Polymer Bulletin

, Volume 76, Issue 1, pp 469–494 | Cite as

An escalation of anticorrosion and microelectrical properties of polyurethane nanocomposites from green Brassica nigra oil

  • V. SelvarajEmail author
  • T. R. Rhagavarshini
  • K. Krishnadevi
Original Paper


Brassica nigra oil-based polyurethane composites have been synthesized and characterized by various analytical techniques such as Fourier transform infrared, NMR, X-ray diffraction, scanning electron microscope, atomic force microscopy, DSC and TGA. Broadband dielectric spectroscopy confirms the improvement in the dielectric properties of the prepared composites (AGO/BNP/PH) with respect to increasing AGO content. The analytical results conclude that graphene oxide-reinforced Brassica nigra oil-based polyurethane nanocomposites show improved thermal, Tg, dielectric constant and decreased dielectric loss with respect to different ratios of amine-functionalized graphene oxide. Further, the corrosion resistance behavior analysis results conclude that the prepared bio-composites have excellent corrosion-resistant property (96.93%) compared to neat Brassica nigra oil-based polyurethane polymer, which can be used as coating material for marine and also in microelectronic applications.


Brassica nigra oil (BNO) Methylene diphenyl diisocyanate (MDI) Amine-functionalized graphene oxide (AGO) Polyurethane 


