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Thermal barrier enhancement of calcium carbonate coatings with nanoparticle additives, and their effect on hydrophobicity

  • Brenda Hutton-PragerEmail author
  • Mohammed Mustafees Khan
  • Clinton Gentry
  • Charlie Brandon Knight
  • Anas Khalaf Anas Al-Abri
Original Research


Nano-TiO2, nanoclay, and cellulose nanocrystals (CNC) were each introduced into calcium carbonate coatings common in paper/paperboard applications, to investigate improvements in thermal barrier performance and hydrophobicity. An in-house apparatus was built in which the temperature was measured on both sides of a coated cellulose substrate in the presence of a constant, applied thermal load. Hence, a temperature difference (ΔT) across the coated substrate was recorded for each coated sample. Thermal conductivity (k), contact angle (CA) and critical surface energy (σc) of the coated samples were also measured. In all cases, the presence of the nanoparticle (NP) additives to the calcium carbonate coatings improved the thermal barrier performance (increased ΔT and reduced k), and showed mild enhancement in the CA compared with coated samples that did not have NP added to the coating. Specifically, with the introduction of 2% CNC into the calcium carbonate coating, ΔT increased by 28.3 °C; k reduced by 0.0142 W/m K; and CA increased by 23°. The effects of thermal load application on the coated sample caused an increase in surface porosity of 7% and a reduction in σc by 13.0 mN/m, potentially indicating a loss of mechanical integrity. Thermal barrier and hydrophobic improvements were less successful with nanoclay additions to the calcium carbonate coatings, however the σc remained constant after thermal load application, indicating a more robust surface against applied heat. This study adds significant information to the little-studied field of thermal barrier improvements to paper coatings for food packaging applications.


