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Chemical Papers

, Volume 71, Issue 2, pp 409–421 | Cite as

Enhancing corrosion resistance of zinc-filled protective coatings using conductive polymers

  • Miroslav Kohl
  • Andréa Kalendová
  • Eva Schmidová
Original Paper

Abstract

Organic coatings containing zinc are amply used for the protection of metals, particularly steel structures. Ways to reduce the zinc content in the coating materials are sought for environmental and financial reasons. Our previous work (Kohl, Prog Org Coat 77:512–517, 2014; Kohl and Kalendová, Mater Sci Forum 818: 171–174, 2015a) suggested that one of the options consists in the use of conductive polymers in the formulation of the zinc coatings. The benefits of conductive polymers include nontoxicity, high stability, electric conductivity and redox potential. Previously we focussed on the effect of conductive polymers added to the organic coatings so as to complete the zinc volume concentration to 67%. The anticorrosion efficiency of the organic coatings was found to improve with increasing polyaniline phosphate or polypyrrole concentrations. Zinc content reduction in the system, however, did not attain more than 5%. The present work focusses on systems where the organic coatings are prepared with zinc having a pigment volume concentration PVC = 50%. Zinc content reduction in the system attains up to 20%. This work examines the mechanical and anticorrosion properties of the organic coatings with reduced zinc contents. The present work was devoted to the feasibility of using of conductive polymers in the formulation of coatings with reduced zinc contents. The conductive polymers included polyaniline, polypyrrole and poly(phenylenediamine); these were synthesised and characterised using physico-chemical methods. Polyphenylenediamine as a potential corrosion inhibitor has not been paid adequate attention so far. Subsequently, organic coatings with reduced zinc contents and containing the pigments at 0.5, 1 and 3% volume concentrations were formulated. The coatings were subjected to mechanical tests and accelerated corrosion tests to assess their mechanical and corrosion resistance. The corrosion resistance of the organic coatings was also studied by linear polarisation. The results of the mechanical tests, accelerated corrosion tests and linear polarisation measurements indicate that the organic coating properties get affected by the conductive polymer type as well as by the pigment volume concentration. The important finding is that the use of conductive polymers in coatings with reduced zinc contents was beneficial in all cases.

Keywords

Coating Corrosion Conductive polymers Zinc 

List of symbols

ASTM

American Standard for Testing and Materials

CP

Conductive polymers

CP-base

Conductive polymers-base

CPVC

Critical pigment volume concentration (%)

CSN

Czech state norm

d50

Mean particle size

DFT

Dry film thickness

e

Electron

e.g.

Exempli gratia

Ecorr

Spontaneous corrosion potential mV

EDX

Energy-dispersive X-ray spectroscopy

EOC

Potential value reached at the end of the previous open circuit period (mV)

Fe

Iron

H

Hydrogen

i.e.

Id est

Icorr

Current density (mV)

ISE

Ion-selective electrode

ISO

International Organization for Standardization

Norm

Normed

oil abs

Oil absorption (g 100 g−1)

PANI

Polyaniline

PANI-EB

Polyaniline base

PANI-ES

Polyaniline salt

PANI-H3PO4

Polyaniline phosphate

PPDA

Poly(phenylenediamine)

PPDA-H3PO4

Poly(p-phenylenediamine) phosphate

PPy

Polypyrrole

PPy-H3PO4

Polypyrrole phosphate

PVC

Pigment volume concentration (%)

Rp

Polarisation resistance (Ω)

SEM

Scanning electron microscope

Greek letters

ρ

Density (g cm−3)

υcorr

Corrosion rate (mm year−1)

χ

Conductivity (mS cm−1)

