Thin films formed by atomic layer deposition (ALD) are being examined for a variety of chemical protection and diffusion barrier applications, yet their stability in various fluid environments is not well characterized. The chemical stability of titania and alumina thin films in air, 18 MΩ water, 1 M KCl, 1 M HNO3, 1 M H2SO4, 1 M HCl, 1 M KOH, and mercury was studied. Films were deposited at 150 °C using trimethylaluminum-H2O and tetrakis(dimethylamido)titanium-H2O chemistries for alumina and titania, respectively. A subset of samples were heated to 450 and 900 °C in inert atmosphere. Films were examined using spectroscopic ellipsometry, atomic force microscopy, optical microscopy, scanning electron microscopy, and X-ray diffraction. Notably, alumina samples were found to be unstable in pure water, acid, and basic environments in the as-synthesized state and after 450 °C thermal treatment. In pure water, a dissolution-precipitation mechanism is hypothesized to cause surface roughening. The stability of alumina films was greatly enhanced after annealing at 900 °C in acidic and basic solutions. Titania films were found to be stable in acid after annealing at or above 450 °C. All films showed a composition-independent increase in measured thickness when immersed in mercury. These results provide stability-processing relationships that are important for controlled etching and protective barrier layers.

Microfluidic systems that leverage unique micro-scale phenomena have been developed to provide rapid, accurate and robust analysis, predominantly for biomedical applications. These attributes, in addition to the ability to access high temperatures and pressures, have motivated recent expanded applications in phase measurements relevant to industrial CO, oil and gas applications. We here present a comprehensive review of this exciting new field, separating microfluidic and nanofluidic approaches. Microfluidics is practical, and provides similar phase properties analysis to established bulk methods with advantages in speed, control and sample size. Nanofluidic phase behaviour can deviate from bulk measurements, which is of particular relevance to emerging unconventional oil and gas production from nanoporous shale. In short, microfluidics offers a practical, compelling replacement of current bulk phase measurement systems, whereas nanofluidics is not practical, but uniquely provides insight into phase change phenomena at nanoscales. Challenges, trends and opportunities for phase measurements at both scales are highlighted.

Thermoresponsive microgels with a hollow capsule architecture have been widely used in drug delivery and molecular encapsulation, and their efficacy is contingent on the internal structure in the deswelling dynamics process. Despite a large number of experimental studies on microgels, proper theoretical methods based on an individual microgel capsule are still a few because of the complexity of the microgels. Herein, we first propose a novel methodology to investigate the structural properties and deswelling dynamics of microgel capsules by integrating a temperature-dependent Morse potential with Langevin dynamics simulation. Different properties, including volume phase transition temperature, temperature-dependent diameter, and structural morphologies of individual microgels, are assessed to rationalize our simulation method, and a good agreement between simulation predictions and experimental observations has been obtained. Depending on the system temperature, the morphological transition of three regimes in the shell structure is identified: scattered nanogels, progressively porous sponge gels, and dense ribbonlike gels. The temperature-switchable sensors composed of microgel capsules on the substrates are devised, which exhibit tunable reflectivity or thickness by simply varying the system temperature. Our mesoscale results provide helpful insights into the transient structure within the networked microgels and the design of smart polymeric nanomaterials, such as biosensors, drug delivery systems, and actuators.

Phase change at the nanoscale is at the heart of many biological and geological phenomena. The recent emergence and global implications of unconventional oil and gas production from nanoporous shale further necessitate a higher understanding of phase behavior at these scales. Here, we directly observe condensation and condensate growth of a light hydrocarbon (propane) in discrete sub-100 nm (∼70 nm) channels. Two different condensation mechanisms at this nanoscale are distinguished, continuous growth and discontinuous growth due to liquid bridging ahead of the meniscus, both leading to similar net growth rates. The growth rates agree well with those predicted by a suitably defined thermofluid resistance model. In contrast to phase change at larger scales (∼220 and ∼1000 nm cases), the rate of liquid condensate growth in channels of sub-100 nm size is found to be limited mainly by vapor flow resistance (∼70% of the total resistance here), with interface resistance making up the difference. The condensation-induced vapor flow is in the transitional flow regime (Knudsen flow accounting for up to 13% of total resistance here). Collectively, these results demonstrate that with confinement at sub-100 nm scales, such as is commonly found in porous shale and other applications, condensation conditions deviate from the microscale and larger bulk conditions chiefly due to vapor flow and interface resistances.