Interference lithography for optical devices and coatings

Interference lithography can create large-area, defect-free nanostructures with unique optical properties. In this thesis, interference lithography will be utilized to create photonic crystals for functional devices or coatings. For instance, typical lithographic processing techniques were used to create 1, 2 and 3 dimensional photonic crystals in SU8 photoresist. These structures were in-filled with birefringent liquid crystal to make active devices, and the orientation of the liquid crystal directors within the SU8 matrix was studied. Most of this thesis will be focused on utilizing polymerization induced phase separation as a single-step method for fabrication by interference lithography. For example, layered polymer/nanoparticle composites have been created through the one-step two-beam interference lithographic exposure of a dispersion of 25 and 50 nm silica particles within a photopolymerizable mixture at a wavelength of 532 nm. In the areas of constructive interference, the monomer begins to polymerize via a free-radical process and concurrently the nanoparticles move into the regions of destructive interference. The holographic exposure of the particles within the monomer resin offers a single-step method to anisotropically structure the nanoconstituents within a composite. A one-step holographic exposure was also used to fabricate self- healing coatings that use water from the environment to catalyze polymerization. Polymerization induced phase separation was used to sequester an isocyanate monomer within an acrylate matrix. Due to the periodic modulation of the index of refraction between the monomer and polymer, the coating can reflect a desired wavelength, allowing for tunable coloration. When the coating is scratched, polymerization of the liquid isocyanate is catalyzed by moisture in air; if the indices of the two polymers are matched, the coatings turn transparent after healing. Interference lithography offers a method of creating multifunctional self-healing coatings that readout when damage has occurred.

Fire protection durability of intumescent coatings after accelerated aging

The most common method of achieve the required fire resistance is by the use of passive fire protection systems, being intumescent coatings the fire protection material frequently used. These are usually considered thin film coatings as they are applied with a dry film thickness (DFT) between 0.3-3 [mm]. The required DFT is obtained by experimental fire resistance tests performed to assess the contribution of this reactive fire protection material to the steel member fire resistance. This tests are done after dry coating and a short time period of atmospheric conditioning, at constant temperature and humidity. As the coatings formulation is mainly made from polymeric basis compounds, it is expected that the environmental factors, such temperature, humidity and UV radiation (UVA and UVB) significantly affect the intumescent coating fire protection performance and its durability. This work presents a research study about the effects of aging on the fire protection performance of intumescent coatings. A commercial water based coating is submitted to an accelerated aging cycle, using a QUV Accelerated Weathering Tester. This tests aim to simulate 10 years of the coating natural aging. The coating durability is tested comparing the fire protection of small steel samples submitted to a radiant heat flux exposure from a cone calorimeter. In total, 28 tests were performed on intumescent coating protected steel specimens, of which 14 specimens were tested before the hydrothermal aging test and other 14 after accelerated aging. The experimental tests results of the steel temperature evolution shows that increasing the intumescent dry coating film thickness, the fire resistance time increases. After the accelerated aging cycles, the coating lose their ability to expand, resulting in an increase of the steel temperature of approximately 200 [ºC], compared to the samples without aging.

Design of functional hybrid coatings with anti-biofouling, self-cleaning and anti-reflecting applications

263 p.

Adaptive coatings based on polyaniline for direct 2D observation of diffusion processes in microfluidic systems

[EN] Therefore the understanding and proper evaluation of the flow and mixing behaviour at microscale becomes a very important issue. In this study, the diffusion behaviour of two reacting solutions of HCI and NaOH were directly observed in a glass/polydimethylsiloxane microfluidic device using adaptive coatings based on the conductive polymer polyaniline that are covalently attached to the microchannel walls. The two liquid streams were combined at the junction of a Y-shaped microchannel, and allowed to diffuse into each other and react. The results showed excellent correlation between optical observation of the diffusion process and the numerical results. A numerical model which is based on finite volume method (FVM) discretisation of steady Navier-Stokes (fluid flow) equations and mass transport equations without reactions was used to calculate the flow variables at discrete points in the finite volume mesh element. The high correlation between theory and practical data indicates the potential of such coatings to monitor diffusion processes and mixing behaviour inside microfluidic channels in a dye free environment.