Subscripts

Corr

Corrosion

Oc

Open circuit period

P

Polarisation

21

21st day

References

  1. Abu-Thabit NY, Makhlouf ASH (2014) 17-Recent advances in polyaniline (PANI)-based organic coatings for corrosion protection. In: Handbook of smart coatings for materials protection. Woodhead Publishing, United Kingdom, pp 459–486Google Scholar
  2. Akbarinezhad E, Ebrahimi M, Sharif F, Attar MM, Faridi HR (2011) Synthesis and evaluating corrosion protection effects of emeraldine base PAni/clay nanocomposite as a barrier pigment in zinc-rich ethyl silicate primer. Prog Org Coat 70:39–44. doi: 10.1016/j.porgcoat.2010.09.016 Google Scholar
  3. AL-Oqla FM, Sapuan SM, Anwer T, Jawaid M, Hoque ME (2015) Natural fiber reinforced conductive polymer composites as functional materials: a review. Synth Met 206:42–54. doi: 10.1016/j.synthmet.2015.04.014 Google Scholar
  4. Armelin E, Ocampo C, Liesa F, Iribarren JI, Ramis X, Alemán C (2007a) Study of epoxy and alkyd coatings modified with emeraldine base form of polyaniline. Prog Org Coat 58:316–322. doi: 10.1016/j.porgcoat.2007.01.005 Google Scholar
  5. Armelin E, Oliver R, Liesa F, Iribarren JI, Estrany F, Alemán C (2007b) Marine paint formulations: conducting polymers as anticorrosive additives. Prog Org Coat 59:46–52. doi: 10.1016/j.porgcoat.2007.01.013 Google Scholar
  6. Armelin E, Pla R, Liesa F, Ramis X, Iribarren JI, Alemán C (2008) Corrosion protection with polyaniline and polypyrrole as anticorrosive additives for epoxy paint. Corros Sci 50:721–728. doi: 10.1016/j.corsci.2007.10.006 Google Scholar
  7. Armelin E, Alemán C, Iribarren JI (2009) Anticorrosion performances of epoxy coatings modified with polyaniline: a comparison between the emeraldine base and salt forms. Prog Org Coat 65:88–93. doi: 10.1016/j.porgcoat.2008.10.001 Google Scholar
  8. Armelin E, Martí M, Liesab F, Iribarren JI, Alemán C (2010) Partial replacement of metallic zinc dust in heavy duty protective coatings by conducting polymer. Prog Org Coat 69:26–30. doi: 10.1016/j.porgcoat.2010.04.023 Google Scholar
  9. Balinta R, Cassidy NJ, Cartmell SH (2014) Conductive polymers: towards a smart biomaterial for tissue engineering. Acta Biomater 10:2341–2353. doi: 10.1016/j.actbio.2014.02.015 Google Scholar
  10. Blinová NV, Stejskal J, Trchová M, Prokeš J, Omastová M (2007) Polyaniline and polypyrrole: a comparative study of the preparation. Eur Polymer J 43:2331–2341. doi: 10.1016/j.eurpolymj.2007.03.045 Google Scholar
  11. Goldschmidt A, Streitberger HJ (2007) Basf handbook on basics of coating technology. Vincentz Network, Germany, pp 345–401. ISBN 973-3-86630-903-6Google Scholar
  12. Guimard NK, Gomez N, Schmidt CHE (2007) Conducting polymers in biomedical engineering. Prog Polym Sci 32:876–921. doi: 10.1016/j.progpolymsci.2007.05.012 Google Scholar
  13. Havlík J, Kalendová A, Veselý D (2007) Electrochemical, chemical and barrier action of zinc dust/anticorrosive pigments containing coatings. J Phys Chem Solids 68:1101–1105. doi: 10.1016/j.jpcs.2006.11.016 Google Scholar
  14. Huang MR, Peng QR, Li XG (2006) Rapid and effective adsorption of lead ions on fine poly(phenylenediamine) microparticles. Chem Eur J 12:4341–4350PubMedGoogle Scholar
  15. Kalendová A (2003) Effects of particle sizes and shapes of zinc metal n the properties of anticorrosive coating. Prog Org Coat 46:324–332. doi: 10.1016/S0300-9440(03)00022-5 Google Scholar
  16. Kalendová A, Veselý D (2009) Study of the anticorrosive efficiency of zincite and periclase-based core–shell pigments in organic coatings. Prog Org Coat 64:5–19. doi: 10.1016/j.porgcoat.2008.07.003 Google Scholar
  17. Kalendová A, Kalenda P, Veselý D (2006) Properties of anticorrosion pigments depending on their chemical composition and PVC value. Pigm Resin Technol 35:188–199. doi: 10.1108/03699420610677181 Google Scholar
  18. Kalendová A, Sapurina I, Stejskal J, Veselý D (2008) Anticorrosion properties of polyaniline-coated pigments in organic coatings. Corros Sci 50:3549–3560. doi: 10.1016/j.corsci.2008.08.044 Google Scholar
  19. Kalendová A, Veselý D, Kalenda D (2010) P. Properties of paints with hematite coated muscovite and talc particles. Appl Clay Sci 48:581–588. doi: 10.1016/j.clay.2010.03.007 Google Scholar
  20. Kalendová A, Veselý D, Kohl M, Stejskal J (2015) Anticorrosion efficiency of zinc-filled epoxy coatings containing conducting polymers and pigments. Prog Org Coat 78:1–20. doi: 10.1016/j.porgcoat.2014.10.009 Google Scholar
