NANOSTRUCTURE INVESTIGATION OF POLYMER SOLUTIONS, POLYMER GELS, AND POLYMER THIN FILMS

This thesis discusses two systems. One is structured hydrogels which are hydrogel systems based on crosslinked poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA) containing micelles which form nanoscale pores within the PDMAEMA hydrogel. The other is nanoporous block copolymer thin films where solvent selectivity is exploited to create nanopores in PS-b-P4VP thin films. Both of these are multicomponent polymer systems which have nanoscale porous structures. 1. Small angle neutron scattering of micellization of anionic surfactants in water, polymer solutions and hydrogels Nanoporous materials have been broadly investigated due to the potential for a wide range of applications, including nano-reactors, low-K materials, and membranes. Among those, molecularly imprinted polymers (MIP) have attracted a large amount of interest because these materials resemble the "lock and key" paradigm of enzymes. MIPs are created by crosslinking either polymers or monomers in the presence of template molecules, usually in water. Initially, functional groups on the polymer or the monomer are bound either covalently or noncovalently to the template, and crosslinking results in a highly crosslinked hydrogel. The MIPs containing templates are immersed in a solvent (usually water), and the large difference in the osmotic pressure between the hydrogel and solvent removes the template molecules from the MIP, leaving pores in the polymer network containing functionalized groups. A broad range of different templates have been used ranging from molecules to nanoscale structures inclucing stereoisomers, virus, and micelles. When micelles are used as templates, the size and shape before and after crosslinking is an important variable as micelles are thermodynamic objects whose structure depends on the surfactant concentration of the solution, temperature, electrolyte concentration and polymer concentration. In our research, the first goal is to understand the micellization of anionic surfactants in polymer solutions and the corresponding hydrogels using small angle neutron scattering (SANS). SANS has been widely used to investigate structures ranging from sub-nanometer to sub-micrometer. Since the scattering lengths of H and D atoms are quite different, the scattering contrast can be enhanced (and varied) through isotopic labeling. It is possible to investigate the structure of micelles in polymer solutions and hydrogels using H/D contrast matching methods with SANS. For this aim, water-soluble and chemically crosslinkgable poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA) was synthesized using group transfer polymerization. In order to control the size and shape of micelles, the degree of quaternization of the polymer was also controlled through the reaction of PDMAEMA with methyl iodide. The micellization of deuterated sodium dodecylsulfate (d-SDS) in (quaternized) PDMAEMA solutions and the corresponding hydrogels was then observed using SANS and the size and shape of d-SDS micelles was obtained by modeling. 2. Nanopatterning using block copolymer/homopolymer blends Block copolymers are well-known to self-assemble into meso- and nano-scale structures. The use of block copolymers for nanostructured patterns has attracted increasing attention due to their potential use as templates and scaffolds for the fabrication of functional nanostructures. In order to realize the potential of these materials, it is necessary to be able to control the orientation of the nanoscale pattern in a precise manner. Numerous methods such as manipulation of the interfacial surface energies, use of electric fields, and controlling the rate of solvent evaporation have developed to control orientation. In addition, it has been shown that nanopores within cylindrical domains oriented normal to the substrate can be generated by several methods. For example, one component can be degraded by UV exposure, or the homopolymer in a block copolymer/homopolymer blend can be extracted in a selective solvent. In our work, polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP)/poly(4-vinylpyridine) (P4VP) films on silicon substrates were prepared using spincoating. The homopolymer was then extracted in ethanol generating pores perpendicular to the substrate. It is noted that the pore size and density were readily controlled by the amount of P4VP homopolymer in the PS-b-P4VP/P4VP solutions, giving simple control of the film structure. It was also possible to make pores more uniform and ordered by annealing in solvent vapor before extracting the homopolymer

Spinor representation in isotropic 3-space via Laguerre geometry

We give a detailed description of the geometry of isotropic space, in parallel to those of Euclidean space within the realm of Laguerre geometry. After developing basic surface theory in isotropic space, we define spin transformations, directly leading to the spinor representation of conformal surfaces in isotropic space. As an application, we obtain the Weierstrass-type representation for zero mean curvature surfaces, and the Kenmotsu-type representation for constant mean curvature surfaces, allowing us to construct many explicit examples.Comment: 30 pages, 9 figure