  1. 1.
    Roiter Y, Minko S (2005) AFM single molecule experiments at the solid–liquid interface: in situ conformation of adsorbed flexible polyelectrolyte chains. J Am Chem Soc 127:15688–15689Google Scholar
  2. 2.
    Isikgora FH, Becer CR (2015) Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers. Polym Chem 6:4497–4559Google Scholar
  3. 3.
    Houton KA, Burslem GM, Wilson AJ (2015) Development of solvent-free synthesis of hydrogen-bonded supramolecular polyurethanes. Chem Sci 6:2382–2388Google Scholar
  4. 4.
    Sadekar AG, Mahadik SS, Bang AN, Larimore ZJ, Wisner CA, Bertino MF, Kalkan AK, Mang JT, Sotiriou-Leventis C, Leventis N (2012) From ‘Green’ aerogels to porous graphite by emulsion gelation of acrylonitrile. Chem Mater 24:26–47Google Scholar
  5. 5.
    Ray D, Das K, Ghosh SN, Bandyopadhyay NR, Sahoo S, Mohanty AK, Misra M (2010) Novel materials from sesame husks and unsaturated polyester resin. Ind Eng Chem 49:6069–6074Google Scholar
  6. 6.
    Hojabri L, Kong X, Narine SS (2009) Fatty acid-derived diisocyanate and biobased polyurethane produced from vegetable oil: synthesis, polymerization, and characterization. Biomacromology 10:884–891Google Scholar
  7. 7.
    Liu W, Zheng Y, Li J, Liu L, Huang X, Zhang J, Kang X, Tang X (2012) Novel polyurethane networks based on hybrid inorganic/organic phosphazene—containing nanotubes with surface active hydroxyl groups. Polym Adv Technol 23:1–7Google Scholar
  8. 8.
    Lligadas G, Ronda JC, Galia M, Cadiz V (2010) Plant oils as platform chemicals for polyurethane synthesis: current state-of-the-art. Biomacromology 11:2825–2835Google Scholar
  9. 9.
    Silva WSD, Lapis AAM, Suarez PAZ, Neto BAD (2011) Enzyme-mediated epoxidation of methyl oleate supported by imidazolium-based ionic liquids. J Mol Catal B Enzym 68:98–103Google Scholar
  10. 10.
    Javni I, Petrovic ZS, Guo A, Fuller R (2000) Thermal stability of polyurethanes based on vegetable oils. J Appl Polym Sci 77:1723–1734Google Scholar
  11. 11.
    Kulkarni RD, Deshpande PS, Mahajan SU, Mahulikar PP (2013) Epoxidation of mustard oil and ring opening with 2-ethylhexanol for biolubricants with enhanced thermo-oxidative and clod flow characteristics. Ind Crops Prod 49:586–592Google Scholar
  12. 12.
    Vedtofte MS, Jakobsen MU, Lauritzen L, Heitmann BL (2012) The role of essential fatty acids in the control of coronary heart disease. Curr Opin Clin Nutr Metab Care 6:592–596Google Scholar
  13. 13.
    Guo A, Cho Y-J, Petrovic ZS (2000) Structure and properties of halogenated and non- halogenated soy-based polyols. J Polym Sci Part A Polym Chem 38:3900–3910Google Scholar
  14. 14.
    Petrović ZS, Zhang W, Javni I (2005) Structure and properties of polyurethanes prepared from triglyceride polyols by ozonolysis. Biomacromol 6:713–719Google Scholar
  15. 15.
    Fleischmann C, Lievenbrück M, Ritter H (2015) Polymers and dyes: developments and applications. Polymers 7:717–746Google Scholar
  16. 16.
    Rajan H, Rajalingam P, Radhakrishnan G (1993) Synthesis and properties of segmented polyurethane using phenolphthalein as chain extenders. J Appl Polym Sci 48:2095–2099Google Scholar
  17. 17.
    Carnaroglio D, Martina K, Palmisano G, Penoni A, Domini C, Cravotto G (2013) One-pot sequential synthesis of isocyanates and urea derivatives via a microwave—assisted Staudinger—aza-Witting reaction, Beilstein. J Org Chem 9:2378–2386Google Scholar
  18. 18.
    Kreye O, Mutlu H, Meier MAR (2013) Sustainable routes to polyurethane precursors. Green Chem 15:1431–1455Google Scholar
  19. 19.
    Zu Y, Tang J, Zhu W, Zhang M, Liu G, Liu Y, Zhang W, Jina M (2011) Graphite oxide supported CaO catalysts for transesterification of soybean oil with methanol. Bioresour Technol 102:8939–8944Google Scholar
  20. 20.
    Bykkam S, Rao KV, Chakra CHS, Thunugunta T (2013) Synthesis and characterization of graphene oxide and its antimicrobial activity against Klebseilla and Staphylococcus. Int J Adv Biotechnol Res 4:142–146Google Scholar
  21. 21.
    Vadivel S, Vanitha M, Muthukrishnaraj A, Balasubramanian N (2014) Graphene oxide–BiOBr composite material as highly efficient photocatalyst for degradation of methylene blue and rhodamine—B dyes. J Water Process Eng 1:17–26Google Scholar
  22. 22.
    Prasanna D, Selvaraj V (2017) Platinum-copper doped poly(sulfonyldiphenol/cyclophosphazene/benzidine)-graphene oxide composite as an electrode material for single stack direct alcohol alkaline fuel cells. RSC Adv 7:34922–34932Google Scholar
  23. 23.
    Magal RT, Selvaraj V (2017) A comparative study for the electrocatalytic oxidation of alcohol on Pt–Au nanoparticles supported copolymer grafted graphene oxide composite for fuel cell application. Ionics 22:1–12Google Scholar
  24. 24.
    Yao RR, Zhao D-L, Bai L-Z, Yao N-N, Xuz L (2014) Facile synthesis and electrochemical performance of hollow grapheme spheres as anode materials for Li-ion batteries. Nanoscale Res Lett 9:368–373Google Scholar
