Graphene-based coatings on polymer films for gas barrier applications

Abstract We used soluble graphene derivatives to fabricate gas barrier coatings on the surface of several industrially relevant commodity polymers. The coatings are prepared using electrochemically exfoliated graphene oxide, featuring both monoatomic thickness and micron-scale lateral size, showing better gas barrier performance as compared to films of commercial graphene products. A 74% decrease of oxygen transmission rate is found using loadings as low as 0.4 wt. % (0.2 vol. %). The coating process is performed using a combination of solution processing, filtering, and transfer. It is a robust and versatile approach, working with different transfer processes, different starting graphite materials and a wide range of well-known polymeric substrates: poly(ethylene terephthalate), poly(lactic acid), poly(hexamethylene adipamide), poly(propylene), and poly(vinyl chloride). The use of 2D sheets as surface coatings instead of bulk additives overcomes common issues related to dispersion of graphene in a polymer matrix, and gives a clear advantage in preserving the mechanical properties of the bulk polymer. Furthermore, it is a scalable approach able to significantly improve the barrier properties of polymeric films for large-scale applications.

[1]  A. Zanelli,et al.  Graphene: The Exfoliation of Graphene in Liquids by Electrochemical, Chemical, and Sonication‐Assisted Techniques: A Nanoscale Study (Adv. Funct. Mater. 37/2013) , 2013 .

[2]  I. Grigorieva,et al.  Unimpeded Permeation of Water Through Helium-Leak–Tight Graphene-Based Membranes , 2011, Science.

[3]  S L Wong,et al.  Impermeable barrier films and protective coatings based on reduced graphene oxide. , 2014, Nature communications.

[4]  Han-Ik Joh,et al.  Multifunctional polyimide/graphene oxide composites via in situ polymerization , 2014 .

[5]  F. Pilati,et al.  Oxygen permeability of novel organic-inorganic coatings: I. Effects of organic-inorganic ratio and molecular weight of the organic component , 2008 .

[6]  M. Prato,et al.  Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. , 2015, Nanoscale.

[7]  V. Palermo.  Not a molecule, not a polymer, not a substrate… the many faces of graphene as a chemical platform. , 2013, Chemical communications.

[8]  C. Macosko,et al.  Graphene/Polymer Nanocomposites , 2010 .

[9]  J. Coleman,et al.  High-yield production of graphene by liquid-phase exfoliation of graphite. , 2008, Nature nanotechnology.

[10]  M. Melucci,et al.  High-contrast visualization of graphene oxide on dye-sensitized glass, quartz, and silicon by fluorescence quenching. , 2009, Journal of the American Chemical Society.

[11]  Mo Song,et al.  Preparation and characterization of high performance of graphene/nylon nanocomposites , 2013 .

[12]  Jaime C. Grunlan,et al.  Super Gas Barrier and Selectivity of Graphene Oxide‐Polymer Multilayer Thin Films , 2013, Advanced materials.

[13]  Guangsu Huang,et al.  Enhanced mechanical and gas barrier properties of rubber nanocomposites with surface functionalized graphene oxide at low content , 2013 .

[14]  Juin-Yih Lai,et al.  Enhancing polymer/graphene oxide gas barrier film properties by introducing new crystals , 2014 .

[15]  S. Nguyen,et al.  Crumpled Graphene Nanosheets as Highly Effective Barrier Property Enhancers , 2010, Advanced materials.

[16]  Vincenzo Palermo,et al.  Charge transport in graphene–polythiophene blends as studied by Kelvin Probe Force Microscopy and transistor characterization , 2011 .

[17]  R. Mülhaupt,et al.  Functionalized Graphene and Carbon Materials as Components of Styrene‐Butadiene Rubber Nanocomposites Prepared by Aqueous Dispersion Blending , 2014 .

[18]  S. Bose,et al.  Recent advances in graphene based polymer composites , 2010 .

[19]  Jung Kyoo Lee,et al.  Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composites , 2011 .

[20]  M. I. Katsnelson,et al.  Proton transport through one-atom-thick crystals , 2014, Nature.

[21]  L. Ambrosio,et al.  The role of reduced graphene oxide on chemical, mechanical and barrier properties of natural rubber composites , 2014 .

[22]  Dowan Kim,et al.  EVOH nanocomposite films with enhanced barrier properties under high humidity conditions , 2014 .

[23]  A. Zanelli,et al.  The Exfoliation of Graphene in Liquids by Electrochemical, Chemical, and Sonication‐Assisted Techniques: A Nanoscale Study , 2013 .

[24]  R. Ruoff,et al.  Graphene-based polymer nanocomposites , 2011 .

[25]  Dibakar Datta,et al.  Graphene-based environmental barriers. , 2012, Environmental science & technology.

[26]  K. Novoselov,et al.  A roadmap for graphene , 2012, Nature.

[27]  M. Tsai,et al.  Transparent polyimide/graphene oxide nanocomposite with improved moisture barrier property , 2012 .

[28]  R. Menéndez,et al.  Graphene-oxide stacking and defects in few-layer films: Impact of thermal and chemical reduction , 2014 .

[29]  A. Zanelli,et al.  Electrochemically exfoliated graphene oxide/iron oxide composite foams for lithium storage, produced by simultaneous graphene reduction and Fe(OH)3 condensation , 2015 .

[30]  Kunnyun Kim,et al.  A graphene oxide oxygen barrier film deposited via a self-assembly coating method , 2012 .

[31]  J. G. Son,et al.  Spin self-assembly of highly ordered multilayers of graphene-oxide sheets for improving oxygen barrier performance of polyolefin films , 2015 .

[32]  A. Zanelli,et al.  Synergic Exfoliation of Graphene with Organic Molecules and Inorganic Ions for the Electrochemical Production of Flexible Electrodes. , 2014, ChemPlusChem.

[33]  Luda Wang,et al.  Selective molecular sieving through porous graphene. , 2012, Nature nanotechnology.

[34]  I. V. Grigorieva,et al.  Precise and Ultrafast Molecular Sieving Through Graphene Oxide Membranes , 2014, Science.

[35]  H. Park,et al.  Graphene and graphene oxide and their uses in barrier polymers , 2014 .