There are two primary objectives of this dissertation research. The first objective was to prepare a library of inorganic-organic hydrogels from methacrylated star polydimethylsiloxane (PDMSstar-MA) and diacrylated poly(ethylene oxide) (PEO-DA) with tunable chemical and physical properties for use as tissue engineering scaffolds. These inorganic-organic hydrogels provide a useful platform to study the effect of scaffold properties on cell behavior in tissue culture. Twenty compositionally unique hydrogels were prepared by photo-crosslinking varing molecular weights (Mn) of PEO-DA (Mn = 3.4k and 6k g/mol) and PDMSstar-MA (Mn = 1.8k, 5k and 7k g/mol) at varying weight ratios (up to 20 wt% PDMSstar-MA). Introduction of PDMSstar-MA caused formation of discrete PDMS-enriched "microparticles" dispersed within the PEO hydrogel matrix. The swelling ratio, mechanical properties in tension and compression, non-specific protein adhesion and cytotoxicity of hydrogels were studied. The second objective was to prepare thermoresponsive nanocomposite hydrogels, which are mechanically robust and can remove adhered cells via thermal modulation. Such hydrogels may be useful as "self-cleaning" membranes for implanted biosensors to extend their lifetime and efficiency. These hydrogels are comprised of a poly(Nisopropylacrylamide) (PNIPAAm) hydrogel matrix and polysiloxane colloidal nanoparticles (~220 nm and 50 nm ave. diameter). Due to the low preparation temperature, the nanocomposite hydrogels exhibited a homogeneous morphology by SEM analysis. The volume phase transition temperature (VPTT, ~33 degrees C) of the nanocomposite hydrogels was not altered versus the pure PNIPAAm hydrogel, which is near body temperature. Generally, nanoparticles led to improve mechanical properties versus pure PNIPAAm hydrogels. When these nanocomposite hydrogels are heated above the VPTT, they become more hydrophobic. When they are reversibly switched from a water-swollen to a deswollen state, the change in surface properties, as well as swelling-deswelling, was effective upon the removal of adhered cells.

During the Fall of 2009, a pilot study was conducted at the McCormick and Baxter (M&B) Superfund Site to evaluate polydimethylsiloxane (PDMS) profilers as a method for sediment cap performance monitoring. The profilers are shielded solid phase microextraction fibers, silica rods coated with polydimethylsiloxane (PDMS) as the sorbent. The deployment explored whether profiling PDMS could be used as a low impact, highly sensitive, long term monitoring strategy at M&B since the sediment operable unit will be transitioning to the “Operable & Maintenance” phase of Superfund cleanup. To evaluate sediment cap performance, a good understanding of the flux of contaminants from the sediment is required. While surface waters can illustrate this flux, they can also contain contaminants originating from upstream sources. The existing sampling plan at M&B uses a conventional porewater pumping sampling technique that measures both dissolved and particulate fractions. PDMS profilers measure only the freely dissolved fraction which has been shown to be a good indicator of bioavailability. These profilers also have lower detection limits (ng/L) and the ability to measure vertical concentration gradients which can help identify sources and mechanisms of the contamination. Each sampler was analyzed at three depths for the USEPA Priority Pollutant List of 16 polycyclic aromatic hydrocarbons (PAHs). PDMS measurements showed clear vertical profiling with large reductions in PAH concentrations through the sediment cap offshore. Nearshore, uniform concentration profiles were observed indicating increased vertical mixing as a result of tidal smearing. Further, ANOVA and Tukey-Kramer HSD analysis of sample variability revealed PAH concentrations were statistically different at two locations compared to the remainder of the sampling locations- indicating areas requiring closer attention. PDMS profilers were co-located at 13 of the 22 conventional porewater extraction sampling locations. The correlation of PDMS and conventional porewater extraction techniques was limited due to the low detection frequency by conventional porewater extraction methods as a result of the higher detection limits by that method. The correlation was good for light molecular weight PAHs with most measurements of the same order of magnitude and improved with increasing depth (due to the greater number of detections). 72% of the direct comparisons between PDMS-derived and conventionally-derived porewater concentrations were of the same order of magnitude. Any comparison between the two datasets is necessarily limited especially for the higher molecular weight PAHs, however, due to the large number of non-detects in the conventionally collected data. / text