Effect of double-side welding on the microstructural characteristics and mechanical performance of dissimilar AA6061-AA5052 aluminium alloys

In this study, cold metal transfer (CMT) based double-side welding process was employed to weld AA5052-H32 and AA6061-T6 plates having a thickness of 6 mm. The microstructure and mechanical integrity of the weldment was examined systematically. Symmetric and defect free joint with full penetration was achieved. The multiple heating and cooling cycles during CMT welding did not affect the weldment while the microstructure comprised of columnar and equiaxed dendrites and the heat affected zone (HAZ) width was < 50 µm at all interfaces. Precipitates such as Al3Mg2, Mg2Si, and α-Al(FeMn)Si were observed in the fusion zone. Intergranular Al-Si eutectic structure along with few microliquefaction cracks were noticed in the α-Al matrix. The maximum tensile properties for double-side welded joint were 214 MPa and 12.30 % with a joint efficiency of 70.68 %. Tensile specimens underwent ductile fracture in the weaker AA5052-H32 side with confined plastic deformation

Enhancement of electrochemical detection performance towards 2,4,6-trinitrotoluene by a bottom layer of ZnO nanorod arrays

The ZnO nanostructure layers have been widely investigated as electrodes for sensors due to their intrinsic advantages such as high active area and low cost. In this work, to enhance the detection properties of ZnO nanostructural electrodes, self-organized ZnO nanorod arrays were synthesized using the chemical bath deposition (CBD) method on FTO glasses and ZnO nanoparticles. The fabricated ZnO electrodes on the two different substrates were characterized by SEM, TEM, XRD, and XPS. Subsequently, the detection performance of ZnO nanorod electrodes was electrochemically measured in a 2,4,6-trinitrotoluene (2,4,6-TNT) solution by CV and EIS. The differences in current densities between the ZnO electrodes were determined by the width of the ZnO nanorods, resulting in a ∼45% higher detection efficiency with F-CBD (the ZnO nanorods on FTO) electrodes compared to S-CBD (the ZnO nanorods on ZnO nanoparticles) electrodes

Some Identities of Fully Degenerate Bernoulli Polynomials Associated with Degenerate Bernstein Polynomials

In this paper, we investigate some properties and identities for fully degenerate Bernoulli polynomials in connection with degenerate Bernstein polynomials by means of bosonic p-adic integrals on Z p and generating functions. Furthermore, we study two variable degenerate Bernstein polynomials and the degenerate Bernstein operators

Synthesis of Benzene Tetracarboxamide Polyamine and Its Effect on Epoxy Resin Properties

Epoxy resins have found various industrial applications in high-performance thermosetting resins, high-performance composites, electronic-packaging materials, adhesives, protective coatings, etc., due to their outstanding performance, including high toughness, high-temperature performance, chemical and environmental resistance, versatile processability and adhesive properties. However, cured epoxy resins are very brittle, which limits their applications. In this work, we attempted to enhance the toughness of cured epoxy resins by introducing benzene tetracarboxamide polyamine (BTCP), synthesized from pyromellitic dianhydride (PMDA) and diamines in N-methyl-2-pyrrolidone (NMP) solvent. During this reaction, increased viscosity and formation of amic acid could be confirmed. The chemical reactions were monitored and evidenced using 1H-NMR spectroscopy, FT-IR spectroscopy, water gel-phase chromatography (GPC) analysis, amine value determination and acid value determination. We also studied the effect of additives on thermomechanical properties using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamical mechanical analysis (DMA), thermomechanical analysis (TMA) and by measuring mechanical properties. The BTCP-containing epoxy resin exhibited high mechanical strength and adhesion strength proportional to the amount of BTCP. Furthermore, field-emission scanning electron microscopy images were obtained for examining the cross-sectional morphology changes of the epoxy resin specimens with varying amounts of BTCP