Surface modification of vulcanized EPDM rubber by Ag (II): Kinetic study of Ag (II) generation and surface characterization

Document Type : Article


1 Petrochemicals Synthesis Department, Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, postal code 14977-1311, Tehran, Iran

2 Engineering department, Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, postal code 14977-1311, Tehran, Iran


Ethylene propylene diene monomer (EPDM) rubber has been widely used in the various outdoor and industrial applications. However, in order to improve its adhesion properties it needs some surface modification. Mediated electrochemical oxidation by Ag (II) was thus employed to evaluate the feasibility of EPDM surface modification. The electrochemical behavior of Ag (I) /Ag (II) redox couple was initially studied at different temperatures in an electro-membrane cell using IrO2/Ta2O5anode. The reversibility of the redox reaction improved at low temperatures. The apparent rate constant for Ag (I) oxidation (k1) at 3 kA m-2 was  (s-1).
The surface chemistry, morphology and wettability of the activated EPDM rubber by Ag (II) were then analyzed and the modified EPDM surface showed a significant decrease in the water contact angle resulting in an increase in the surface free energy and improved wettability. ATR analysis revealed presence of oxygen-containing polar groups on the modified rubber surface. SEM results showed that the short treatment time at room temperature only changed the morphology of the rubber surface, which is attributed to the etching of the outermost surface.