Thermal barrier Nanoparticles CNC Paper coating Food packaging 



The authors gratefully acknowledge funding of this work by a NASA Seed grant, award #NNX15AH78H, 01/01/2017–09/31/2018, and USDA NIFA, award # 2018-67022-27972, 06/01/2018–05/31/2020.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Arbatan T, Zhang L, Fang X-Y, Shen W (2012) Cellulose nanofibers as binder for fabrication of superhydrophobic paper. Chem Eng J 210:74–79. CrossRefGoogle Scholar
  2. Balu B, Breedveld V, Hess DW (2008) Fabrication of “roll-off” and “sticky” superhydrophobic cellulose surfaces via plasma processing. Langmuir 24(9):4785–4790. CrossRefGoogle Scholar
  3. Diaz JA, Ye Z, Wu X, Moore AL, Moon RJ, Martini A, Boday DJ, Youngblood JP (2014) Thermal conductivity in nanostructured films: from single cellulose nanocrystals to bulk films. Biomacromol 15(11):4096–4101. CrossRefGoogle Scholar
  4. Dogome K, Enomae T, Isogai A (2013) Method for controlling surface energies of paper substrates to create paper-based printed electronics. Chem Eng Process 68:21–25. CrossRefGoogle Scholar
  5. Drummond AF, Varajao C, Gilkes RJ, Hart RD (2001) The relationships between kaolinite crystal properties and the origin of materials for a brazilian kaolin deposit. Clays Miner 49(1):44–59CrossRefGoogle Scholar
  6. Ferrández-Rives M, Beltrán-Osuna Á, Gómez-Tejedor J, Gómez Ribelles J (2017) Electrospun PVA/bentonite nanocomposites mats for drug delivery. Materials 10(12):1448. CrossRefGoogle Scholar
  7. Fu B, Tang G, Li Y (2017) Electron–phonon scattering effect on the lattice thermal conductivity of silicon nanostructures. Phys Chem Chem Phys 19(42):28517–28526. CrossRefGoogle Scholar
  8. Gao T, Jelle BP (2013) Thermal conductivity of TiO2 nanotubes. J Phys Chem C 117(3):1401–1408. CrossRefGoogle Scholar
  9. Ghule K, Ghule AV, Chen B-J, Ling Y-C (2006) Preparation and characterization of ZnO nanoparticles coated paper and its antibacterial activity study. Green Chem 8(12):1034. CrossRefGoogle Scholar
  10. Gottesman R, Shukla S, Perkas N, Solovyov LA, Nitzan Y, Gedanken A (2011) Sonochemical coating of paper by microbiocidal silver nanoparticles. Langmuir 27(2):720–726. CrossRefGoogle Scholar
  11. Holman JP (2010) Heat transfer, 10th edn. McGraw Hill Higher Education, BostonGoogle Scholar
  12. Hubbe MA, Ferrer A, Tyagi P, Yin Y, Salas C, Pal L, Rojas OJ (2017) Nanocellulose in thin films, coatings, and plies for packaging applications: a review. BioResources 12(1):2142–2233CrossRefGoogle Scholar
  13. Hutton BH, Parker IH (2008) Immediate consolidation behaviour of aqueous pigment coatings applied to porous substrates. Chem Eng Sci 63(13):3348–3357. CrossRefGoogle Scholar
  14. Jamshidi S, Sundararaj U (2015) Improvement of barrier properties of rotomolded PE containers with nanoclay (p. 070014). Presented at the PROCEEDINGS OF PPS-30: the 30th International Conference of the Polymer Processing Society—Conference Papers, Cleveland, Ohio, USA.
  15. Jiménez-Pérez JL, Gutiérrez Fuentes R, Sánchez-Sosa R, Zapata Torres MG, Correa-Pacheco ZN, Sánchez Ramírez JF (2015) Thermal diffusivity study of nanoparticles and nanorods of titanium dioxide (TiO2) and titanium dioxide coated with cadmium sulfide (TiO2CdS). Mater Sci Semicond Process 37:62–67. CrossRefGoogle Scholar
  16. Kabza K, Gestwicki JE, McGrath JL (2000) Contact angle goniometry as a tool for surface tension measurements of solids, using Zisman plot method. J Chem Educ 77(1):63–65CrossRefGoogle Scholar
  17. Karapanagiotis I, Grosu D, Aslanidou D, Aifantis KE (2015) Facile method to prepare superhydrophobic and water repellent cellulosic paper. J Nanomater 2015:1–9. CrossRefGoogle Scholar
  18. Kiefer J, Rasul NH, Ghosh PK, von Lieres E (2014) Surface and bulk porosity mapping of polymer membranes using infrared spectroscopy. J Membr Sci 452:152–156. CrossRefGoogle Scholar
  19. Lee W, Kang PK, Kim AS, Lee S (2018) Impact of surface porosity on water flux and structural parameter in forward osmosis. Desalination 439:46–57. CrossRefGoogle Scholar
  20. Mahalik N (2014) Advances in packaging methods, processes and systems. Challenges 5(2):374–389. CrossRefGoogle Scholar
  21. Martínez-Abad A, Lagaron JM, Ocio MJ (2012) Development and characterization of silver-based antimicrobial ethylene-vinyl alcohol copolymer (EVOH) films for food-packaging applications. J Agric Food Chem 60(21):5350–5359. CrossRefGoogle Scholar
