Polyurethane-based Nanocomposite Film as Barrier Coating: Effect of Weight Content of TiO2 Nanoparticles on the Surface Wettability, Moisture Permeability, Mechanical Durability, and Thermal Stability

Document Type : Original Article

Authors

Chemical Engineering Department, Hamedan University of Technology, P.O. Box: 65155, Hamedan, Iran.

Abstract

The surface wettability, moisture permeability, mechanical durability, and thermal stability of polyurethane (PU) and PU@TiO2 nanocomposite films at different weight contents of TiO2 nanoparticles (NPs) were studied experimentally. An increase in the NPs wt. % led to an increase in the hydrophobic property, thermal stability and mechanical durability of the films. The water contact angle (WCA) increased from 94.7o to 98.9o with the films' surface roughness due to NP agglomeration. The curing temperature (Tc) influenced the films wettability at Tc ≤ 140 °C, while film surface segregation was observed at Tc > 160 °C. The WCA of pure PU increased from 93.4o to 107.1o with an increase in Tc from 60 to 200 oC, respectively. Moisture permeability improved with the incorporation of 5 wt. % NPs. Due to the more porous structure of the 7 wt.% sample, its water absorption rate was slightly higher than that of the 5 wt.% sample. The glass transition temperature and melting temperature of the 7 wt.% sample were 88.2 and 185.5 oC, respectively, while the enthalpy of fusion was determined to be 22.82 J/g. The tensile strength and elongation at the break of the films slightly decreased with an increase in the NPs wt. %. The kinetic model of water absorption indicated that the effective diffusion coefficient (Deff) is highly influenced by the porous structure of the film. Deff decreased from 2.4×10-8 to 1.4×10-10 cm2.s-1 as the NP weight content increased from 3 to 7 wt.%, while the permeability coefficient (Peff) exhibited an increase from 3.2×10-11 to 8.0×10-11 mg.cm(Pa.s)-1. Additionally, relative humidity showed a greater effect on Deff than NP weight content, while the opposite was observed for Peff. 

