In modulus measurement by depth-sensing indentation, previous considerations assume elastic recovery to be the sole process during unloading, but in reality creep and thermal drift may also occur, causing serious errors in the measured modulus. In this work, the problem of indentation on a linear viscoelastic half-space is solved using the correspondence principle between elasticity and linear viscoelasticity. The correction term due to creep in the apparent contact compliance is found to be equal to the ratio of the indenter displacement rate at the end of the load hold to the unloading rate. A condition for nullifying the effect of thermal drift on modulus measurement is also proposed. With this condition satisfied, the effect of thermal drift on the calculated modulus is negligible irrespective of the magnitude of the drift rate.

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Polymer nanocomposite films (PNCFs) with extremely high concentrations of nanoparticles are important components in energy storage and conversion devices and also find use as protective coatings in various applications. PNCFs with high loadings of nanoparticles, however, are difficult to prepare because of the poor processability of polymer-nanoparticle mixtures with high concentrations of nanoparticles even at an elevated temperature. This problem is exacerbated when anisotropic nanoparticles are the desired filler materials. Here we report a straightforward method for generating PNCFs with extremely high loadings of nanoparticles. Our method is based on what we call capillary rise infiltration (CaRI) of polymer into a dense packing of nanoparticles. CaRI consists of two simple steps: (1) the preparation of a two-layer film, consisting of a porous layer of nanoparticles and a layer of polymer and (2) annealing of the bilayer structure above the temperature that imparts mobility to the polymer (e.g., glass transition of the polymer). The second step leads to polymer infiltration into the interstices of the nanoparticle layer, reminiscent of the capillary rise of simple fluid into a narrow capillary or a packing of granules. We use in situ spectroscopic ellipsometry and a three-layer Cauchy model to follow the capillary rise of polystyrene into the random network of nanoparticles. The infiltration of polystyrene into a densely packed TiO2 nanoparticle layer is shown to follow the classical Lucas-Washburn type of behaviour. We also demonstrate that PNCFs with densely packed anisotropic TiO2 nanoparticles can be readily generated by spin coating anisotropic TiO2 nanoparticles atop a polystyrene film and subsequently thermally annealing the bilayer film. We show that CaRI leads to PNCFs with modulus, hardness and scratch resistance that are far superior to the properties of films of the component materials. In addition, CaRI fills in cracks that may exist in the nanoparticle layer, leading to the healing of nanoparticle films and the formation of defect-free PNCFs. We believe this approach is widely applicable for the preparation of PNCFs with extremely high loading of nanoparticles and potentially provides a unique approach to study capillarity-induced transport of polymers under extreme confinement.

A nanoindenter XP with scanning capabilities was used to perform nanoindentations on GaN and ZnO nanowires with radii in the range of 20–50nm, positioned on a silicon substrate and bonded to the substrate at their ends with platinum. Since the geometry of indentation of a nanowire differs significantly from the indentation of a half-space, the standard Oliver-Pharr method [W. C. Oliver and G. M. Pharr, J. Mater. Res. 7, 1564 (1992)] of analysis may not be used. A two interface contact model has been developed for the nanoindentation of a nanowire on a flat substrate, with the two interfaces, indenter/nanowire and nanowire/substrate, being in a series. The contact at the indenter/nanowire interface is modeled as an elliptical contact at the sphere (indenter)/cylinder interface. The contact at the nanowire/substrate interface is modeled as a contact at the cylinder/half-space interface under some concentrated forces applied on top of the cylinder. Under these latter conditions the cylinder may be expected to recede from the half-space when the load is applied. In order to predict the contact stiffness for the two interfaces, the theories of Hertzian contacts and receding contacts have been reviewed, generalized, and used. Considering the possible adhesion at the nanowire/substrate interface and the fixed ends of the nanowire, we have considered two limits for the contact at the nanowire/substrate interface: one with and one without separation at the interface; thus, we obtain two bounds for the contact stiffness and hardness. The model has been used to analyze the nanoindentation data for GaN and ZnO nanowires. We found that the hardness of the GaN nanowire is 46.7±5.6GPa, which is much higher than that of the ZnO nanowire, 3.4±0.9GPa. We also found that the Oliver-Pharr hardness [W. C. Oliver and G. M. Pharr, J. Mater. Res. 7, 1564 (1992)] may be the rough lower bound of the hardness and the Joslin-Oliver hardness [D. L. Joslin and W. C. Oliver, J. Mater. Res. 5, 123 (1990)] may be the rough upper bound of the hardness.

Obtaining quantitative electrical information with scanning probe microscopy techniques poses a significant challenge since the nature of the probe/sample contact is frequently unkown. For example, obtaining quantitative kinetic data from the recently developed atomic force microscopy (AFM) impedance technique requires normalization by the probe/sample contact area. In this paper, a methodology is proposed that enables the extraction of quantitative information from the AFM impedance technique. This methodology applies results from nanoindentation experiments and contact mechanics theory to characterize AFM probe contacts. Using these results, probe/sample contact forces (which can be accurately measured in the AFM) may be converted into probe/sample contact area estimates. These contact area estimates, when included in model of the probe/sample contact, enable the extraction of quantitative data. This methodology is applied to the recently developed AFM impedance measurement technique, enabling a quantitative study of the oxygen reduction reaction (ORR) at nanometer length scales. Using the AFM impedance system, kinetic data for the (ORR) at nanoscale Platinum/Nafion contacts is extracted. The kinetic data obtained from the AFM impedance technique match previous bulk measurements—affirming the technique’s quantitative potential.

Alternating tangential flow (ATF) filtration has been used with success in the Biopharmaceutical industry as a lower shear technology for cell retention with perfusion cultures. The ATF system is different than tangential flow filtration; however, in that reverse flow is used once per cycle as a means to minimize fouling. Few studies have been reported in the literature that evaluates ATF and how key system variables affect the rate at which ATF filters foul. In this study, an experimental setup was devised that allowed for determination of the time it took for fouling to occur for given mammalian (PER.C6) cell culture cell densities and viabilities as permeate flow rate and antifoam concentration was varied. The experimental results indicate, in accordance with D'Arcy's law, that the average resistance to permeate flow (across a cycle of operation) increases as biological material deposits on the membrane. Scanning electron microscope images of the post-run filtration surface indicated that both cells and antifoam micelles deposit on the membrane. A unique mathematical model, based on the assumption that fouling was due to pore blockage from the cells and micelles in combination, was devised that allowed for estimation of sticking factors for the cells and the micelles on the membrane. This model was then used to accurately predict the increase in transmembane pressure during constant flux operation for an ATF cartridge used for perfusion cell culture.