Acrylic acid (AAc) grafted polyethylene terephthalate (PET) films were prepared by γ irradiation. The graft films showed little metal ion adsorption due to compact structure of the graft chains as shown by the scanning electron microscopy (SEM) images which restricted the access of metal ions to the functional groups. Therefore, the graft films were modified with KOH treatment for expansion of the graft chains to facilitate the access of metal ions to the functional groups. The modified films were used to study the selective Cu2+ adsorption from aqueous solution containing Cu2+, Co2+, and Ni2+. Langmuir and Freundlich isotherm models were used for interpretation of selective equilibrium adsorption data and Langmuir model showed better fitting with experimental data. Again pseudo-first-order and pseudo-second-order equations were used for interpretation of selective kinetic adsorption data and pseudo-second-order equation showed better prediction of experimental data. The adsorbent film showed high selectivity towards Cu2+ in presence of Cu2+, Co2+, and Ni2+ in the pH range of 1.5 to 4.5. Desorption and reuse of the adsorbent film were also studied which indicated that the film can be used repeatedly for selective Cu2+ sorption from aqueous solution. 1. Introduction In recent years, heavy metals have received much public attention as potential hazards for human life and health ignited by the well-known environmental destruction cases: Minamata disease (organic mercury poisoning) and itai-itai disease (cadmium poisoning) and the stricter environmental regulations on the discharge of heavy metals make it necessary to develop efficient and low cost technologies for their removal [1]. About heavy metal pollution it should be also realized that to prevent heavy metal poisoning, immediate detoxification of heavy-metal wastewater through appropriate treatment is essential. Because, unlike many organic pollutants, heavy metals are not decomposed by microbiological activity, rather heavy metals can be enriched by organisms and the type of bonding can be converted to more poisonous metal-organic complexes and the polluted areas can become widened by diffusion in the environment. But the conventional methods for removal of hazardous metal ions from wastewater such as precipitation, ion exchange, activated carbon adsorption, and electrolytic method have limitations like high cost, low removal rate or difficulty for regeneration, and reuse. Therefore, many researches focused on the study of alternative low-cost-effective adsorbents from sawdust [2], sporopollenin [3,
References
[1]
J. Ui, Ed., Industrial Pollution in Japan (the Japanese Experience Series), United Nations University Press, Tokyo, Japan, 1992, http://www.unu.edu/unupress/unupbooks/uu35ie/uu35ie00.htm.
[2]
M. ??iban, M. Kla?nja, and B. ?krbi?, “Modified softwood sawdust as adsorbent of heavy metal ions from water,” Journal of Hazardous Materials, vol. 136, no. 2, pp. 266–271, 2006.
[3]
N. ünlü and M. Ersoz, “Adsorption characteristics of heavy metal ions onto a low cost biopolymeric sorbent from aqueous solutions,” Journal of Hazardous Materials, vol. 136, no. 2, pp. 272–280, 2006.
[4]
M. Arslan, Z. Temo?in, and M. Yi?ito?lu, “Removal of cadmium (II) from aqueous solutions using sporopollenin,” Fresenius Environmental Bulletin, vol. 13, no. 7, pp. 616–619, 2004.
[5]
R. Schmuhl, H. M. Krieg, and K. Keizer, “Adsorption of Cu(II) and Cr(VI) ions by chitosan: kinetics and equilibrium studies,” Water SA, vol. 27, no. 1, pp. 1–7, 2001.
[6]
Y. S. Ho, J. C. Y. Ng, and G. McKay, “Removal of lead(II) from effluents by sorption on peat using second-order kinetics,” Separation Science and Technology, vol. 36, no. 2, pp. 241–261, 2001.
[7]
S. R. Shukla and V. D. Sakhardande, “Column studies on metal ion removal by dyed cellulosic materials,” Journal of Applied Polymer Science, vol. 44, no. 5, pp. 903–910, 1992.
[8]
Y. S. Al-Degs, M. I. El-Barghouthi, A. A. Issa, M. A. Khraisheh, and G. M. Walker, “Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic studies,” Water Research, vol. 40, no. 14, pp. 2645–2658, 2006.
[9]
R. Co?kun and C. Soykan, “Lead(II) adsorption from aqueous solution by poly(ethylene terephthalate)-g-acrylamide fibers,” Journal of Polymer Research, vol. 13, no. 1, pp. 1–8, 2006.
[10]
H. B?g, A. R. Türker, R. Co?kun, M. Sa?ak, and M. Yigitoglu, “Determination of zinc, cadmium, cobalt and nickel by flame atomic absorption spectrometry after preconcentration by poly(ethylene terephthalate) fibers grafted with methacrylic acid,” Spectrochimica Acta B, vol. 55, no. 7, pp. 1101–1108, 2000.
[11]
O. Bozkaya, M. Yi?ito?lu, and M. Arslan, “Investigation on selective adsorption of Hg(II) ions using 4-vinyl pyridine grafted poly(ethylene terephthalate) fiber,” Journal of Applied Polymer Science, vol. 124, no. 2, pp. 1256–1264, 2012.
[12]
R. Co?kun, C. Soykan, and M. Sa?ak, “Adsorption of copper(II), nickel(II) and cobalt(II) ions from aqueous solution by methacrylic acid/acrylamide monomer mixture grafted poly(ethylene terephthalate) fiber,” Separation and Purification Technology, vol. 49, no. 2, pp. 107–114, 2006.