Main Subjects

1. Da Maia, J., Pereira, F., Dutra, J., Mello, S., Becerra,
E., and Massi, M. \In
uence of gas and treatment time
on the surface modi cation of EPDM rubber treated
at afterglow microwave plasmas", Applied Surface
Science, 285, pp. 918-926 (2013).
2. Oliveira, Jr. M., Mello, S., da Silva Sobrinho, A.,
Grigorov, K., Massi, M., and Maciel, H. \Surface
modi cation of EPDM rubber by microwave excited
plasmas", Surface Engineering, 26, pp. 519-524 (2010).
3. Dutra, J.C.N., Massi, M., Otani, C., De Cassia
Lazzarini Dutra, R., Diniz, M.F., and Urruchi, W.I.
\Surface modi cation of EPDM rubber by reactive
argon-oxygen plasma process", Molecular Crystals and
Liquid Crystals, 374, pp. 45-52 (2002).
4. Grythe, K.F. and Hansen, F.K. \Surface modi cation
of EPDM rubber by plasma treatment", Langmuir, 22,
pp. 6109-6124 (2006).
5. Santos, R.P., de Oliveira Junior, M.S., da Costa Mattos,
E., Diniz, M.F., and Dutra, R.D.C.L. \Study by
FT-IR technique and adhesive properties of vulcanized
EPDM modi ed with plasma", Journal of Aerospace
Technology and Management, 5, pp. 65-74 (2013).
6. Brewis, D., Briggs, D., Dahm, R., and Fletcher, I.
\A ToF-SIMS study of electrochemical pretreatments
for polymers", Surface and Interface Analysis, 29, pp.
572-581 (2000).
7. Brewis, D. and Dahm, R. \A review of electrochemical
pretreatments of polymers", International Journal of
Adhesion and Adhesives, 21, pp. 397-409 (2001).
8. Panizza, M., Duo, I., Michaud, P., Cerisola, G., and
Comnellis, C. \Electrochemical generation of silver (II)
at boron-doped diamond electrodes", Electrochemical
and Solid-State Letters, 3, pp. 550-551 (2000).
9. Jones, C., Del Campo, J., Nevins, P., and Legg, S. \Decontamination/
destruction technology demonstration
for organics in transuranic waste", AEA Technology
Engineering Services, Inc. (US) (2002).
10. Bringmann, J., Ebert, K., Galla, U., and Schmieder,
H. \Electrochemical mediators for total oxidation of
chlorinated hydrocarbons: formation kinetics of Ag
(II), Co (III), and Ce (IV)", Journal of Applied Electrochemistry,
25, pp. 846-851 (1995).
11. Lehmani, A., Turq, P., and Simonin, J.P. \Oxidation
kinetics of water and organic compounds by silver
(II) using a potentiometric method", Journal of The
Electrochemical Society, 143, pp. 1860-1866 (1996).
12. Fleischmann, M., Pletcher, D., and Ra nski, A. \The
kinetics of the silver (I)/silver (II) couple at a platinum
electrode in perchloric and nitric acids", Journal of
Applied Electrochemistry, 1, pp. 1-7 (1971).
13. Smith, W., Purdy, G., and McKee, S., Comparison of
Silver (II), Cobalt (III), and Cerium (IV) as Electron
Transfer Mediators in the MEO Mixed Waste Treatment
Process, Los Alamos National Lab., NM (United
States) (1997).
14. Farmer, J., Hickman, R., Wang, F., Lewis, P.,
and Summers, L., Initial Study of the Complete
Mediated Electrochemical Oxidation of Ethylene Glycol,
Lawrence Livermore National Lab., CA (United
States) (1991).
15. Panizza, M. and Cerisola, G. \Direct and mediated
anodic oxidation of organic pollutants", Chemical Reviews,
109, pp. 6541-6549 (2009).
16. Racaud, C., Savall, A., Rondet, P., Bertrand, N., and
Groenen Serrano, K. \New electrodes for silver (II)
electrogeneration: Comparison between Ti/Pt, Nb/Pt,
and Nb/BDD", Chemical Engineering Journal, 211,
pp. 53-59 (2012).
17. Po lczynski, P., Jurczakowski, R., and Grochala, W.
\Stabilization and strong oxidizing properties of Ag(II)
in a
uorine-free solvent", Chemical Communications,
49, pp. 7480-7482 (2013).
18. Mokhtari, S., Mohammadi, F., and Nekoomanesh, M.
\Surface modi cation of PP-EPDM used in automotive
industry by mediated electrochemical oxidation",
Iranian Polymer Journal, 25, pp. 309-320 (2016).
19. Mokhtari, S., Mohammadi, F., and Nekoomanesh, M.
\Mediated electrochemical degradation of polystyrene
by silver (II): Optimization and kinetic studies", Int.
J. Chem. Tech. Res., 5, pp. 2656-2671 (2013).
20. Ronagh-Baghbani, M., Mohammadi, F., and Naderi,
G. \Surface characterization of polybutadiene and
natural rubbers oxidized by silver (II)", Soft Materials,
14, pp. 187-198 (2016).
21. Ronagh-Baghbani, M., Naderi, G., and Mohammadi,
F. \Mediated electrochemical oxidation of
vulcanized polybutadiene/organoclay nanocompositecharacterization
and kinetic study", Polymer Degradation
and Stability, 131, pp. 30-41 (2016).
Sh. Mokhtari et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 1371{1383 1383
22. Klink, M.J., Ebenso, E., and Crouch, A.M. \Physicochemical
characterization of di erent preparation
routes of binary and ternary metal oxides on titanium
substrates", Int. J. Electrochem. Sci., 7, pp. 3018-3030
23. Mokhtari, S., Mohammadi, F., and Nekoomanesh, M.
\E ect of process parameters on the concentration,
current eciency and energy consumption of electrogenerated
silver (II)", Chemical Papers, 69, pp. 1219-
1230 (2015).
24. Rance, P., Nikitina, G., Korolev, V., Kirshin, M.Y.,
Listopadov, A., and Egorova, V. \Features of electrolysis
of nitric acid solutions of silver: I. behavior of Ag
(II) in HNO3 Solutions", Radiochemistry, 45, pp. 346-
352 (2003).
25. Denuault, G., Fleischmann, M., and Pletcher, D. \A
microelectrode study of the mechanism of the reactions
of silver (II) with manganese (II) and chromium (III) in
sulphuric acid", Journal of Electroanalytical Chemistry
and Interfacial Electrochemistry, 280, pp. 255-265
26. Leung, P., Ponce de Leon, C., Low, C., and Walsh, F.
\Ce (III)/Ce (IV) in methanesulfonic acid as the positive
half cell of a redox
ow battery", Electrochimica
Acta, 56, pp. 2145-2153 (2011).
27. Bard, A.J. and Faulkner, L.R., Electrochemical Methods:
Fundamentals and Applications, Wiley New York
28. Trasatti, S. and Petrii, O. \Real surface area measurements
in electrochemistry", Pure and Applied Chemistry,
63, pp. 711-734 (1991).
29. Nicholson, R.S. \Theory and application of cyclic
voltammetry for measurement of electrode reaction
kinetics", Analytical Chemistry, 37, pp. 1351-1355
30. Matheswaran, M., Balaji, S., Chung, S.J., and Moon,
I.S. \Silver-mediated electrochemical oxidation: Production
of silver (II) in nitric acid medium and in situ
destruction of phenol in semi-batch process", Journal
of Industrial and Engineering Chemistry-Seoul, 13, pp.
231-243 (2007).
31. Basak, G.C., Bandyopadhyay, A., Neogi, S., and
Bhowmick, A.K. \Surface modi cation of argon/ oxygen
plasma treated vulcanized ethylene propylene diene
polymethylene surfaces for improved adhesion with
natural rubber", Applied Surface Science, 257, pp.
2891-2904 (2011).
32. Moraes, J.H. and Sobrinho, H.S. \Surface improvement
of EPDM rubber by plasma treatment", J. Phys.
D: Appl. Phys., 40, pp. 7747-7752 (2007).
33. Bohm, K. \Compost quality determination using infrared
spectroscopy and multivariate data analysis",
Institute of Waste Management, Vienna, University of
Natural Resources and Applied Life Sciences, PhD, p.
104 (2009).
34. Ronagh-Baghbani, M. \Mediated electrochemical oxidation
of polybutadiene rubber and polybutadiene/
organoclay nano composite by silver (II)", PHD
Thesis, Iran Polymer and Petrochemical Institute