  25. 25.
    Huang T, Xin Y, Li T, Nutt S, Zuliang Lai C (2013) Modified graphene/polyimide nanocomposite : reinforcing and tribological effects. Appl Mater Interfaces 5:4878–4891Google Scholar
  26. 26.
    Wu G, He X, Xu L, Zhang H, Yan Y (2015) Synthesis and characterization of bio based polyurethane/SiO2 nanocomposite from natural sapium sebiferum oil. RSC Adv 5:27097–27106Google Scholar
  27. 27.
    Chang C-H, Huang T-C, Peng C-W, Yeh T-C, Lu H-I, Hung W-I, Weng C-J, Yang T-I, Yeh J-M (2012) Novel anticorrosion coatings prepared from polyaniline/graphene composites. Carbon 50:5044–5051Google Scholar
  28. 28.
    Zheludkevich ML, Shchukin DG, Yasakau KA, Mohwald H, Ferreira MGS (2007) Anticorrosion coatings with self-healing effect based on nanocontainers impregnated with corrosion inhibitor. Chem Mater 19:402–411Google Scholar
  29. 29.
    Pu N-W, Shib G-N, Liu Y-M, Sun X, Chang J-K, Sun C-L, Ger M-D, Chen C-Y, Wang P-C, Peng Y-Y, Wu C-H, Lawes S (2015) Graphene grown on stainless steel as a high-performance and ecofriendly anti-corrosion coating for polymer electrolyte membrane fuel cell bipolar plates. J Power Sources 282:248–256Google Scholar
  30. 30.
    Sharmin E, Zafar F, Akram D, Alam M, Ahmad S (2015) Recent advances in vegetable oils based environment friendly coatings: a review. Ind Crops Prod 76:215–229Google Scholar
  31. 31.
    Gouda OE, Mahmoud SF, El-Gendy AA, Haiba AS (2014) Improving the dielectric properties of high density polyethylene by incorporating clay-nanofiller. World J Eng Technol 2:289–297Google Scholar
  32. 32.
    Prateek VK Thakur, Gupta RK (2016) Recent progress on ferroelectric polymer-based nanocomposites for high energy density capacitors: synthesis, dielectric properties, and future aspects. Chem Rev 116:4260–4317Google Scholar
  33. 33.
    Khamsen N, Onwimol D, Teerakawanich N, Dechanupaprittha S, Kanokbannakorn W, Hongesombut K, Srisonphan S (2016) Rice (Oryza sativa L.) seed sterilization and germination enhancement via atmospheric hybrid non thermal discharge plasma. ACS Appl Mater Interfaces 8:19268–19275Google Scholar
  34. 34.
    Chao-Lung H, Le Anh-Tuan B, Chun-Tsun C (2011) Effect of rice husk ash on the strength and durability characteristics of concrete. Constr Build Mater 25:3768–3772Google Scholar
  35. 35.
    Wu C, Huang X, Wang G, Wu X, Yang K, Li S, Jiang P (2012) Hyperbranched-polymer functionalization of graphene sheets for enhanced mechanical and dielectric properties of polyurethane composites. J Mater Chem 22:7010–7019Google Scholar
  36. 36.
    Wu C, Huang X, Wu X, Xie L, Yang K, Jiang P (2013) Graphene oxide-encapsulated carbon nanotube hybrids for high dielectric performance nanocomposites with enhanced energy storage density. Nanoscale 5:3847–3855Google Scholar
  37. 37.
    Yang H, Li F, Shan C, Han D, Zhang Q, Niu L, Ivask A (2009) Covalent functionalization of chemically converted graphene sheets via silane and its reinforcement. J Mater Chem 19:4632–4638Google Scholar
  38. 38.
    Wu X, Zhang X, Yang S, Chen H, Wang D (2000) The study of epoxidized rapeseed oil used as a potential biodegradable lubricant. J Am Oil Chem Soc 77:561–563Google Scholar
  39. 39.
    Zhang C, Li Y, Chen R, Kessler MR (2014) Polyurethanes from solvent-free vegetable oil-based polyols. ACS Sustain Chem Eng 2:2465–2476Google Scholar
  40. 40.
    Daniel L, Ardiyanti AR, Schuur B, Manurung R, Broekhuis AA, Heeres HJ (2011) Synthesis and properties of highly branched Jatropha curcas L. oil derivatives. Eur J Lipid Sci Technol 113:18–30Google Scholar
  41. 41.
    Seresht RJ, Jahanshahi M, Rashidi AM, Ghoreyshi AA (2013) Synthesis and characterization of thermally-reduced graphene. Iran J Energy Environ 4:53–59Google Scholar
  42. 42.
    Zhang J, Tang JJ, Zhang JX (2015) Polyols prepared from ring-opening epoxidized soybean oil by a castor oil-based fatty diol. Int J Polym Sci 22:1–8Google Scholar
  43. 43.
    Dai H, Yang L, Lin B, Wang C, Shi G (2009) Synthesis and characterization of the different soy-based polyols by ring opening of epoxidized soybean oil with methanol, 1,2-ethanediol and 1,2-propanediol. J Am Oil Chem Soc 86:261–267Google Scholar
  44. 44.
    Shaik MR, Alam M, Alandis NM (2015) Development of sustainable resource based poly(urethane-etheramide)/Fe2O3 nanocomposite as anticorrosive coating materials. J Polym Eng 35:813–916Google Scholar
  45. 45.
    Saucedo-Rivalcoba V, Martínez-Hernández AL, Martínez-Barrera G, Velasco-Santos C, Rivera Armenta JL, Castaño VM (2011) Removal of hexavalent chromium from water by polyurethane-keratin hybrid membranes. Water Air Soil Pollut 218:557–571Google Scholar
  46. 46.
    Shamsi R, Sadeghi GMM (2016) Novel polyester diol obtained from PET waste and its application in the synthesis of polyurethane and carbon nanotube-based composites: swelling behavior and characteristic properties. RSC Adv 6:38399–38415Google Scholar
