title: Thermodynamic and structural insights into nanocomposites engineering by comparing two materials assembly techniques for graphene.
abstract: Materials assembled by layer-by-layer (LBL) assembly and vacuum-assisted flocculation (VAF) have similarities, but a systematic study of their comparative advantages and disadvantages is missing. Such a study is needed from both practical and fundamental perspectives aiming at a better understanding of structure-property relationships of nanocomposites and purposeful engineering of materials with unique properties. Layered composites from polyvinyl alcohol (PVA) and reduced graphene (RG) are made by both techniques. We comparatively evaluate their structure, mechanical, and electrical properties. LBL and VAF composites demonstrate clear differences at atomic and nanoscale structural levels but reveal similarities in micrometer and submicrometer organization. Epitaxial crystallization and suppression of phase transition temperatures are more pronounced for PVA in LBL than for VAF composites. Mechanical properties are virtually identical for both assemblies at high RG contents. We conclude that mechanical properties in layered RG assemblies are largely determined by the thermodynamic state of PVA at the polymer/nanosheet interface rather than the nanometer scale differences in RG packing. High and nearly identical values of toughness for LBL and VAF composites reaching 6.1 MJ/m(3) observed for thermodynamically optimal composition confirm this conclusion. Their toughness is the highest among all other layered assemblies from RG, cellulose, clay, etc. Electrical conductivity, however, is more than 10× higher for LBL than for VAF composites for the same RG contents. Electrical properties are largely determined by the tunneling barrier between RG sheets and therefore strongly dependent on atomic/nanoscale organization. These findings open the door for application-oriented methods of materials engineering using both types of layered assemblies.
authors: Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, USA.
authors: Jian
authors: J
authors: Zhu
authors: Huanan
authors: H
authors: Zhang
authors: Nicholas A
authors: NA
authors: Kotov
mesh_terms: D004560:Electricity; D004738:Engineering / Q000379:methods*; D006108:Graphite / Q000737:chemistry*; D055595:Mechanical Phenomena; D008958:Models, Molecular; D008968:Molecular Conformation; D053761:Nanocomposites / Q000737:chemistry*; D036103:Nanotechnology / Q000379:methods*; D011142:Polyvinyl Alcohol / Q000737:chemistry; D013696:Temperature; D013816:Thermodynamics; D014618:Vacuum
chemical_list: D006108:Graphite; D011142:Polyvinyl Alcohol