We study the mechanics of pressurized graphene membranes using an experimental configuration that allows the determination of the elasticity of graphene and the adhesion energy between a substrate and a graphene (or other two-dimensional solid) membr
ane. The test consists of a monolayer graphene membrane adhered to a substrate by surface forces. The substrate is patterned with etched microcavities of a prescribed volume and when they are covered with the graphene monolayer it traps a fixed number (N) of gas molecules in the microchamber. By lowering the ambient pressure, and thus changing the pressure difference across the graphene membrane, the membrane can be made to bulge and delaminate in a stable manner from the substrate. Here we describe the analysis of the membrane/substrate as a thermodynamic system and explore the behavior of the system over representative experimentally-accessible geometry and loading parameters. We carry out companion experiments and compare them to the theoretical predictions and then use the theory and experiments together to determine the adhesion energy of graphene/SiO2 interfaces. We find an average adhesion energy of 0.24 J/m2 which is lower, but in line with our previously reported values. We assert that this test, which we call the constant N blister test, is a valuable approach to determine the adhesion energy between two-dimensional solid membranes and a substrate, which is an important, but not well-understood aspect of behavior. The test also provides valuable information that can serve as the basis for subsequent research to understand the mechanisms contributing to the observed adhesion energy. Finally, we show how in the limit of a large microcavity, the constant N test approaches the behavior observed in a constant pressure blister test and we provide an experimental observation that suggests this behavior.
Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robu
st to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size selective membranes because of its atomic thickness, high mechanical strength, relative inertness, and impermeability to all standard gases. However, pores that can exclude larger molecules, but allow smaller molecules to pass through have to be introduced into the material. Here we show UV-induced oxidative etching can create pores in micrometre-sized graphene membranes and the resulting membranes used as molecular sieves. A pressurized blister test and mechanical resonance is used to measure the transport of a variety of gases (H2, CO2, Ar, N2, CH4, and SF6) through the pores. The experimentally measured leak rates, separation factors, and Raman spectrum agree well with models based on effusion through a small number of angstrom-sized pores.
As mechanical structures enter the nanoscale regime, the influence of van der Waals forces increases. Graphene is attractive for nanomechanical systems because its Youngs modulus and strength are both intrinsically high, but the mechanical behavior o
f graphene is also strongly influenced by the van der Waals force. For example, this force clamps graphene samples to substrates, and also holds together the individual graphene sheets in multilayer samples. Here we use a pressurized blister test to directly measure the adhesion energy of graphene sheets with a silicon oxide substrate. We find an adhesion energy of 0.45 pm 0.02 J/m2 for monolayer graphene and 0.31 pm 0.03 J/m2 for samples containing 2-5 graphene sheets. These values are larger than the adhesion energies measured in typical micromechanical structures and are comparable to solid/liquid adhesion energies. We attribute this to the extreme flexibility of graphene, which allows it to conform to the topography of even the smoothest substrates, thus making its interaction with the substrate more liquid-like than solid-like.
