A synthesis of acrylonitrile (AN)/butyl acrylate (BA)/fumaronitrile (FN) and AN/EHA (ethyl hexyl acrylate)/FN terpolymers was carried out by redox polymerization using sodium bisulfite (SBS) and potassium persulphate (KPS) as initiator at 40 °C. The effect of comonomers, BA and EHA and termonomer, FN on the glass transition temperature (Tg) and stabilization temperature was studied using Differential Scanning Calorimetry (DSC). The degradation behavior and char yield were obtained by Thermogravimetric Analysis. The conversions of AN, comonomers (BA and EHA) and FN were 55%-71%, 85%-91% and 76%-79%, respectively. It was found that with the same comonomer feed (10%), the Tg of AN/EHA copolymer was lower at 63 °C compared to AN/BA copolymer (70 °C). AN/EHA/FN terpolymer also exhibited a lower Tg at 63 °C when compared to that of the AN/BA/FN terpolymer (67 °C). By incorporating BA and EHA into a PAN system, the char yield was reduced to ~38.0% compared to that of AN (~47.7%). It was found that FN reduced the initial cyclization temperature of AN/BA/FN and AN/EHA/FN terpolymers to 228 and 221 °C, respectively, in comparison to that of AN/BA and AN/EHA copolymers (~260 °C). In addition, FN reduced the heat liberation per unit time during the stabilization process that consequently reduced the emission of volatile group during this process. As a result, the char yields of AN/BA/FN and AN/EHA/FN terpolymers are higher at ~45.1% and ~43.9%, respectively, as compared to those of AN/BA copolymer (37.1%) and AN/EHA copolymer (38.0%).
In this paper, the adsorptive performance of synthesized thiourea (TU) modified poly(acrylonitrile-co-acrylic acid) (TU-P(AN-co-AA)) polymeric adsorbent for capturing p-nitrophenol (PNP) from aqueous solution was investigated. TU-P(AN-co-AA) was synthesized via the redox polymerization method with acrylonitrile (AN) and acrylic acid (AA) as the monomers, then modified chemically with thiourea (TU). Characterization analysis with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental microanalysis for CHNS, zeta potential measurement, Brunauer-Emmett-Teller (BET) surface analysis and thermal analyses were carried out to determine the morphology and physico-chemical properties of the synthesized polymer. The characterization results indicated successful surface modification of polymer with TU. The performance of TU-P(AN-co-AA) for the removal of PNP was investigated under various experimental parameters (adsorbent dosage, initial adsorbate concentration, contact time and temperature). The results demonstrated that the Freundlich isotherm model and pseudo-second-order kinetic model best described the equilibrium and kinetic data, respectively. Thermodynamic studies showed that the uptake of PNP by TU-P(AN-co-AA) was spontaneous and exothermic in nature. The results of the regeneration studies suggested that the TU-P(AN-co-AA) polymer is a reusable adsorbent with great potential for removing PNP from wastewater.
In this study, simultaneous adsorption of cationic dyes was investigated by using binary component solutions. Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TMPAA) polymer was used as an adsorbent for uptake of cationic dyes (malachite green, MG and methylene blue, MB) from aqueous solution in a binary system. Adsorption tests revealed that TMPAA presented high adsorption of MG and MB at higher pH and higher dye concentrations. It suggested that there are strong electrostatic attractions between the surface functional groups of the adsorbent and cationic dyes. The equilibrium analyses explain that both extended Langmuir and extended models are suitable for the description of adsorption data in the binary system. An antagonistic effect was found, probably due to triangular (MG) and linear (MB) molecular structures that mutually hinder the adsorption of both dyes on TMPAA. Besides, the kinetic studies for sorption of MG and MB dyes onto adsorbent were better represented by a pseudo-second-order model, which demonstrates chemisorption between the polymeric TMPAA adsorbent and dye molecules. According to experimental findings, TMPAA is an attractive adsorbent for treatment of wastewater containing multiple cationic dyes.
This paper describes the preparation, characterisation, and potential application of flexible palm oil-based polyurethane foam (PUF) as a support for iron-silica (Fe-Si) adsorbent. Fe-Si/polyurethane composite (Fe-Si/PUC) was prepared by impregnating Fe-Si adsorbent onto the surface of PUF by using a novel immersion-drying method. Morphological analysis of Fe-Si/PUC proved that Fe-Si was successfully impregnated onto the surface of PUF. Compression test and thermogravimetric analysis were carried out to determine the flexibility and thermal stability of Fe-Si/PUC, respectively. The Fe-Si/PUC removed 90.0% of 10 ppm methylene blue (MB) from aqueous solution in 60 min. The reusability study showed that Fe-Si/PUC removed 55.9% of MB on the seventh cycle. Hence, the synthesis of Fe-Si/PUC opens up a new path of implementing palm oil-based PUF to assist in the recovery of an adsorbent for environmental clean-up. The mechanism of physical interaction during the impregnation of Fe-Si adsorbent onto PUF was proposed in this paper.