[13]
R. Co?kun, C. Soykan, and M. Sa?ak, “Removal of some heavy metal ions from aqueous solution by adsorption using poly(ethylene terephthalate)-g-itaconic acid/acrylamide fiber,” Reactive and Functional Polymers, vol. 66, no. 6, pp. 599–608, 2006.
[14]
M. Arslan, “Preparation and use of amine-functionalized glycidyl methacrylate-g-poly(ethylene terephthalate) fibers for removal of chromium(VI) from aqueous solution,” Fibers and Polymers, vol. 11, no. 3, pp. 325–330, 2010.
[15]
M. Yi?ito?lu and M. Arslan, “Adsorption of hexavalent chromium from aqueous solutions using 4-vinyl pyridine grafted poly(ethylene terephthalate) fibers,” Polymer Bulletin, vol. 55, no. 4, pp. 259–268, 2005.
[16]
M. Yi?ito?lu and M. Arslan, “Selective removal of Cr(VI) ions from aqueous solutions including Cr(VI), Cu(II) and Cd(II) ions by 4-vinly pyridine/2-hydroxyethylmethacrylate monomer mixture grafted poly(ethylene terephthalate) fiber,” Journal of Hazardous Materials, vol. 166, no. 1, pp. 435–444, 2009.
[17]
M. Karaki?la, “The adsorption of Cu(II) ion from aqueous solution upon acrylic acid grafted poly(ethylene terephthalate) fibers,” Journal of Applied Polymer Science, vol. 87, no. 8, pp. 1216–1220, 2002.
[18]
H. H. Abdel-Razik and E. Kenawy, “Synthesis, characterization, and amidoximation of diaminomaleodinitrile- functionalized polyethylene terephthalate grafts for collecting heavy metals from wastewater,” Journal of Applied Polymer Science, vol. 125, no. 2, pp. 1136–1145, 2012.
[19]
X. Ping, M. Wang, and X. Ge, “Radiation induced graft copolymerization of n-butyl acrylate onto poly(ethylene terephthalate) (PET) films and thermal properties of the obtained graft copolymer,” Radiation Physics and Chemistry, vol. 80, no. 5, pp. 632–637, 2011.
[20]
J. J. Max and C. Chapados, “Infrared spectroscopy of aqueous carboxylic scids: comparison between different scids and their salts,” Journal of Physical Chemistry A, vol. 108, no. 16, pp. 3324–3337, 2004.
[21]
T. Kobayashi, H. Ying Wang, and N. Fujii, “Molecular imprint membranes of polyacrylonitrile copolymers with different acrylic acid segments,” Analytica Chimica Acta, vol. 365, no. 1–3, pp. 81–88, 1998.
[22]
W. J. MacKnight, L. W. McKenna, B. E. Read, and R. S. Stein, “Properties of ethylene-melhacrylic acid copolymers and their sodium salts: infrared studies,” Journal of Physical Chemistry, vol. 72, no. 4, pp. 1122–1126, 1968.
[23]
H. Yan, J. Dai, Z. Yang, H. Yang, and R. Cheng, “Enhanced and selective adsorption of copper(II) ions on surface carboxymethylated chitosan hydrogel beads,” Chemical Engineering Journal, vol. 174, no. 2-3, pp. 586–594, 2011.
[24]
H. Irving and R. J. P. Williams, “The stability of transition-metal complexes,” Journal of the Chemical Society, pp. 3192–3210, 1953.
[25]
B. L. Rivas, L. N. Schiappacasse, U. E. Pereira, and I. Moreno-Villoslada, “Interactions of polyelectrolytes bearing carboxylate and/or sulfonate groups with Cu(II) and Ni(II),” Polymer, vol. 45, no. 6, pp. 1771–1775, 2004.
[26]
I. Langmuir, “The adsorption of gases on plane surfaces of glass, mica and platinum,” The Journal of the American Chemical Society, vol. 40, no. 9, pp. 1361–1403, 1918.
[27]
H. M. F. Freundlich, “über die adsorption in l?sungen,” Zeitschrift Für Physikalische Chemie A, vol. 57, pp. 385–470, 1906.
[28]
M. Rafatullah, O. Sulaiman, R. Hashim, and A. Ahmad, “Adsorption of copper (II), chromium (III), nickel (II) and lead (II) ions from aqueous solutions by meranti sawdust,” Journal of Hazardous Materials, vol. 170, no. 2-3, pp. 969–977, 2009.
[29]
Y. S. Ho, “Review of second-order models for adsorption systems,” Journal of Hazardous Materials, vol. 136, no. 3, pp. 681–689, 2006.
[30]
C. Namasivayam and D. J. S. E. Aras?, “Removal of congo red from wastewater by adsorption onto waste red mud,” Chemosphere, vol. 34, no. 2, pp. 401–417, 1997.
[31]
S. Rengaraj, J. Yeon, Y. Kim, Y. Jung, Y. Ha, and W. Kim, “Adsorption characteristics of Cu(II) onto ion exchange resins 252H and 1500H: kinetics, isotherms and error analysis,” Journal of Hazardous Materials, vol. 143, no. 1-2, pp. 469–477, 2007.
[32]
Y. Li, Q. Y. Yue, and B. Y. Gao, “Adsorption kinetics and desorption of Cu(II) and Zn(II) from aqueous solution onto humic acid,” Journal of Hazardous Materials, vol. 178, no. 1–3, pp. 455–461, 2010.
[33]
S. Deng and Y. P. Ting, “Fungal biomass with grafted poly(acrylic acid) for enhancement of Cu(II) and Cd(II) biosorption,” Langmuir, vol. 21, no. 13, pp. 5940–5948, 2005.