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Main Subjects

References

  1. Bayer O. Das di-isocyanat-Polyadditionsverfahren (Polyurethane). Angew Chem. 1947;59(1):257-272. https://doi.org/10.1002/ange.19470590901
  2. Xiao Ch, Bai Y, Pu Y, Luo H, Xiao S, He B. Effect of polymer architecture and hard/soft segment ratio on the surface morphology and mechanical properties of polyurethane films for potential orthodontic treatment. J Appl Polym Sci. 2020; 137(1):e49363. https://doi. org/10.1002/app.49363
  3. Ma Y, Wu LF, Li SL, Han X, Peng XY, Feng YM, Ji YM, Yang YK, Liu F. Regulating the structure of thermoplastic polyurethane elastomers with a diol chain extender to strength Performance. J Appl Polym Sci. 2023;140(22):e53921. https://doi.org/10.1002/ app. 53921
  4. Shi Zh, Sheng Y, Wu J, Cui J, Lin W, Ngai T. Porous waterborne polyurethane films templated from pickering foams for fabrication of synthetic leather. Langmuir. 2024;40(1):475-4761. https://doi.org/10. 1021/acs.langmuir.3c03514
  5. Kasanen J, Suvanto M, Pakkanen TT. UV stability of polyurethane binding agent on multilayer photo-catalytic TiO2 coating. Polym Test. 2011; 30 (2): 381-389. https://doi.org/10.1016/j.polymertesting.2011. 02.006
  6. Kianpour Gh, Bagheri R, Pourjavadi A, Ghanbari H. In situ synthesized TiO2-polyurethane nanocomposite for bypass graft application: In vitro endothelialization and degradation. Mat Sci Eng C. 2020; 114(1): 111043. https://doi.org/10.1016/j.msec.2020.111043
  7. Jakhmola S, Das S, Dutta K. Emerging research trends in the field of polyurethane and its nanocomposites: Chemistry, synthesis, characterization, application in coatings and future perspectives. J Coat Technol Res. 2024; 21(1):137-172. https://doi.org/10.1007/s11998-023-00841-z 
  8. Samimi A. Use of polyurethane coating to prevent corrosion in oil and gas pipelines transfer. IJIAS 2012; 1(2):186-193. http://www.issr-journals.org/ijias.
  9. Sabah Khadim N, AbdulKareem Abdulaali N, Saleh HM. Study of Heavy metal ions adsorption using grafted polyurethane with iron oxide nanoparticles as adsorbent. J Nanostruct. 2023;13(1):173-183. https://doi.org/10.22052/JNS.2023.01.019.
  10. Hanoon RS, Al-Lami AKA, Abbas AM. Polyurethane/Silver nanoparticle composite thermal behavior and electrical conductivity enhancement. J Nanostruct. 2024;14(1):38-47. https://doi.org/10. 22052/JNS.2024.01.004
  11. Pei A, Malho J-M, Ruokolainen J, Zhou Q, Berglund LA. Strong nanocomposite reinforcement effects in polyurethane elastomer with low volume fraction of cellulose nanocrystals. Macromol. 2011; 44(11):4422-4427. https://doi.org/10.1021/ma200318k.
  12. Madbouly SA, Xia Y, Kessler MR. Sustainable polyurethane-lignin aqueous dispersions and thin films: Rheological behavior and thermomechanical properties. ACS Appl Polym Mater. 2020; 2(11): 5198-5207. https://doi.org/10.1021/acsapm.0c00954.
  13. Zhang Y, Liu Z, Han Y, et al. Preparation and performance of waterborne polyurethane composite coatings for electromagnetic interference shielding. J Coat Technol Res. 2025;22(3):1079-1086. https:// doi.org/10.1007/s11998-024-01033-z
  14. Chen D, Liu Y, Zhang Z, Li Sh, Yang K, Li Zh. Ingeniously incorporating hollow mesoporous silica into waterborne polyurethane film to improve water vapor permeability. Mat Lett. 2022; 326(1):132994. https://doi.org/10.1016/j.matlet.2022.132994
  15. Pavlicevic J, Spirkova M, Aroguz A, Jovicic M, Kojic D, Govedarica D, Ikonic B. The effect of TiO2 particles on thermal properties of polycarbonate-based polyurethane nanocomposite films. J Thermal Anal Calor.2019;60(1):1-14. https://doi.org/10.1007/s10973 -019-08750-3
  16. Krol P, Szlachta M, Pielichowska K. Hydrophilic and hydrophobic films based on polyurethane cationomers containing TiO2 nanofiller. Prog Org Coat. 2022;162 (1):106524. https://doi.org/10.1016/j.porgcoat.2021. 106524.
  17. Bahramian A. Poly (ethylene terephthalate)-based nanocomposite films as greenhouse covering material: Environmental sustainability, mechanical durability, and thermal stability. J Appl Polym Sci. 2020; 138(1):e49991. https://doi.org/10.1002/app.49991
