Keywords

Polymer, nanoparticle, semiconductors, superhydrophobic surface, antireflection coating, microvalve, optoelectronic property, layer-by-layer process, electrospinning

Abstract

A wide variety of nanomaterials ranging from polymer assemblies to organic and inorganic nanostructures (particles, wires, rods etc) have been actively pursued in recent years for various applications. The synthesis route of these nanomaterials had been driven through two fundamental approaches - 'Top down' and 'Bottom up'. The key aspect of their application remained in the ability to make the nanomaterials suitable for targeted location by manipulating their structure and functionalizing with active target groups. Functional nanomaterials like polyelectrolyte based multilayered thin films, nanofibres and graphene based composite materials are highlighted in the current research. Multilayer thin films were fabricated by conventional dip coating and newly developed spray coating techniques. Spray coating technique has an advantage of being applied for large scale production as compared to the dip coating technique. Conformal hydrophobic/hydrophilic and superhydrophobic/hydrophilic thermal switchable surfaces were fabricated with multilayer films of poly(allylaminehydrochloride) (PAH) and silica nanoparticles by the dip coating technique, followed by the functionalization with thermosensitive polymer-poly(N-isopropylacrylamide)(PNIPAAM) and perfluorosilane. The thermally switchable superhydrophobic/ hydrophilic polymer patch was integrated in a microfluidic channel to act as a stop valve. At 70 degree centigrade, the valve was superhydrophobic and stopped the water flow (close status) while at room temperature, the patch became hydrophilic, and allowed the flow (open status). Spray-coated multilayered film of poly(allylaminehydrochloride) (PAH) and silica nanoparticles was fabricated on polycarbonate substrate as an anti-reflection (AR) coating. The adhesion between the substrate and the coating was enhanced by treating the polycarbonate surface with aminopropyltrimethoxylsilane (APTS) and sol-gel. The coating was finally made abrasion-resistant with a further sol-gel treatment on top of AR coating, which formed a hard thin scratch-resistant film on the coating. The resultant AR coating could reduce the reflection from 5 to 0.3% on plastic. Besides multilayered films, the fabrication of polyelectrolyte based electrospun nanofibers was also explored. Ultrathin nanofibers comprising 2-weak polyelectrolytes, poly(acrylic acid) (PAA) and poly(allylaminehydrochloride) (PAH) were fabricated using the electrospinning technique and methylene blue (MB) was used as a model drug to evaluate the potential application of the fibers for drug delivery. The release of MB was controlled in a nonbuffered medium by changing the pH of the solution. Temperature controlled release of MB was obtained by depositing temperature sensitive PAA/poly(N-isopropylacrylamide) (PNIPAAM) multilayers onto the fiber surfaces. The sustained release of MB in a phosphate buffered saline (PBS) solution was achieved by constructing perfluorosilane networks on the fiber surfaces as capping layers. The fiber was also loaded with a real life anti-depressant drug (2,3-tertbutyl-4-methoxyphenol) and fiber surface was made superhydrophobic. The drug loaded superhydrophobic nanofiber mat was immersed under water, phosphate buffer saline and surfactant solutions in three separated experiments. The rate of release of durg was monitored from the fiber surface as a result of wetting with different solutions. Time dependent wetting of the superhydrophobic surface and consequently the release of drug was studied with different concentrations of surfactant solutions. The results provided important information about the underwater superhydrophobicity and retention time of drug in the nanofibers. The nanostructured polymers like nanowires, nanoribbons and nanorods had several other applications too, based on their structure. Different self-assembled structures of semiconducting polymers showed improved properties based on their architectures. Poly(3-hexylthiophene) (P3HT) supramolecular structures were fabricated on P3HT-dispersed reduced graphene oxide (RGO) nanosheets. P3HT was used to disperse RGO in hot anisole/N, N-dimethylformamide solvents, and the polymer formed nanowires on RGO surfaces through a RGO induced crystallization process. The Raman spectroscopy confirmed the interaction between P3HT and RGO, which allowed the manipulation of the composite's electrical properties. Such a bottom-up approach provided interesting information about graphene-based composites and inspired to study the interaction between RGO and the molecular semiconductor-tetrasulphonate salt of copper phthalocyanine (TSCuPc) for nanometer-scale electronics. The reduction of graphene oxide in presence of TSCuPc produced a highly stabilized aqueous composite ink with monodispersed graphene sheets. To demonstrate the potential application of the donor (TSCuPc)'acceptor (graphene) composite, the RGO/TSCuPc suspension was successfully incorporated in a thin film device and the optoelectronic property was measured. The conductivity (dark current) of the composite film decreased compared to that of pure graphene due to the donor molecule incorporation, but the photoconductivity and photoresponsivity increased to an appreciable extent. The property of the composite film overall improved with thermal annealing and optimum loading of TSCuPc molecules.

Notes

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Graduation Date

2010

Advisor

Zhai, Lei

Degree

Doctor of Philosophy (Ph.D.)

College

College of Sciences

Department

Chemistry

Degree Program

Chemistry

Format

application/pdf

Identifier

CFE0003292

URL

http://purl.fcla.edu/fcla/etd/CFE0003292

Language

English

Release Date

August 2010

Length of Campus-only Access

None

Access Status

Doctoral Dissertation (Open Access)

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Chemistry Commons

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