Design of Nanophotonic Antireflection Coatings for III-V Thin-Film Photovoltaics

Thin-film photovoltaics have provided a critical design avenue to help decrease the overall cost of solar power. However, a major drawback of thin-film solar cell technology is decreased optical absorption, making compact, high-quality antireflection coatings of critical importance to ensure that all available light enters the cell. In this thesis, we describe high efficiency thin-film InP and GaAs solar cells that utilize a periodic array of nanocylinders as antireflection coatings. We use coupled optical and electrical simulations to find that these nanophotonic structures reduce the solar-weighted average reflectivity of InP and GaAs solar cells to around 1.3 %, outperforming the best double-layer antireflection coatings. The coupling between Mie scattering resonances and thin-film interference effects accurately describes the optical enhancement provided by the nanocylinders. The spectrally resolved reflectivity and J-V characteristics of the devices under AM1.5G solar illumination are determined via the coupled optical and electrical simulations, resulting in predicted power conversion efficiencies > 23 %. We conclude that the nanostructured coatings reduce reflection without negatively affecting the electronic properties of the InP and GaAs solar cells by separating the nanostructured optical components from the active layer of the device.

Considerations associated with the testing of external pipeline coatings

Reliable testing methodologies for the assessment of protective coatings are critical for ensuring the integrity and durability of pipeline coatings (such as field joint coatings) and the mitigation of pipeline corrosion. Currently the failure of joint coatings is one of the major concerns in corrosion protection of pipelines, although they represent only approximately 5% of the coated area in a pipeline system. This paper presents an overview of major testing methodologies currently used in the pipeline industry for the selection, testing, and life prediction of coatings, in particular field joint coatings. Particular focus is on the discussion of difficulties and limitations in testing methods for assessing pipeline coating cracking, cathodic disbondment and loss of adhesion. It is shown that there are limitations in current methodologies in evaluating the coating flexibility - a key parameter for avoiding coatings cracking during hydrostatic testing, cyclic pressure operation and field bending. Methodologies for assessing the effect of holidays in coatings on the cathodic disbondment of pipeline coating under excessively negative cathodic protection (CP) voltages also require improvement. Furthermore, methods for understanding the effects of coating wet adhesion on pipeline coating, cracking and disbondment also need attention. Some preliminary results for addressing some of these issues are also presented in this paper.

Experimental and stochastic approaches to assessing the strain demand of pipelines and flexibility requirements for coatings

A criterion for selecting a coating for an energy pipeline is that the coating should have a suitable flexibility to meet the high strain demand during hydrostatic testing and during field bending. This requires knowledge of the level of strain demand for the pipeline, and also the maximum strain that could be
tolerated by the coating system. Whereas average strains imposed during manufacturing and construction are reasonably well predicted, there is insufficient understanding on the factors leading to localised deformation of the pipe. Significant work has been carried out in the past to develop tests for assessing
the coatings’ ability to handle a certain amount of strain based on bend testing, tensile testing and burst testing. However, there is a concern as to whether these tests properly represent localised micro-strains associated with construction activities including field bending and pressure testing, particularly pressure testing of pipelines designed for operation at 80% of specified minimum yield strength (SMYS). Consequently coatings considered "suitable" for modern pipelines may fail. The first issue discussed in this paper is main factors affecting strain localisation. The non-deterministic distributions of heterogeneities over the pipe provide a ground to consider the mechanisms of localisation as a stochastic process. An approach is proposed to quantify the maximum localised strain demand through cold field bending and hydrostatic experiments. Another issue discussed in this paper is the experimental assessment of coating flexibility under the effects of localised strains. Preliminary mandrel tests have been carried out to assess the uniformity of the imposed strain. Although mandrel testing has been shown to be a useful method for relative comparison of coating flexibility, it has several weaknesses that could significantly affect the reliability and reproducibility of the results.

