• Journal of Environmental Health Sciences
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• v.45 no.6
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• pp.561-568
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• 2019

Objectives: The most commonly detected heavy metals in rocks and soils, including Pb, Cd, Cu, Fe, Mn and As, are representative pollutants discharged from abandoned mines and have been listed as potential sources of contamination in drinking water. This study focused on increasing the removal efficiency of heavy metals from drinking water resources by surface modification of natural adsorbents to reduce potential health risks. Methods: Iron oxide coating and graft polymerization with zeolites and talc was conducted for bipolar surface modification to increase the combining capacity of heavy metals for their removal from water. The removal efficiency of heavy metals was measured before and after the surface modification. Results: The removal efficiency of Pb, Cu, and Cd by surface modified zeolite showed 100, 92, and 61.5%, respectively, increases compared to 64, 64, and 38% for non-modified zeolite. This implies that bipolar surface modified natural adsorbents have a good potential use in heavy metal removal. The more interesting finding is the removal increase for As, which has both cation and anion characteristics showing 27% removal efficiency where as non-modified zeolite showed only 2% removal. Conclusions: Zeolite is one of the most widely used adsorptive materials in water treatment processes and bipolar surface modification of zeolite increases its applicability in the removal of heavy metals, especially As.

• Journal of Adhesion and Interface
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• v.12 no.1
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• pp.1-10
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• 2011

An automated reaction calorimeter was used to directly monitor the rate of emulsion polymerization of vinyl acetate using poly(vinyl alcohol) (PVAs) having different degrees of blockiness. By using this technique in conjunction with other off-line measurements of the evolution of particle size distributions, important details of the process were observed. No constant graft rate period was observed for both low and high initial monomer-water ratios. The gel effect was observed for the low monomer-water ratio recipe. The particle size distributions were broad (particle diameter 40~100 nm) and bimodal. Continuous nucleation was observed to be accompanied by 'limited aggregation' and flocculation during the particle growth stages. It was speculated to be due to the occurrence of the extensive 'limited aggregation' and chain transfer to PVA leading to grafting.

• Polymer(Korea)
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• v.24 no.3
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• pp.306-313
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• 2000

Polycaprolactone (PCL) macromer containing terminal methacrylate group was synthesized by ring-opening polymerization. The number average molecular weight of PCL macromer was 11600 g/mole and polydispersity index was 1.09. The synthesized PCL macromer was copolymerized with styrene by stable free radical polymerization using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), benzoyl peroxide, and well-defined poly(styrene-g-caprolactone)s were synthesized. The synthesized copolymers was characterized by $^1$H-NMR and gel permeation chromatography equipped with multiangle laser light scattering detector. Thermal properties of graft copolymers were investigated by DSC.

• Applied Chemistry for Engineering
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• v.4 no.3
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• pp.627-636
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• 1993

Anionic acrylic resin utilizing macromer(TBMA-g-MMA) copolymer was synthesized by preparing (TBMA) macromer using anionic living polymerization, followed by graft copolymerization with MMA macromer. To control the anionic site content in graft copolymer, the relative composition((TBMA) macromer/MMA ratio) of the graft copolymer was controlled at 7/3, 10/90, 15/85, 20/80, 30/70, 40/60, 50/50 in weight content. In the course of anionic living polymerization of(TBMA) macromer, broad molecular weight distribution (1.4~1.5) was obtained by using n-butyllithium-diphenyethylene initiatior system at $-78^{\circ}C$. To introduce the double bond at the end of chain in termination step, methacryloyl chloride was reacted after insertion of benzaldehyde as capping material. Moreover, TBMA parts in graft copolymer were hydrolyzed in the presence of p-toluenesulfonic acid catalyst, and neutralization of graft copolymer with triethylamine was granted acrylic resin to anionic site. Molecular weight and molecular weight distribution of(TBMA) macromer were determined by GPC, and the hydrolysis of TBMA with neutralization of acrylic resin were determined by IR and NMR. From water dispersion and stability point of view, stable dispersion state appeared at low molecular weight(TBMA) macromer with a small TBMA content as a result of scrutiny about the relation to TBMA content and branch length for(TBMA) macromer molecular weight in graft copolymer.

• Journal of Environmental Science International
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• v.17 no.11
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• pp.1255-1263
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• 2008

The efficiency of PP-g-AA and PP-g-St nonwoven fabric synthesized by photoinduced polymerization as an adsorbent for removal $NH_3-N$ from waste water was evaluated. The results evidently indicate that the adsorption capacities of $NH_3-N$ onto PP-g-AA nonwoven fabric were extremely superior to those onto sulfonated PP-g-St nonwoven fabric, PK and zeolite. PP-g-AA nonwoven fabric showed the maximum adsorption capacity of $NH_3-N$ at the degree of grafting of 80 wt.%. The adsorption behaviour of $NH_3-N$ onto PP-g-AA and sulfonated PP-g-St nonwoven fabric was controlled by an ion exchange reaction, and tended to be similar to both trends of Langmiur and Freundlish isotherm. Futhermore, PP-g-AA non-woven fabric could be regenerated more than 5 times by a simple washing with 0.1N HCl with no decrease of adsorption capacity and no degradation of physical properties. Also sulfonated PP-g-St nonwoven fabric could be regenerated by washing with 0.1N ${H_2}{O_4}$. However, their regeneration efficiency was significantly low because grafting layer acted as functional radical for adsorption was continuously desquamated in the adsorption or regeneration processes, which resulted in decrease of adsorption capacity and weight of adsorbent. All results obtained from this study indicate that the $NH_3-N$ removal capacity of PP-g-AA non-woven fabric was extremely superior to those of PP-g-St non-woven fabric, PK and zeolite.