  47. 47.
    Zhang C, Madbouly SA, Kessler MR (2015) Biobased polyurethanes prepared from different vegetable oils. ACS Appl Mater Interfaces 7:1226–1233Google Scholar
  48. 48.
    Wang S-K, Sung CSP (2002) Spectroscopic characterization of model urea, urethane compound, and diamine extender for polyurethane–urea. Macromolecules 35:877–882Google Scholar
  49. 49.
    Zhang S, Ren Z, He S, Zhu Y, Zhu C (2007) FTIR spectroscopic characterization of polyurethane-urea model hard segments (PUUMHS) based on three diamine chain extenders. Spectrochim Acta Part A 66:188–193Google Scholar
  50. 50.
    Kima HS, Yeuma JH, Choib SW, Leec JY, Cheonga IW (2009) Urushiol/polyurethane–urea dispersions and their film properties. Prog Org Coat 65:341–347Google Scholar
  51. 51.
    Li L, Wang X, Li Z, Bi W, Li Y, Qi Y, Dong Q (2016) The synthesis and curing kinetics study of a new fluorinated polyurethane with fluorinated side chains attached to soft blocks. New J Chem 40:596–605Google Scholar
  52. 52.
    Paul D, Paul S, Roohpour N, Wilks M, Vadgama P (2013) Antimicrobial, mechanical and thermal studies of silver particle-loaded polyurethane. J Funct Biomater 4:358–375Google Scholar
  53. 53.
    Baig U, Sanagi MM, Khan AA (2014) Preparation of organic–inorganic polyurethane–Al2O3 anion exchange fibrous composite and its application in development of membrane electrode for determination of chromium (VI) in water. RSC Adv 4:63831–63839Google Scholar
  54. 54.
    Rostamizadeh S, Hemmasi A, Zekri N (2017) Magnetic amine-functionalized graphene oxide as a novel and recyclable bifunctional nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives. Nanochem Res 2:29–41Google Scholar
  55. 55.
    Liaw D-J (1997) The relative physical and thermal properties of polyurethane elastomers: effect of chain extenders of bisphenols, diisocyanate, and polyol structures. J Appl Polym Sci 66:1251–1265Google Scholar
  56. 56.
    Popescu LM, Rusti CF, Piticescu RM, Buruiana T, Valero T, Kintzios S (2013) Synthesis and characterization of acid polyurethane–hydroxyapatite composites for biomedical applications. J Compos Mater 47:603–612Google Scholar
  57. 57.
    Sanchis MR, Calvo O, Fenollar O, Garcia D, Balart R (2008) Characterization of the surface changes and the aging effects of low-pressure nitrogen plasma treatment in a polyurethane film. Polym Test 27:75–83Google Scholar
  58. 58.
    Lu H, Fookes B, Obeng Y, Machinski S, Richardson KA (2002) Quantitative analysis of physical and chemical changes in CMP polyurethane pad surfaces. Mater Charact 49:35–44Google Scholar
  59. 59.
    Meera KMS, Sankar RM, Jaisankar SN, Mandal AB (2013) Physicochemical studies on polyurethane/siloxane crosslinked films for hydrophobic surfaces by sol–gel process. J Phys Chem B 117:2682–2694Google Scholar
  60. 60.
    Chen X, Wu L, Zhou S, You B (2003) In situ polymerization and characterization of polyester-based polyurethane/nano-silica composites. Polym Int 52:993–998Google Scholar
  61. 61.
    Kumar RS, Ariraman M, Alagar M (2015) Studies on dielectric properties of GO reinforced bisphenol-Z polybenzoxazine hybrids. RSC Adv 5:23787–23797Google Scholar
  62. 62.
    Krishnadevi K, Selvaraj V (2017) Development of cyclophosphazene and rice husk ash incorporated epoxy composites for high performance applications. Polym Bull 74:1791–1815Google Scholar
  63. 63.
    Wang Z, Nelson JK, Hillborg H, Zhao S, Schadler LS (2012) Graphene oxide filled nanocomposite with novel electrical and dielectric properties. Adv Mater 24:3134–3137Google Scholar
  64. 64.
    Pourhashem S, Vaezi MR, Rashidi A, Bagherzadeh MR (2017) Exploring corrosion protection properties of solvent based epoxy-graphene oxide nanocomposite coatings on mild steel. Corros Sci 115:78–92Google Scholar
  65. 65.
    Mo M, Zhao W, Chen Z, Yu Q, Zeng Z, Wu X, Xue Q (2015) Excellent tribological and anti-corrosion performance of polyurethane composite coatings reinforced with functionalized graphene and graphene oxide nanosheets. RSC Adv 5:56486–56497Google Scholar
  66. 66.
    Krishnadevi K, Selvaraj V (2016) Cyclotriphosphazene and TiO2 reinforced nanocomposite coated on mild steel plates for antibacterial and corrosion resistance applications. Appl Surf Sci 366:148–157Google Scholar
  67. 67.
    Sirajunnisa A, Fazal Mohamed MI, Subramania A, Venkatraman BR (2014) The Inhibitive effect of Ziziphus jujuba leaves extract on the alkaline corrosion of aluminium. Eur J Appl Sci Technol 1:23–31Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • V. Selvaraj
    • 1
    Email author
  • T. R. Rhagavarshini
    • 1
  • K. Krishnadevi
    • 2
  1. 1.Nanotech Research Laboratory, Department of ChemistryUniversity College of Engineering Villupuram (A Constituent College of Anna University, Chennai-25)VillupuramIndia
  2. 2.Department of ChemistryVignan UniversityGunturIndia

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