The method of pre-irradiation grafting was used with the aid of electron beam (EB) accelerator to accomplish the grafting of polyamide 6 fibers (PA6) with glycidyl methacrylate (GMA). The extent to which GMA was grafted on PA6 was found to be markedly influenced by the absorbed dose of radiation and the reaction time of grafting. Trimethylamine (TMA) was afterwards employed for the functionalization of GMA-grafted fibers (PA6-g-GMA). A range of analyses (e.g., FTIR, FESEM, XRD, BET, and pHpzc) were carried out to determine the physiochemical and morphological properties of the fibrous adsorbent. p-Nitrophenol (PNP) adsorption from aqueous solution was conducted with the resulting TMA-(PA6-g-GMA) adsorbent. The adsorption behaviour of PNP on the fibrous adsorbent was clarified by investigating the adsorption kinetics and isotherm. According to the results, the adsorption of PNP on TMA-(PA6-g-GMA) reflected the pseudo-second order model. Meanwhile, the isotherm analysis revealed that the best description of the equilibrium data was provided by Redlich-Peterson model, followed closely by Langmuir isotherm model. The achieved adsorption capacity was highest at 176.036 mg/g. Moreover, the adsorption was indicated by the thermodynamic analysis to be spontaneous and exothermic. Regeneration and recycling of the adsorbent was possible for a minimum of five cycles with no reduction in adsorption capacity. It was concluded that the fibrous adsorbent could have applications for the removal of PNP at industrial pilot scale.
Proper remediation of aquatic environments contaminated by toxic organic dyes has become a research focus globally for environmental and chemical engineers. This study evaluates the adsorption potential of a polymer-based adsorbent, thiourea-modified poly(acrylonitrile-co-acrylic acid) (T-PAA) adsorbent, for the simultaneous uptake of malachite green (MG) and methylene blue (MB) dye ions from binary system in a continuous flow adsorption column. The influence of inlet dye concentrations, pH, flow rate, and adsorbent bed depth on adsorption process were investigated, and the breakthrough curves obtained experimentally. Results revealed that the sorption capacity of the T-PAA for MG and MB increase at high pH, concentration and bed-depth. Thomas, Bohart-Adams, and Yoon-Nelson models constants were calculated to describe MG and MB adsorption. It was found that the three dynamic models perfectly simulate the adsorption rate and behavior of cationic dyes entrapment. Finally, T-PAA adsorbent demonstrated good cyclic stability. It can be regenerated seven times (or cycles) with no significant loss in adsorption potential. Overall, the excellent sorption capacity and multiple usage make T-PAA polymer an attractive adsorbent materials for treatment of multicomponent dye bearing effluent in a fixed-bed column system.
Emerging dye pollution from textile industrial effluents is becoming more challenging for researchers worldwide. The contamination of water by dye effluents affects the living organisms in an ecosystem. Methylene blue (MB) and malachite green (MG) are soluble dyes with a high colour intensity even at low concentration and are hazardous to living organisms. The adsorption method is used in most wastewater plants for the removal of organic pollutants as it is cost-effective, has a high adsorption capacity, and good mechanical stabilities. In this study, a composite adsorbent was prepared by impregnating iron modified silica (FMS) onto polyurethane (PU) foam to produce an iron modified silica/polyurethane (FMS/PU) composite. The composite adsorbent was utilised in batch adsorption of the cationic dyes MB and MG. The effect of adsorption parameters such as the adsorbent load, pH, initial dye concentration, and contact time were discussed. Adsorption kinetics and isotherm were implemented to understand the adsorption mechanism for both dyes. It was found that the adsorption of MB and MG followed the pseudo-second order model. The Langmuir model showed a better fit than the Freundlich model for the adsorption of MB and MG, indicating that the adsorption occurred via the monolayer adsorption system. The maximum adsorption capacity of the FMS/PU obtained for MB was 31.7 mg/g, while for MG, it was 34.3 mg/g. The thermodynamic study revealed that the adsorption of MB and MG were exothermic and spontaneous at room temperature. In addition, the regeneration of FMS/PU was conducted to investigate the composite efficiency in adsorbing dyes for several cycles. The results showed that the FMS/PU composite could be regenerated up to four times when the regeneration efficiency dropped drastically to less than 20.0%. The impregnation of FMS onto PU foam also minimised the adsorbent loss into the environment.