• Membrane Journal
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• v.19 no.4
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• pp.333-340
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• 2009

This paper is designed with the purpose of improving the efficiency of the sulfonic acid ion exchange membranes by radiation induced graft polymerization. It has been shown that the porous hollow fiber membranes could cause permeability blocking between pores and ion exchanged graft chains. Addition of crosslinker such as N-ethylene glycol dimethacrylate will permit to increase the permeation flux. In this research, the ethylene glycol dimethacrylate (EDMA) and diethylene glycol dimethacrylate (DDMA) with different length are used as crosslinkers. The ion exchanged cross-linked membrane (EDMA, DDMA) containing sulfonic acid group by radiation induced grafted polymerization are sn died for adsorb metal ions (Pb). It has been shown that adsorbed metal ions ($Pb^{2+}$) for the EDMA and DDMA membranes with the density of sulfonic acid groups, 1.40 mmol/g and 2.14 mmol/g, respectively are 13.82 mg/g, 17.37 mg/g, accordingly.

• Membrane Journal
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• v.31 no.4
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• pp.268-274
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• 2021

One of the chronic problems in the issue of global warming is the emission of greenhouse gases. Carbon dioxide (CO₂), which accounts for the highest proportion of various greenhouse gases, has been continuously researched by humans to separate it. From this point of view, a poly(vinyl alcohol) (PVA)-based copolymer with acrylic acid monomer was utilized in a gas separation membrane in this study. We employed a free radical polymerization to fabricate PVA-g-PAA (VAA) graft copolymer. It was utilized in the form of a composite membrane on a polysulfone substrate. The proper amount of acrylic acid reduced the crystallinity of PVA and increased CO₂ solubility in separation membranes. In this perspective, we suggest the novel approach in CO₂ separation membrane area by grafting and solution-diffusion.

• Membrane Journal
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• v.18 no.2
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• pp.132-137
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• 2008

Nanofiltration membranes were prepared based on coating a sulfonated comb-like copolymer layer on top of a poly(vinylidene fluoride) (PVDF) support. The comb-like copolymer comprising poly(vinyl chloride) backbone and poly(styrene sulfonic acid) side chains, i.e. PVC-g-PSSA was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. The successful synthesis of graft copolymers were confirmed by nuclear magnetic resonance ($^1H$-NMR), FT-IR spectroscopy and wide angle X-ray scattering (WAXS). Composite nanofiltration membranes consisting PVC-g-PSSA as a top layer exhibited the increase of both rejections and solution flux with increasing PSSA concentration. This performance enhancement is presumably due to the increase of SO3H groups and membrane hydrophilicity. The rejections of composite membranes containing 71 wt% of PSSA were 88% for $Na_2SO_4$ and 33% for NaCl, and the solution flux were 26 and $34L/m^2h$, respectively, at 0.3 MPa pressure.

• Polymer(Korea)
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• v.36 no.4
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• pp.470-477
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• 2012

A tyrosinase-immobilized biosensor was developed based on various amine-modified multi-walled carbon nanotube (MWNT) supports for the detection of phenolic compounds. MWNTs with various amine groups were prepared by radiation-induced graft polymerization of glycidyl methacrylate (GMA) onto MWNT supports and the subsequent amination of poly(GMA) graft chains. The physical and chemical properties of the poly(GMA)-grafted MWNT supports and the aminated MWNT supports were investigated by SEM, XPS, and TGA. Furthermore, the electrochemical properties of the prepared tyrosinase-modified biosensor based on MWNT supports with amine groups were also investigated. The response of the enzymatic biosensor was in the range of 0.1-0.9 mM for the concentration of phenol in a phosphate buffer solution. Various parameters influencing biosensor performance have been optimized: binder effects, pH, temperature, and the response to various phenolic compounds. The biosensor was tested on phenolic compounds contained in two different commercial red wines.

• Membrane Journal
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• v.21 no.1
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• pp.39-45
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• 2011

An amphiphilic graft copolymer consisting of a poly(vinyl chloride) (PVC) backbone and poly(styrene sulfonic acid) (PSSA) side chains (PVC-g-PSSA) was synthesized via atom transfer radical polymerization (ATRP). This polymer electrolyte membrane was ion-exchanged to Ag ions by immersing in 10 wt% $AgNO_3$ aqueous solution and templated the growth of Ag nanoparticles by a reducing agent. The formation of Ag nanoparticles was confirmed using UV-visible spectroscopy and X-ray diffraction (XRD). Transmission electron microscopy (TEM) revealed that utilization of $NaBH_4$ was the most effective in the formation of Ag nanoparticles with 10~15 nm in size. The formation of Ag nanoparticles was also strongly affected by the concentration of reducing agent and reduction time.