Reaction Control in Quiescent Systems of Free-Radical Retrograde-Precipitation Polymerization

Free-radical retrograde-precipitation polymerization, FRRPP in short, is a novel polymerization process discovered by Dr. Gerard Caneba in the late 1980s. The current study is aimed at gaining a better understanding of the reaction mechanism of the FRRPP and its thermodynamically-driven features that are predominant in controlling the chain reaction. A previously developed mathematical model to represent free radical polymerization kinetics was used to simulate a classic bulk polymerization system from the literature. Unlike other existing models, such a sparse-matrix-based representation allows one to explicitly accommodate the chain length dependent kinetic parameters. Extrapolating from the past results, mixing was experimentally shown to be exerting a significant influence on reaction control in FRRPP systems. Mixing alone drives the otherwise severely diffusion-controlled reaction propagation in phase-separated polymer domains. Therefore, in a quiescent system, in the absence of mixing, it is possible to retard the growth of phase-separated domains, thus producing isolated polymer nanoparticles (globules). Such a diffusion-controlled, self-limiting phenomenon of chain growth was also observed using time-resolved small angle x-ray scattering studies of reaction kinetics in quiescent systems of FRRPP. Combining the concept of self-limiting chain growth in quiescent FRRPP systems with spatioselective reaction initiation of lithography, microgel structures were synthesized in a single step, without the use of molds or additives. Hard x-rays from the bending magnet radiation of a synchrotron were used as an initiation source, instead of the more statistally-oriented chemical initiators. Such a spatially-defined reaction was shown to be self-limiting to the irradiated regions following a polymerization-induced self-assembly phenomenon. The pattern transfer aspects of this technique were, therefore, studied in the FRRP polymerization of N-isopropylacrylamide (NIPAm) and methacrylic acid (MAA), a thermoreversible and ionic hydrogel, respectively. Reaction temperature increases the contrast between the exposed and unexposed zones of the formed microgels, while the irradiation dose is directly proportional to the extent of phase separation. The response of Poly (NIPAm) microgels prepared from the technique described in this study was also characterized by small angle neutron scattering.

BARIUM CONCENTRATIONS IN ROCK SALT BY LASER INDUCED BREAKDOWN SPECTROSCOPY

Time-REsolved Laser Induced Breakdown Spectroscopy (TRELIBS) was used to determine the elemental concentration of barium in Texas Dome rock salt. TRELIBS allows for an efficient and in situ concentration analysis technique that detects a wide range of elements with no sample preparation. TRELIBS measurements were made in the 545nm to 594nm wavelength range. The proximity of a strong barium emission line (553.5481 nm) to the sodium doublet (588.9950 nm and 589.5924 nm) allowed for measurement within a single frame of the spectrograph. This barium emission line was compared to the sodium doublet for relative intensity. A homemade calibration sample containing known amounts of barium and sodium was used to determine the relative concentrations. By approximating the sodium content in the rock salt as 50%, we determined the absolute concentration of barium in the salt to be (0.13±0.03)%.

Implementation of porous silicon technology for a fluidic flow-through optical sensor for pH measurements

This work presents an innovative integration of sensing and nano-scaled fluidic actuation in the combination of pH sensitive optical dye immobilization with the electro-osmotic phenomena in polar solvents like water for flow-through pH measurements. These flow-through measurements are performed in a flow-through sensing device (FTSD) configuration that is designed and fabricated at MTU. A relatively novel and interesting material, through-wafer mesoporous silica substrates with pore diameters of 20 -200 nm and pore depths of 500 µm are fabricated and implemented for electro-osmotic pumping and flow-through fluorescence sensing for the first time. Performance characteristics of macroporous silicon (> 500 µm) implemented for electro-osmotic pumping include, a very large flow effciency of 19.8 µLmin-1V-1 cm-2 and maximum pressure effciency of 86.6 Pa/V in comparison to mesoporous silica membranes with 2.8 µLmin-1V-1cm-2 flow effciency and a 92 Pa/V pressure effciency. The electrical current (I) of the EOP system for 60 V applied voltage utilizing macroporous silicon membranes is 1.02 x 10-6A with a power consumption of 61.74 x 10-6 watts. Optical measurements on mesoporous silica are performed spectroscopically from 300 nm to 1000 nm using ellipsometry, which includes, angularly resolved transmission and angularly resolved reflection measurements that extend into the infrared regime. Refractive index (n) values for oxidized and un-oxidized mesoporous silicon sample at 1000 nm are found to be 1.36 and 1.66. Fluorescence results and characterization confirm the successful pH measurement from ratiometric techniques. The sensitivity measured for fluorescein in buffer solution is 0.51 a.u./pH compared to sensitivity of ~ 0.2 a.u./pH in the case of fluorescein in porous silica template. Porous silica membranes are efficient templates for immobilization of optical dyes and represent a promising method to increase sensitivity for small variations in chemical properties. The FTSD represents a device topology suitable for application to long term monitoring of lakes and reservoirs. Unique and important contributions from this work include fabrication of a through-wafer mesoporous silica membrane that has been thoroughly characterized optically using ellipsometry. Mesoporous silica membranes are tested as a porous media in an electro-osmotic pump for generating high pressure capacities due to the nanometer pore sizes of the porous media. Further, dye immobilized mesoporous silica membranes along with macroporous silicon substrates are implemented for continuous pH measurements using fluorescence changes in a flow-through sensing device configuration. This novel integration and demonstration is completely based on silicon and implemented for the first time and can lead to miniaturized flow-through sensing systems based on MEMS technologies.

Non-invasive method to predict viscosity and size using total internal reflection fluorescence microscopy (TIRFM) system

This study develops an automated analysis tool by combining total internal reflection fluorescence microscopy (TIRFM), an evanescent wave microscopic imaging technique to capture time-sequential images and the corresponding image processing Matlab code to identify movements of single individual particles. The developed code will enable us to examine two dimensional hindered tangential Brownian motion of nanoparticles with a sub-pixel resolution (nanoscale). The measured mean square displacements of nanoparticles are compared with theoretical predictions to estimate particle diameters and fluid viscosity using a nonlinear regression technique. These estimated values will be confirmed by the diameters and viscosities given by manufacturers to validate this analysis tool. Nano-particles used in these experiments are yellow-green polystyrene fluorescent nanospheres (200 nm, 500 nm and 1000 nm in diameter (nominal); 505 nm excitation and 515 nm emission wavelengths). Solutions used in this experiment are de-ionized (DI) water, 10% d-glucose and 10% glycerol. Mean square displacements obtained near the surface shows significant deviation from theoretical predictions which are attributed to DLVO forces in the region but it conforms to theoretical predictions after ~125 nm onwards. The proposed automation analysis tool will be powerfully employed in the bio-application fields needed for examination of single protein (DNA and/or vesicle) tracking, drug delivery, and cyto-toxicity unlike the traditional measurement techniques that require fixing the cells. Furthermore, this tool can be also usefully applied for the microfluidic areas of non-invasive thermometry, particle tracking velocimetry (PTV), and non-invasive viscometry.