The aim of the project was to modify polydimethylsiloxane (PDMS) surfaces in order to minimize adsorption of proteins. PDMS is used in micro-fluidic devices that control the delivery of samples to a sensor chip in Biacore instrumentation. These instruments are used to characterize interactions between biomolecules with a detection principle based on surface plasmon resonance (SPR). To minimize adsorption of proteins poly-ethylene-oxide (PEO) based surfactants, were added to the buffer. The added PEO surfactants were P20, Pluronic F-127 and Brij 35. Interaction of these surfactants with the sensor chip in Biacore instruments was also examined. Creating a more hydrophilic surface layer on PDMS by oxidation was also examined. When surfactants were continuously added to protein samples, as in dynamically coating of PDMS surfaces, Brij 35 resulted in the strongest reduction in protein adsorption. Brij 35 was also the surfactant that was easiest to remove from both PDMS and the sensor surfaces. Pluronic bound strongest to surfaces, and is most suitable when only adding surfactant to the buffer in a pre-coating step. All surfactants did reduce protein adsorption considerably (99% or more) and addition is necessary when working with protein solutions and hydrophobic surfaces as PDMS. Another alternative is oxidation of PDMS surface, which is an easy procedure that decreased the protein adsorption to about 10% compared to adsorption to untreated surface.

This thesis focuses on the design, fabrication and characterization of polymeric smart structures that are able to alter their geometry and thus their properties upon the application of external stimuli in a reversible and controllable manner. Two different responsive structures are studied that both contain poly dimethyl-siloxane (PDMS) and differ in the design, geometry, and actuation mechanism. The first structure is a surface decorated by a square array of posts (cilia) made of PDMS reinforced with magnetic particles and is actuated magnetically. The structures are meant to mimic cilia, a hair-like structure found in nature. The physical parameters necessary for the magnetic response of the cilia including physical dimensions and filler concentration are investigated. In addition, the elastic modulus of the composites is measured and the microstructure is examined in order to determine the dispersion and homogeneity of the composites. The second structure is a planar hetero-structure consisting of a PDMS substrate and a nanoporous (NP) metal foam film which is actuated thermally or chemically by tuning the generation and release of residual stresses at the NP metal foam/PDMS interface. The effect of strain, applied to the PDMS substrate prior to the deposition of the NP metal foam and the effect of the PDMS and NP metal foam thicknesses on the shape/size of the planer hetero-structure after the actuation is investigated.

abstract: Membranes are a key part of pervaporation processes, which is generally a more efficient process for selective removal of alcohol from water than distillation. It is necessary that the membranes have high alcohol permeabilities and selectivities. Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71) demonstrated promising alcohol separation abilities. In this dissertation, we present fundamental studies on the synthesis of ZIF-71/PDMS MMMs. Free-standing ZIF-71/ PDMS membranes with 0, 5, 25 and 40 wt % ZIF-71 loadings were prepared and the pervaporation separation for ethanol and 1-butanol from water was measured. ZIF-71/PDMS MMMs were formed through addition cure and condensation cure methods. Addition cure method was not compatible with ZIF-71 resulting in membranes with poor mechanical properties, while the condensation cure method resulted in membranes with good mechanical properties. The 40 wt % ZIF-71 loading PDMS nanocomposite membranes achieved a maximum ethanol/water selectivity of 0.81 ± 0.04 selectivity and maximum 1-butnaol/water selectivity of 5.64 ± 0.15. The effects of synthesis time, temperature, and reactant ratio on ZIF-71 particle size and the effect of particle size on membrane performance were studied. Temperature had the greatest effect on ZIF-71 particle size as the synthesis temperature varied from - 20 to 35 ºC. The ZIF-71 synthesized had particle diameters ranging from 150 nm to 1 μm. ZIF-71 particle size is critical in ZIF-71/PDMS composite membrane performance for alcohol removal from water through pervaporation. The membranes made with micron sized ZIF-71 particles showed higher alcohol/water selectivity than those with smaller particles. Both alcohol and water permeability increased when larger sized ZIF- 71 particles were incorporated. ZIF-71 particles were modified with four ligands through solvent assisted linker exchange (SALE) method: benzimidazole (BIM), 5-methylbenzimidazole (MBIM), 5,6- dimethylbenzimidazole (DMBIM) and 4-Phenylimidazole (PI). The morphology of ZIF- 71 were maintained after the modification. ZIF-71/PDMS composite membranes with 25 wt% loading modified ZIF-71 particles were made for alcohol/water separation. Better particle dispersion in PDMS polymer matrix was observed with the ligand modified ZIFs. For both ethanol/water and 1-butanol/water separations, the alcohol permeability and alcohol/water selectivity were lowered after the ZIF-71 ligand exchange reaction. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2017

No description available.

