The zeta potential of planar sapphire substrates for three different crystallographic orientations was measured by a streaming potential technique in the presence of KCl and (CH3)4NCl electrolytes. The streaming potential was measured for large single crystalline C-plane (0001), A-plane (1120), and R-plane (1102) wafers over a full pH range at three or more ionic strengths ranging from 1 to 100 mM. The roughness of the epi-polished wafers was verified using atomic force microscopy to be on the order of atomic scale, and X-ray photoelectron spectroscopy (XPS) was used to ensure that the samples were free of silica and other contaminants. The results reveal a shift in the isoelectric point (iep) of the three samples by as much as two pH units, with the R-plane surface exhibiting the most acidic behavior and the C-plane samples having the highest iep. The iep at all ionic strengths was tightly centered around a single pH for each wafer. These values of iep are substantially different from the range of pH 8-10 consistently reported in the literature for alpha-Al2O3 particles. Particle zeta potential measurements were performed on a model powder using phase analysis light scattering, and the iep was confirmed to occur at pH 8. Modified Auger parameters (MAP) were calculated from XPS spectra of a monolayer of iridium metal deposited on the sapphire by electron beam deposition. A shift in MAP consistent with the observed differences in iep of the surfaces confirms the effect of surface structure on the transfer of charge between the Ir and sapphire, hence accounting for the changes in acidity as a function of crystallographic orientation.
The electroosmotic behavior of the rutile polymorph of titanium dioxide was explored as a function of the crystallographic orientation. Atomic force microscopy (AFM) was employed to make high-resolution force spectroscopy measurements between a silica sphere attached to a traditional, contact-mode AFM cantilever and TiO2(110), TiO2(100), and TiO2(001) surfaces in aqueous solutions. Measurements were taken in multiple solution conditions across a broad range of pH values, and the resultant force-distance curves were used to deduce relative behaviors of each orientation of rutile, with particular interest in changes of the isoelectric point (iep). Differences in the iep as a function of orientation are explained in terms of differences in both the coordination number and density of acidic and basic sites on the surface. The results were supported by angle-resolved X-ray photoelectron spectroscopy (XPS) measurements of a nominal monolayer of palladium metal deposited on each of the three orientations studied. The palladium monolayer served as a means of probing the relative electron affinities of the three surfaces studied, which were exhibited in shifts of the palladium XPS peak that corresponded to differences in the binding energy as a function of the substrate orientation. The correlation between the rutile orientation and the shift in the palladium binding energy corresponded directly to the relationship between the isoelectric point and the orientation, with the surface of lowest isoelectric point exhibiting the highest Pd binding energy.
Optimized physical properties (e.g., bulk, surface/interfacial, and mechanical properties) of active pharmaceutical ingredients (APIs) are key to the successful integration of drug substance and drug product manufacturing, robust drug product manufacturing operations, and ultimately to attaining consistent drug product critical quality attributes. However, an appreciable number of APIs have physical properties that cannot be managed via routes such as form selection, adjustments to the crystallization process parameters, or milling. Approaches to control physical properties in innovative ways offer the possibility of providing additional and unique opportunities to control API physical properties for both batch and continuous drug product manufacturing, ultimately resulting in simplified and more robust pharmaceutical manufacturing processes. Specifically, diverse opportunities to significantly enhance API physical properties are created if allowances are made for generating co-processed APIs by introducing nonactive components (e.g., excipients, additives, carriers) during drug substance manufacturing. The addition of a nonactive coformer during drug substance manufacturing is currently an accepted approach for cocrystals, and it would be beneficial if a similar allowance could be made for other nonactive components with the ability to modify the physical properties of the API. In many cases, co-processed APIs could enable continuous direct compression for small molecules, and longer term, this approach could be leveraged to simplify continuous end-to-end drug substance to drug product manufacturing processes for both small and large molecules. As with any novel technology, the regulatory expectations for co-processed APIs are not yet clearly defined, and this creates challenges for commercial implementation of these technologies by the pharmaceutical industry. The intent of this paper is to highlight the opportunities and growing interest in realizing the benefits of co-processed APIs, exemplified by a body of academic research and industrial examples. This work will highlight reasons why co-processed APIs would best be considered as drug substances from a regulatory perspective and emphasize the areas where regulatory strategies need to be established to allow for commercialization of innovative approaches in this area.
In this study, a Schulze ring shear tester and the discrete element method (DEM) are employed to investigate the effect of polydispersity on the binary shear flows. Both experimental results and DEM simulations show that the preshear stresses are greater for binary blends than for monodispersed particles. The flowability of these mixtures is strongly affected by the solid fraction, with minimal flow function values correlating to maximum packing fraction. However, minimum flow function values are not observed at the same packing fractions where the maximum preshear stress occurs. Using DEM, it is demonstrated that the decrease of angular velocity of larger particles due to the addition of small adhesive particles reduces and the fraction of large‐small particle contact both make contributions to shear stress difference. A mechanism is proposed to quantify the effects of these two factors.
. The overall theme of the conference was "Operations Research and Computing: Algorithms and Software for Analytics." Conference tracks included computational optimization, integer programming, stochastic optimization, constraint programming, heuristics, modeling languages and systems, data mining. There were also several tracks on application areas including homeland security, health applications, and energy systems.The papers included in this volume represent a cross section of these conference tracks. A total of twenty-five papers were submitted for publication in the conference proceedings. After peer review, nineteen of these papers were selected for inclusion in this volume. We would like to thank the peer reviewers for their hard work and responsiveness in reviewing these submissions.We would also like to take this opportunity to thank everyone involved in the organization of the conference and the production of this conference proceedings volume. In particular, we would like to thank the other members of the organizing committee, Xi Chen (poster session chair), José Dulá (social events), Craig Larson (plenary chair), and Yongjia Song (who managed the EasyChair system and scheduling of sessions.) The organizers of previous ICS conferences, Bill Hart, J. P. Watson, and Bruce Golden, provided invaluable advice and support. VCU librarians Sam Byrd, Jimmy Glaphery, and Margaret Henderson helped with planning the open access conference proceedings. Courtney Gahagan designed the cover of the volume. The human pyramids featured on the cover are part of a tradition of the ICS conferences. The editors thank the photographers and the subjects for agreeing to be featured on the cover. Finally, we would like to thank INFORMS staff Miranda Walker, Kathleen Luckey, and Mirko Janc, who helped to edit and produce the conference proceedings volume.The pyramid builders pictured on the cover are:
Single crystal sapphire substrates were lithographically patterned with a system of parallel platinum electrodes, which were used to manipulate 1.58μm silica particles inplane, in the presence of an aqueous solution. Observation of the motion of these particles revealed the adhesion of some of them to the sapphire surface near the platinum working electrode, even in the range of pH where the zeta potentials of silica and sapphire are of the same sign. This phenomenon suggests the existence of localized differences in pH, attributable to the presence of potential determining ions produced in the faradaic processes occurring at the electrodes during the electrophoretic manipulation of silica particles. Atomic force microscopy (AFM) was used to corroborate this hypothesis, measuring the forces between a silica particle and a sapphire substrate in the presence of an applied field. The resultant force-distance curves demonstrate a change in the interaction forces between particle and substrate as a function of distance from the electrode. Variations in this interaction correspond to localized differences in the zeta potential of the substrate, which, in turn, are related to localized differences in pH. Quantification of these spatial variations in pH as a function of time yields further information about the diffusion of these faradaically produced potential determining ions across the substrate.
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