  21. Kang ET, Neoh KG, Tan KL (1998) Polyaniline: a polymer with many interesting intrinsic redox states. Prog Polym Sci 23:277–324. doi: 10.1016/S0079-6700(97)00030-0 Google Scholar
  22. Király A, Ronkay F (2015) Temperature dependence of electrical properties in conductive polymer composites. Polym Testing 43:154–162. doi: 10.1016/j.polymertesting.2015.03.011 Google Scholar
  23. Kohl M, Kalendová A (2014) Assessment of the impact of polyaniline salts on corrosion properties of organic coatings. KOM 58:113–119. doi: 10.1515/kom-2015-0004 Google Scholar
  24. Kohl M, Kalendová A (2015a) The effect of polypyrrole on corrosive properties of organic coatings containing high amounts of zinc metal particles. Mater Sci Forum 818:171–174. doi: 10.4028/www.scientific.net/MSF.818.171 Google Scholar
  25. Kohl M, Kalendová A (2015b) Effect of polyaniline salts on the mechanical and corrosion properties of organic protective coatings. Prog Org Coat 86:96–107. doi: 10.1016/j.porgcoat.2015.04.006 Google Scholar
  26. Kohl M, Kalendová A (2015c) Anticorrosion properties of organic coatings containing polyphenylenediamine phosphate. Adv Sci Technol 9:47–50. doi: 10.12913/22998624/60782 Google Scholar
  27. Kohl M, Kalendová A, Stejskal J (2014) The effect of polyaniline phosphate on mechanical and corrosive properties of protective organic coatings containing high amounts of zinc metal particles. Prog Org Coat 77:512–517. doi: 10.1016/j.porgcoat.2013.11.018 Google Scholar
  28. Li XG, Huang MR, Duan W (2002) Novel multifunctional polymers from aromatic diamines by oxidative polymerizations. Chem Rev 102:2925–3030. doi: 10.1021/cr010423z PubMedGoogle Scholar
  29. Nascimento GM, Ricardo HS, Temperini MLA (2010) Structural characterization of poly-para-phenylenediamine–montmorillonite clay nanocomposites. Synth Met 160:2397–2403. doi: 10.1016/j.synthmet.2010.09.016 Google Scholar
  30. Nguyen TD, Nguyen TA, Pham MC, Piro B, Normand B, Takenouti H (2004) Mechanism for protection of iron corrosion by an intrinsically electronic conducting polymer. J Electroanal Chem 572:225–234. doi: 10.1016/j.jelechem.2003.09.028 Google Scholar
  31. Schaefer K, Miszczyk A (2013) Improvement of electrochemical action of zinc-rich paints by addition of nanoparticulate zinc. Corros Sci 66:380–391. doi: 10.1016/j.corsci.2012.10.004 Google Scholar
  32. Schultze JW, Karabulut H (2005) Application potential of conducting polymers. Electrochim Acta 50:1739–1745. doi: 10.1016/j.electacta.2004.10.023 Google Scholar
  33. Shreepathi S, Bajaj P, Mallik BP (2010) Electrochemical impedance spectroscopy investigations of epoxy zinc rich coatings: role of Zn content on corrosion protection mechanism. Electrochim Acta 55:5129–5134. doi: 10.1016/j.electacta.2010.04.018 Google Scholar
  34. Somboonsub B, Srisuwan S, Invernale MA, Thongyai S, Praserthdam P, Scola DA, Sotzing GA (2010) Comparison of the thermally stable conducting polymers PEDOT, PANi, and PPy using sulfonated poly(imide) templates. Polymer 51:4472–4476. doi: 10.1016/j.polymer.2010.08.008 Google Scholar
  35. Stejskal J (2015) Polymers of phenylenediamines. Prog Polym Sci 41:1–31. doi: 10.1016/j.progpolymsci.2014.10.007 Google Scholar
  36. Vernitskaya TV, Efimov ON (1997) Polypyrrole a conducting polymer; its synthesis, properties and applications. Russ Chem Rev 66:443–457Google Scholar
  37. Veselý D, Kalendová A, Manso MV (2012) Properties of calcined kaolins in anticorrosion paints depending on PVC, chemical composition and shape of particles. Prog Org Coat 62:82–91. doi: 10.1016/j.porgcoat.2011.11.017 Google Scholar
  38. Vliet CH (1998) Reduction of zinc and volatile organic solvents in two-pack anti-corrosive primers, a pilot study. Prog Org Coat 34:220–226. doi: 10.1016/S0300-9440(98)00027-7 Google Scholar
  39. Xie Y, Wang D (2016) Supercapacitance performance of polypyrrole/titanium nitride/polyaniline coaxial nanotube hybrid. J Alloy Compd 665:323–332. doi: 10.1016/j.jallcom.2016.01.089 Google Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2016

Authors and Affiliations

  • Miroslav Kohl
    • 1
  • Andréa Kalendová
    • 1
  • Eva Schmidová
    • 2
  1. 1.Faculty of Chemical Technology, Institute of Chemistry and Technology of Macromolecular MaterialsUniversity of PardubicePardubiceCzech Republic
  2. 2.Jan Perner Transport Faculty, Educational and Research Centre in TransportUniversity of PardubicePardubiceCzech Republic

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