  22. McLaren C (2005) Heat stress from enclosed vehicles: moderate ambient temperatures cause significant temperature rise in enclosed vehicles. Pediatrics 116(1):e109–e112. CrossRefGoogle Scholar
  23. Mohamed AMA, Abdullah AM, Younan NA (2015) Corrosion behavior of superhydrophobic surfaces: a review. Arab J Chem 8(6):749–765. CrossRefGoogle Scholar
  24. Nazir MS, Mohamad Kassim MH, Mohapatra L, Gilani MA, Raza MR, Majeed K (2016) Characteristic properties of nanoclays and characterization of nanoparticulates and nanocomposites. In: Jawaid M, el K. Qaiss A, Bouhfid R (eds) Nanoclay reinforced polymer composites. Springer Singapore, Singapore, pp 35–55. CrossRefGoogle Scholar
  25. Nemati M, Khademi Eslam H, Talaeipour M, Bazyar B, Samariha A (2016) Effect of nanoclay on flammability behavior and morphology of nanocomposites from wood flour and polystyrene materials. BioResources 11(1):748–758Google Scholar
  26. Rawat K, Agarwal S, Tyagi A, Verma AK, Bohidar HB (2014) Aspect ratio dependent cytotoxicity and antimicrobial properties of nanoclay. Appl Biochem Biotechnol 174(3):936–944. CrossRefGoogle Scholar
  27. Roy S, Junk M, Sundar S (2006) Understanding the porosity dependence of heat flux through glass fiber insulation. Math Comput Model 43(5–6):485–492. CrossRefGoogle Scholar
  28. Rutter T, Hutton-Prager B (2018) Investigation of hydrophobic coatings on cellulose-fiber substrates with in situ polymerization of silane/siloxane mixtures. Int J Adhes Adhes 86:13–21. CrossRefGoogle Scholar
  29. Sanchez-Garcia MD, Lopez-Rubio A, Lagaron JM (2010) Natural micro and nanobiocomposites with enhanced barrier properties and novel functionalities for food biopackaging applications. Trends Food Sci Technol 21(11):528–536. CrossRefGoogle Scholar
  30. Sand A, Kniivilä J, Toivakka M, Hjelt T (2011) Structure formation mechanisms in consolidating pigment coatings—simulation and visualisation. Chem Eng Process 50(5–6):574–582. CrossRefGoogle Scholar
  31. Shen T, Gnanakaran S (2009) The stability of cellulose: a statistical perspective from a coarse-grained model of hydrogen-bond networks. Biophys J 96(8):3032–3040. CrossRefGoogle Scholar
  32. Sigma-Aldrich (n.d.) Whatman (R) qualitative filter paper, Grade 1. Retrieved November 6, 2018, from
  33. Sofla MRK, Brown RJ, Tsuzuki T, Rainey TJ (2016) A comparison of cellulose nanocrystals and cellulose nanofibres extracted from bagasse using acid and ball milling methods. Adv Nat Sci Nanosci Nanotechnol 7(3):035004. CrossRefGoogle Scholar
  34. Sothornvit R, Rhim J-W, Hong S-I (2009) Effect of nano-clay type on the physical and antimicrobial properties of whey protein isolate/clay composite films. J Food Eng 91(3):468–473. CrossRefGoogle Scholar
  35. Sui J, Zheng L, Zhang X, Chen Y, Cheng Z (2016) A novel equivalent agglomeration model for heat conduction enhancement in nanofluids. Sci Rep 6(1):19560. CrossRefGoogle Scholar
  36. Tian X, Li Y, Wan S, Wu Z, Wang Z (2017) Functional surface coating on cellulosic flexible substrates with improved water-resistant and antimicrobial properties by use of ZnO nanoparticles. J Nanomater 2017:1–9. CrossRefGoogle Scholar
  37. Timofeeva EV, Gavrilov AN, McCloskey JM, Tolmachev YV, Sprunt S, Lopatina LM, Selinger JV (2007) Thermal conductivity and particle agglomeration in alumina nanofluids: experiment and theory. Phys Rev E 76(6):061203. CrossRefGoogle Scholar
  38. Tomić MD, Dunjić B, Likić V, Bajat J, Rogan J, Djonlagić J (2014) The use of nanoclay in preparation of epoxy anticorrosive coatings. Prog Org Coat 77(2):518–527. CrossRefGoogle Scholar
  39. Uddin F (2008) Clays, nanoclays, and montmorillonite minerals. Metall Mater Trans A 39(12):2804–2814. CrossRefGoogle Scholar
  40. Vazquez G, Alvarez E, Navaza JM (1995) Surface tension of alcohol + water from 20 to 50 °C. J Chem Eng Data 40:611–614CrossRefGoogle Scholar
  41. Yahiaoui F, Benhacine F, Ferfera-Harrar H, Habi A, Hadj-Hamou AS, Grohens Y (2015) Development of antimicrobial PCL/nanoclay nanocomposite films with enhanced mechanical and water vapor barrier properties for packaging applications. Polym Bull 72(2):235–254. CrossRefGoogle Scholar
  42. Zhang W, Lu P, Qian L, Xiao H (2014) Fabrication of superhydrophobic paper surface via wax mixture coating. Chem Eng J 250:431–436. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of Chemical EngineeringThe University of MississippiUniversityUSA

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