Microfluidics is both a science and a technology offering great and perhaps even revolutionary capabilities to impact the society in the future. However, due to the scaling effects there are unknown phenomena and technology barriers about fluidics in microchannel, material properties in microscale and interactions with fluids are still missing. A systematic investigation has been performed aiming to develop "A Customer Programmable Microfluidic System". This innovative Polydimethylsiloxane (PDMS)-based microfluidic system provides a bio-compatible platform for bio-analysis systems such as Lab-on-a-chip, micro-total-analysis system and biosensors as well as the applications such as micromirrors. The system consists of an array of microfluidic devices and each device containing a multilayer microvalve. The microvalve uses a thermal pneumatic actuation method to switch and/or control the fluid flow in the integrated microchannels. It provides a means to isolate samples of interest and channel them from one location of the system to another based on needs of realizing the customers' desired functions. Along with the fluid flow control properties, the system was developed and tested as an array of micromirrors. An aluminum layer is embedded into the PDMS membrane. The metal was patterned as a network to increase the reflectivity of the membrane, which inherits the deformation of the membrane as a mirror. The deformable mirror is a key element in the adaptive optics. The proposed system utilizes the extraordinary flexibility of PDMS and the addressable control to manipulate the phase of a propagating optical wave front, which in turn can increase the performance of the adaptive optics. Polydimethylsiloxane (PDMS) has been widely used in microfabrication for microfluidic systems. However, few attentions were paid in the past to mechanical properties of PDMS. Importantly there is no report on influences of microfabrication processes which normally involve chemical reactors and biologically reaction processes. A comprehensive study was made in this work to study fundamental issues such as scaling law effects on PDMS properties, chemical emersion and temperature effects on mechanical properties of PDMS, PDMS compositions and resultant properties, as well as bonding strength, etc. Results achieved from this work will provide foundation of future developments of microfluidics utilizing PDMS.

No / Gold on polydimethylsiloxane (PDMS) stretchable conductors were prepared using a novel approach by interlacing an hydrogenated amorphous carbon (a-C : H) layer between the deposited metal layer and the elastomer. AFM analysis of the a-C : H film surface before gold deposition shows nanoscale buckling, the corresponding increase in specific surface area corresponds to a strain compensation for the first 4–6% of bi-axial tensile loading. Without this interlayer, the deposited gold films show much smaller and uni-directional ripples as well as more cracks and delaminations. With a-C : H interlayer, the initial electrical resistivity of the metal film decreases markedly (280-fold decrease to 8 × 10−6 Ω cm). This is not due to conduction within the carbon interlayer; both a-C : H/PDMS and PDMS substrates are electrically insulating. Upon cyclic tensile loading, both films become more resistive, but return to their initial state after 20 tensile cycles up to 60% strain. Profiling experiments using secondary ion mass spectroscopy and x-ray photoelectron spectroscopy indicate that the a-C : H layer intermixes with the PDMS, resulting in a graded layer of decreasing stiffness. We believe that both this graded layer and the surface buckling contribute to the observed improvement in the electrical performance of these stretchable conductors.

No / This paper presents a novel method to prepare stretchable conductors and pressure sensors based on the gold/polydimethylsiloxane (PDMS) system. The gold films were sputtered onto structured PDMS surfaces produced with a photolithographic surface treatment with the aim of reducing tensile strains in the gold film. Scanning electron microscopy (SEM) and atomic force microscopy analyses showed that these 3D patterns reduce cracks and delaminations in the gold film. Electrical measurements indicate that the patterns also protect the films against repeated tensile cycling, although the un-patterned samples remained conducting as well after the completion of 120 cycles. The extrapolated resistivity value of the patterned sample (4.5 × 10−5 Ωcm) compares well with previously published data. SEM micrographs indicate that the pattern features deflect the cracks and therefore toughen the gold film. However, x-ray photoelectron spectroscopy and contact angle analyses indicate that the patterning process also slightly modifies the surface chemistry. This patterning method was used to prepare capacitive strain gauges with pressure sensitivity (ΔZ/Z)/P of 0.14 kPa−1 in the sub-kPa regime. Such stretchable and potentially conformal low-pressure sensors have not been produced before and could prove advantageous for many smart fabric applications.

No description available.