  18. Pegoretti A, Fambri L, Penati A, Kolarik J. Hydrolytic resistance of model poly(ether urethane ureas) and poly(esterurethane ureas). J Appl Polym Sci. 1998;70(3):577-586. https://doi.org/10.1002/ (SICI)1097-4628(19981017)70:3<577::AID-APP20> 3.0.CO;2-X.
  19. Burgaz E, Kendirlioglu C. Thermomechanical behavior and thermal stability of polyurethane rigid nanocomposite foams containing binary nanoparticle mixtures. Polym Test. 2019;77(1):105930. https:// doi .org/10.1016/j.polymertesting.2019.105930.
  20. Lin Ch-Y, Liao K-H, Su Ch-F, Kuo Ch-H, Hsieh K-H. Smart temperature-controlled water vapor permeable polyurethane film. J Memb Sci. 2007; 299 (1-2):91-96. https://doi.org/10.1016/j.memsci.2007.04. 028.
  21. Li K, Peng J, Zhang M, Heng J, Li D, Mu Ch. Comparative study of the effects of anatase and rutile titanium dioxide nanoparticles on the structure and properties of waterborne polyurethane. Colloid Surf A: Physicochem Eng Asp. 2015; 470(1):92-99. https://doi.org/10.1016/j.colsurfa.2015.01.072.
  22. Rudlong AM, Goddard JM. Synthesis and characterization of hydrophobic and low surface tension polyurethane. Coating. 2023; 13(7):1133. https://doi.org/10.3390/coatings13071133.
  23. Xue M, Ji Y, Ou J, Wang F, Li Ch, Lei Sh, Li W. Surface wettability and strong adhesion of medical polyurethane elastomer porous films by microphase separation. AIP Adv. 2019;9(1):075309. https://doi. org/10.1063/1.5111008.
  24. Mirzadeh S, Asefnejad Az, Khonakda HA, Jafari SH. Improved surface properties in spray-coated PU/TiO2/graphene hybrid nanocomposites through nonsolvent-induced phase separation. Surf Coat Technol. 2021;405(1):126507. https://doi.org/10.1016/ j.surfcoat.2020.126507.
  25. Bhaliya JD, Raju Kutcherlapati SN, Dhore N, Punugupati N, Lekha Sunkara K, Misra S, and Kumar Joshi ShSh, Soybean oil-derived, non-isocyanate polyurethane-TiO2 nanocomposites with enhanced thermal, mechanical, hydrophobic and antimicrobial properties, RSC Sustain. 2025; 3(1):1434-1447. https://doi.org/10.1039/d4su00587b.
  26. Possart W, Zimmer B. Water in Polyurethane Networks: Physical and chemical ageing effects and mechanical parameters. Contin Mech Thermodyn. 2024; 36(1):261-287. https://doi.org/10.1007/s00161-022-01082-y.
  27. Turan D. Water Vapor Transport properties of polyurethane films for packaging of respiring foods. Food Eng Rev. 2019;13(1):54-65. https://doi.org/10. 1007/s12393-019-09205-z
  28. Dolmaire N, Espuche E, Mechin F, Pascault J-P. Water transport properties of thermoplastic polyurethane films. J Polym Sci Part B Polym Phys. 2004; 42(3):473-492. https://doi.org/10.1002/polb. 10708.
  29. Barrie JA, Numm A, Sheer A. The sorption and diffusion of water in polyurethane elastoners. In: Hopfenberg HB, ed. Permeability of Plastic Films and Coatings. pp. 167-168. 1974.
  30. Zisman WA. Relation of the equilibrium contact angle to liquid and solid constitution. Adv Chem. 1964; 9(43):1-51. https://doi.org/10.1021/ba-1964-0043.ch001.
  31. Schmid M, Dallmann K, Bugnicourt E, Cordoni D, Wild F, Lazzeri A, Noller K. Properties of whey-protein-coated films and laminates as novel recyclable food packaging materials with excellent barrier properties. Int J Polym Sci. 2012;1(1):1-7. https://doi .org/10.1155/2012/562381
  32. Crank J. The mathematics of diffusion. 2nd Ed. Clarendon Press, Oxford; 1979.
  33. Deb S, Braden M, Bonfield W. Water absorption characteristics of modified hydroxyapatite bone cements. Biomater. 1995;16(14):1095-1100. https:// doi. org/10.1016/0142-9612(95)98906-U
  34. Zare Y, Study of Nanoparticles aggregation/ agglomeration in polymer particulate nanocomposites by mechanical properties, Composites Part A Appl Sci Manuf. 2016; 84(1):158-164. https://doi.org/10.1016/j. compositesa.2016.01.020.
  35. Wang C, Xu Z, Xia Y, Zhang Ch, Fang H, Sun K. Water transport mechanism and performance evaluation in polyurethane materials: A state-of-the-art review. Polym Test. 2024; 138(1):108554. https:// doi.org/10.1016/j.polymertesting.2024.108554.
  36. Wang Y, Hansen ChJ, Wu Ch-Ch, Robinette EJ, Peterson AM. Effect of surface wettability on the interfacial adhesion of a thermosetting elastomer on glass. RSC Adv. 2021; 11(49):31142-31151. https:// doi.org/10.1039/D1RA05930D.
