To remove chromium from wastewater effectively, two types of nitrogen-containing fabric adsorbents, having amidoxime ligand groups and quaternary ammonium anion exchange groups, respectively, were prepared by radiation grafting. In brief, the amidoxime adsorbent is obtained by grafting of acrylonitrile (AN)/methacrylic acid (MAA) onto a nonwoven fabric and subsequent amidoximation with hydroxylamine, while the ammonium adsorbent is obtained by grafting of chloromethylstyrene (CMS) followed by quaternization with trimethylamine. The AN/MAA-grafting reaches a high degree of grafting more than 100%, and the resulting amidoxime adsorbent reaches a high amidoxime density of 4.53 mmol/g. On the other hand, the CMS-grafting reaches a much higher degree of grafting above 200%, and the resulting ammonium adsorbent reaches a high ammonium density of 3.51 mmol/g. FTIR/ATR and TGA/DTA are used for the characterization of the grafted fabrics as well as the relevant fabric adsorbents. Furthermore, the chromium removal of the prepared fabric adsorbent is tested in both batch and column modes. It has been confirmed that the chromium removal was largely dependent on the pH of the solution. At pH 5.0, the amidoxime adsorbent shows a high Cr(III) adsorption capacity of 31.68 mg/g, while the ammonium adsorbent shows a much higher Cr(VI) adsorption capacity of 130.65 mg/g.

This paper investigates the selectivity of GMA-based-non-woven fabrics adsorbent towards copper ion (Cu) functionalized with several aliphatic amines. The aliphatic amines used in this study were ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). The non-woven polyethylene/polypropylene fabrics (NWF) were grafted with glycidyl methacrylate (GMA) via pre-radiation grafting technique, followed by chemical functionalization with the aliphatic amine. To prepare the ion recognition polymer (IRP), the functionalized amine GMA-grafted-NWF sample was subjected to radiation crosslinking process along with the crosslinking agent, divinylbenzene (DVB), in the presence of Cu ion as a template in the matrix of the adsorbent. Functionalization with different aliphatic amine was carried out at different amine concentrations, grafting yield, reaction temperature, and reaction time to study the effect of different aliphatic amine onto amine density yield. At a concentration of 50% of amine and 50% of isopropanol, EDA, DETA, TETA, and TEPA had attained amine density around 5.12, 4.06, 3.04, and 2.56 mmol/g-ad, respectively. The amine density yield decreases further as the aliphatic amine chain grows longer. The experimental condition for amine functionalization process was fixed at 70% amine, 30% isopropanol, 60 °C for grafting temperature, and 2 h of grafting time for attaining 100% of grafting yield (Dg). The prepared adsorbents were characterized comprehensively in terms of structural and morphology with multiple analytical tools. An adsorptive removal and selectivity of Cu ion by the prepared adsorbent was investigated in a binary metal ion system. The IRP samples with a functional precursor of EDA, the smallest aliphatic amine had given the higher adsorption capacity and selectivity towards Cu ion. The selectivity of IRP samples reduces as the aliphatic amine chain grows longer, EDA to TEPA. However, IRP samples still exhibited remarkably higher selectivity in comparison to the amine immobilized GMA-g-NWF at similar adsorption experimental conditions. This observation indicates that IRP samples possess higher selectivity after incorporation of the ion recognition imprint technique via the radiation crosslinking process.

A simplified radiation-induced emulsion graft polymerization (SREG) method is proposed. This method involves a convenient and easy degassing process of a monomer solution using a commercially available sealed glass jar. A loaded weight on the lid of the jar was used to control the jar’s internal pressure as the degassing of the monomer solution took place using a vacuum pump. The degassing method was highly reproducible, resulting from no bumping of the monomer solution. The initial grafting velocity was proportional to the absorbed doses of pre-irradiation between 5 and 20 kGy. This result indicates that dissolved oxygen was sufficiently eliminated from the monomer solution at such a level where the remaining oxygen had little effect on the grafting reaction at a dose of 5 kGy. The method was then applied to the fabrication of a heavy metal adsorbent that possessed a sufficient adsorption capacity of Co(II) ions. The SREG method is applicable to the fabrication of a wide variety of functional graft polymers because high-dose-rate gamma-ray radiation and expensive experimental equipment are not necessary.

Reversible addition-fragmentation chain transfer (RAFT) agent was added into a simultaneous radiation grafting system and its effects on graft polymerization and homopolymerization were investigated. Chloromethylstyrene (CMS) was graft polymerized onto ethylene-tetrafluoroethylene copolymer (ETFE) films under γ-ray sources via simultaneous irradiation. The non-grafted poly(CMS) in the grafted films were extracted by xylene at 120 °C. The poly(CMS) was characterized by NMR and GPC instruments. Addition of the RAFT agent suppressed both graft polymerization and homopolymerization. However, under a high concentration of RAFT agent, the homopolymerization in the monomer solution could occur through a typical RAFT polymerization while polymerization in the ETFE films proceeded via RAFT and conventional radical polymerization, resulting in poly(CMS) in the ETFE films with molecular weight dispersity higher than 1.0 but lower than that without RAFT agent. Furthermore, it was found that the molecular weight of the poly(CMS) in the ETFE films was several times higher than that of the poly(CMS) in the monomer solution.