHA sample is attributed to
the physical cross-linking effect of RHA nanoparticles, leading to the formation of hydrogel network with a
much faster rate than that of neat hydrogel sample. Thus, the amount of water-soluble

FTIR
FTIR analysis was performed to investigate the structure of the synthesized materials. Figure 2 shows the FTIR
spectra of NaAlg, RHA, Hyd, Hyd/RHA, Hyd/RHA/NPK, and pure NPK fertilizer. In the FTIR spectra of RHA
(Fig. 2a), the main vibrational modes of SiOSi bonds that appeared at 460, 784, and 1085 cm-1 wavenumbers
are attributed to the angular deformation and symmetric and asymmetric stretching vibrations, respectively.
Also, the absorption band at 3580 cm-1 is related to vicinal silanol with hydrogen-bonded water [37, 38]. In Fig.
2b for NaAlg, two absorption bands at 1105 and 1022 cm-1 corresponded to the stretching vibration of the COH
group. The two peaks that appeared at 1647 and 1402 cm-1 are assigned to asymmetric and symmetric stretching
vibrations of the carboxylate (COO-) group, respectively. Additionally, the absorption bands between 900 and
1200 cm-1 are related to OCO stretching of ether groups and CO stretching of alcoholic groups, while a
broad peak appeared at 3350 cm-1 corresponding to the hydroxyl (OH) stretching vibration [39]. As shown in
Fig. 2ce for Hyd, Hyd/RHA, and Hyd/RHA/NPK, respectively, significant characteristic peaks appeared at
1670, 1645, and 1625 cm-1, attributed to the carbonyl groups of AA and AAm as well as the NH bending
which have overlapped together. Also, overlapped absorption bands of OH and NH groups are identified by
broad and intense peaks between 3300 and 3500 cm-1. The stretching vibration of the CN group in the IR
spectra of Hyd, Hyd/RHA, and Hyd/ RHA/NPK was observed at 1323, 1350, and 1370 cm-1, respectively [40,
41]. Moreover, the peaks appeared between 2808 and 2908 cm-1 and corresponded to the combined stretching of
CH2 groups in both AA and AAm in the hydrogel structure [2]. As can be clearly seen in Fig. 2d, e, the
characteristic peaks of RHA appeared with a slight shift in the IR spectra of Hyd/RHA and Hyd/RHA/NPK,
which confirmed the presence of RHA in the superabsorbent hydrogel composition. Also, according to the IR
spectra of the Hyd sample (Fig. 2c), the characteristic absorption bands of etheric (OCO) and alcoholic
groups (CO) of NaAlg chain disappeared, which is an evidence for the grafting reaction of NaAlg with the
AA and AAm monomers [42]. As shown in Fig. 2f for NPK fertilizer, two peaks appeared at 3344 and 3444 cm-
1 are related to stretching modes of OH and NH groups in NPK fertilizer composition. Also, the peaks found
at 2804, 1458, 1152, and 1060 cm-1 indicate the OH stretching, the P=O stretching, the POH stretching, and
the HOPOH bending, respectively. Moreover, the absorption band which corresponds to PO 4 vibration
appeared at 553 cm-1. The stretching vibrations of ON=P and ONO2 bonds in ammonium dihydrogen
phosphate appeared as low-intensity absorption bands between 700 and 900 cm-1. Also, the C=O absorption
band of urea appeared at 16001700 cm-1 as a sharp peak [2]. According to the FTIR spectra of Hyd/RHA/NPK
and Hyd/RHA, the appearance of NPK characteristic peaks in the IR spectra of Hyd/RHA/NPK confirms the
successful encapsulation of the NPK fertilizer compound within the superabsorbent nanocomposite network.
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