Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications.

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

Quantification of the Mass and Viscoelasticity of Interfacial Films on Tin Anodes Using EQCM-D.

Electrochemical quartz crystal microbalance coupled with dissipation (EQCM-D) is employed to investigate the solid electrolyte interphase (SEI) formation and Li insertion/deinsertion into thin film electrodes of tin. Based on the frequency change we find that the initial SEI formation process is rapid before Li insertion but varies significantly with increasing concentration of the additive fluoroethylene carbonate (FEC) in the electrolyte. The extent of dissipation, which represents the film rigidity, increases with cycle number, reflecting film thickening and softening. Dissipation values are almost twice as large in the baseline electrolyte (1.2 M LiPF6 in 3:7 wt % ethylene carbonate:ethyl methyl carbonate), indicating the film in baseline electrolyte is roughly twice as soft as in the FEC-containing cells. More importantly, we detail how quantitative data about mass, thickness, shear elastic modulus, and shear viscosity in a time-resolved manner can be obtained from the EQCM-D response. These parameters were extracted from the frequency and dissipation results at multiple harmonics using the Sauerbrey and Voigt viscoelastic models. From these modeled results we show the dynamic mass changes for each half cycle. We also demonstrate that different amounts of FEC additive influence the SEI formation behavior and result in differences in the estimated mass, shear modulus and viscosity. After three cycles, the film in baseline electrolyte exhibits a 1.2 times larger mass change compared with the film in the FEC-containing electrolyte. The shear elastic modulus of films formed in the presence of FEC is larger than in the baseline electrolyte at early stages of lithiation. Also with lithiation is a marked increase in film viscosity, which together point to a much stiffer and more homogeneous SEI formed in the presence of FEC.

Characterization of surface modifications by white light interferometry: applications in ion sputtering, laser ablation, and tribology experiments.

In materials science and engineering it is often necessary to obtain quantitative measurements of surface topography with micrometer lateral resolution. From the measured surface, 3D topographic maps can be subsequently analyzed using a variety of software packages to extract the information that is needed. In this article we describe how white light interferometry, and optical profilometry (OP) in general, combined with generic surface analysis software, can be used for materials science and engineering tasks. In this article, a number of applications of white light interferometry for investigation of surface modifications in mass spectrometry, and wear phenomena in tribology and lubrication are demonstrated. We characterize the products of the interaction of semiconductors and metals with energetic ions (sputtering), and laser irradiation (ablation), as well as ex situ measurements of wear of tribological test specimens. Specifically, we will discuss: i. Aspects of traditional ion sputtering-based mass spectrometry such as sputtering rates/yields measurements on Si and Cu and subsequent time-to-depth conversion. ii. Results of quantitative characterization of the interaction of femtosecond laser irradiation with a semiconductor surface. These results are important for applications such as ablation mass spectrometry, where the quantities of evaporated material can be studied and controlled via pulse duration and energy per pulse. Thus, by determining the crater geometry one can define depth and lateral resolution versus experimental setup conditions. iii. Measurements of surface roughness parameters in two dimensions, and quantitative measurements of the surface wear that occur as a result of friction and wear tests. Some inherent drawbacks, possible artifacts, and uncertainty assessments of the white light interferometry approach will be discussed and explained.

Modeling of adhesion in tablet compression--I. Atomic force microscopy and molecular simulation.

Adhesion problems during tablet manufacturing have been observed to be dependent on many formulation and process factors including the run time on the tablet press. Consequently, problems due to sticking may only become apparent towards the end of the development process when a prolonged run on the tablet press is attempted for the first time. It would be beneficial to predict in a relative sense if a formulation or new chemical entity has the potential for adhesion problems early in the development process. It was hypothesized that favorable intermolecular interaction between the drug molecules and the punch face is the first step or criterion in the adhesion process. Therefore, the rank order of adhesion during tablet compression should follow the rank order of these energies of interaction. The adhesion phenomenon was investigated using molecular simulations and contact mode atomic force microscopy (AFM). Three model compounds were chosen from a family of "profen" compounds. Silicon nitride AFM tips were modified by coating a 20-nm iron layer on the surfaces by sputter coating. Profen flat surfaces were made by melting and recrystallization. The modified AFM probe and each profen surface were immersed in the corresponding profen saturated water during force measurements using AFM. The work of adhesion between iron and ibuprofen, ketoprofen, and flurbiprofen in vacuum were determined to be -184.1, -2469.3, -17.3 mJ. m(-2), respectively. The rank order of the work of adhesion between iron and profen compounds decreased in the order: ketoprofen > ibuprofen > flurbiprofen. The rank order of interaction between the drug molecules and the iron superlattice as predicted by molecular simulation using Cerius(2) is in agreement with the AFM measurements. It has been demonstrated that Atomic Force Microscopy is a powerful tool in studying the adhesion phenomena between organic drug compounds and metal surface. The study has provided insight into the adhesion problems occurring during tablet compression and a direction for continued study.