  37. Alam M, Alandis NM, Zafar F, Sharmin E, Al-Mohammadi YM. Polyurethane-TiO2 nanocomposite coatings from sunflower-oil-based amide diol as soft segment. J. Macromol Sci Part A Chem. 2018;55 (10): 698-708. https://doi.org/10.1080/10601325.2018.149 6945.
  38. Le Gac PY, Choqueuse D, Melot D. Description and modeling of polyurethane hydrolysis used as thermal insulation in oil offshore conditions. Polym Test. 2013;32(8):1588-1593. https://doi.org/10.1016/j. poly-mertesting.2013.09.005.
  39. Jin X, van der Sman RGM, van Maanen JFC. Moisture sorption isotherms of broccoli interpreted with the Flory-Huggins free volume theory. Food Biophys. 2014;9(1):1-9. https://doi.org/10.1007/ s11483- 013-9320-7.
  40. Sui H, Ju X, Liu X, Cheng K, Luo Y, Zhong F. Primary thermal degradation effects on the poly-urethane film. Polym Degrad Stab. 2014;101 (1):109-113. https://doi.org/10.1016/j.polymdegradstab. 2013. 12.023.
  41. Lu Q-W, Macosko ChW, Horrion J. Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene. Macromol Symp. 2003; 198(1):221-232. https://doi.org/10.1002/masy.200351102.
  42. Coutinho FMB, Delpech MC. Degradation profile of films cast from aqueous polyurethane dispersions. Polym Degrad Stab. 2000; 70(1):49-57. https://doi. org/10.1016/S0141-3910(00)00124-0
  43. Zhou H, Liu Y, Lu Y, Tran K. Monitoring the reaction kinetics of waterborne 2-pack polyurethane coatings in the dispersion and during film formation. CJCE 2022;100(4):703-713. https://doi.org/10.1002/ cjce.24287
  44. Branca C, Di Blasi C, Casu A, Morone V. and Costa C, Reaction kinetics and morphological changes of a rigid polyurethane foam during combustion, Thermochim Acta. 2003;399(1-2):127-137. https:// doi. org/10.1016/S0040-6031(02)00455-0.
  45. Somani KP, Patel NK, Kansara SS, Rakshit AK. Effect of chain length of polyethylene glycol and crosslink density (NCO/OH) on properties of castor oil based polyurethane elastomers. Polym Sci Part A: Polym Chem. 2006;43(4-5):797-811. https://doi.org/ 10.1002/pola.20944 .
  46. Morel A, Salaun F, Bedek G, Dupont D, Giraud S. Water vapor permeability of thermosensitive poly-urethane films obtained from isophorone diisocyanate and polyester or polyether polyol. J Mater Sci. 2017; 52(1):1014-1027. https://doi.org/10.1007/s10853-016-0483-8.
  47. da Silva VD, dos Santos LM, Subda SM, Ligabue R, Seferin M, Carone CLP, Einloft S. Synthesis and characterization of polyurethane/titanium dioxide nanocomposites obtained by in situ polymerization. Polym Bull. 2013;70(1):1819-1833. https://doi.org/ 10.1007/s00289-013-0916-6.
  48. kheyrandish M, Bafande F, Sheikh Arabi M, Features and methods of making nanofibers by electrospinning, phase separation and self-assembly, Jorjani Biomedicine J. 2022;10(1):13-25, https://doi.org/10. 29252/ jorjanibiomedj.10.1.13.
  49. Liu Y, Yang L, Ma C, Zhang Y. Thermal behavior of sweet potato starch by non-isothermal thermos-gravimetric analysis. Materials. 2019;12(5):699. https://doi.org/10.3390/ma12050699.
  50. Hakke VS,Landge VK, Sonawane ShH, Uday G, Babu Bh, Ashokkumar M, Erico MM. The physical, mechanical, thermal and barrier properties of starch nanoparticle (SNP)/Polyurethane (PU) nanocomposite films synthesized by an ultrasound-assisted process. Ultrason Sonochem. 2022; 88 (1):106069. https://doi. org/10.1016/j.ultsonch.2021.106069.
  51. Zhang SW, Liu R, Jiang JQ, Yang C, Chen M, Liu XY. Facile Synthesis of Waterborne UV-Curable Polyurethane/Silica Nanocomposites and Morphology, Physical Properties of Its Nanostructured Films. Prog Org Coat. 2011;70(1):1-8. https://doi.org/10.1016/j. porgcoat.2010.09.005
  52. Mergler Y, Schaake R. Relation between strain hardening and wear resistance of polymers, J Appl Polym Sci. 2004;92(1):2689. https://doi.org/10.1002/ app.20251.
  53. Woo SH, Park J, Min BR. Relationship between permeate flux and surface roughness of membranes with similar water contact angle values, Sep Purif Technol. 2015;146(1):187-191. http://dx.doi.org/10. 1016/j.seppur.2015.03.048.
Progress in Color, Colorants and Coatings
Volume 19, Issue 4 - Serial Number 63
October 2026
Pages 485-506

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