Communication - an approach to measuring local electrochemical impedance for monitoring cathodic disbondment of coatings

An electrochemically integrated multi-electrode array has been used for monitoring and visualizing the cathodic disbondment of
defective coatings by measuring local electrochemical impedance. Compared with the conventional electrochemical impedance and
local current measurement approaches, this new approach significantly enhances the sensitivity of detecting the propagation of
coating disbondment by eliminating the effects of the dominating low impedance regions, such as those that arise at coating defects,
and thus increases the visibility of higher impedance regions deep in the disbonded coating. Furthermore, it facilitates the probing
of electrode processes and mechanisms in selected local electrode regions.

Microstructure and hardness characterisation of laser coatings produced with a mixture of AISI 420 stainless steel and Fe-C-Cr-Nb-B-Mo steel alloy powders

Fe-C-Cr-Nb-B-Mo alloy powder and AISI 420 SS powder are deposited using laser cladding to increase the hardness for wear resistant applications. Mixtures from 0 to 100 wt.% were evaluated to understand the effect on the elemental composition, microstructure, phases, and microhardness. The mixture of carbon, boron and niobium in the Fe-C-Cr-Nb-B-Mo alloy powder introduces complex carbides into a Fe-based matrix of AISI 420 SS which increases its hardness. Hardness increased linearly with increasing Fe-C-Cr-Nb-B-Mo alloy, but substantial micro-cracking was observed in the clad layer at additions of 60 wt.% and above; related to a transition from a hypoeutectic alloy containing α-Fe/α' dendrites with an (Fe,Cr)2B and γ-Fe eutectic to primary and continuous carbo-borides M2B (where M represents Fe and Cr) and M23(B,C)6 carbides (where M represents Fe, Cr, Mo) with MC particles (where M represents Nb and Mo). The highest average hardness, for an alloy without micro-cracking, of 952 HV was observed in a 40 wt.% alloy. High stress abrasive scratch testing was conducted on all alloys at various loads (500, 1500, 2500 N). Alloy content was found to have a strong effect on the wear mode and the abrasive wear rate, and the presence of micro-cracks was detrimental to abrasive wear resistance.

Fluorine-free superhydrophobic coatings with pH-induced wettability transition for controllable oil-water separation

We present a simple, environmentally friendly approach to fabricating superhydrophobic coatings with pH-induced wettability transition. The coatings are prepared from a mixture of silica nanoparticles and decanoic acid-modified TiO2. When the coating is applied on cotton fabric, the fabric turns superhydrophobic in air but superoleophilic in neutral aqueous environment. It is permeable to oil fluids but impermeable to water. However, when the coated fabric is placed in basic aqueous solution or ammonia vapor, it turns hydrophilic but underwater superoleophobic, thus allowing water to penetrate through but blocking oil. Therefore, such a unique, selective water/oil permeation feature makes the treated fabric have capability to separate either oil or water from a water-oil mixture. It may be useful for development of smart oil-water separators, microfluidic valves, and lab-on-a-chip devices.

Conductive polymer coatings

Conducting polymer-coated textiles possess a wide range of electrical properties. The surface resistivity is influenced by concentrations of the reactants, the thickness of the coating, the nature of the substrate surface, the extent of penetration of the polymer into the textile structure, and the strength of the binding of the coating to the textile surface. Low resistivity in fabric results from highly doped thicker coatings that penetrate well into the textile structure, thus enabling good electrical contact between fibers. Microwave studies showed that conductive textiles are not highly effective as electromagnetic shielding materials owing to their medium-level conductivity and therefore large skin depth. Combined with the fact that coatings are around 1. ?m thick, they cannot act as effective reflective barriers to electromagnetic radiation. However, because they are highly absorptive in the microwave region, absorbing materials can be designed in conjunction with conductive textiles. Study of Fourier transform-infrared spectra of aged polypyrrole films has shown an increase in intensity of an ?,?-unsaturated conjugated carbonyl peak that may be linked to the increase in resistance but cannot be the only factor, because the rate of electrical decay was influenced by several factors such as temperature, the type and concentration of the dopant, and the aging time, all of which signify a complex mechanism of degradation of conductivity. Degradation is a major concern for conductive textile systems that needs to be characterized before considering these materials for potential applications.