Ion-assisted functional monolayer coating of nanorod arrays in hydrogen plasmas

Uniformity of postprocessing of large-area, dense nanostructure arrays is currently one of the greatest challenges in nanoscience and nanofabrication. One of the major issues is to achieve a high level of control in specie fluxes to specific surface areas of the nanostructures. As suggested by the numerical experiments in this work, this goal can be achieved by manipulating microscopic ion fluxes by varying the plasma sheath and nanorod array parameters. The dynamics of ion-assisted deposition of functional monolayer coatings onto two-dimensional carbon nanorod arrays in a hydrogen plasma is simulated by using a multiscale hybrid numerical simulation. The numerical results show evidence of a strong correlation between the aspect ratios and nanopattern positioning of the nanorods, plasma sheath width, and densities and distributions of microscopic ion fluxes. When the spacing between the nanorods and/or their aspect ratios are larger, and/or the plasma sheath is wider, the density of microscopic ion current flowing to each of the individual nanorods increases, thus reducing the time required to apply a functional monolayer coating down to 11 s for a 7-μm-wide sheath, and to 5 s for a 50-μm-wide sheath. The computed monolayer coating development time is consistent with previous experimental reports on plasma-assisted functionalization of related carbon nanostructures [B. N. Khare et al., Appl. Phys. Lett. 81, 5237 (2002)]. The results are generic in that they can be applied to a broader range of plasma-based processes and nanostructures, and contribute to the development of deterministic strategies of postprocessing and functionalization of various nanoarrays for nanoelectronic, biomedical, and other emerging applications.

Room temperature gas sensing properties of ultrathin carbon nanotubes by surfactant-free dip coating

Large-scale production of reliable carbon nanotubes (CNTs) based gas sensors involves the development of scalable and reliable processes for the fabrication of films with controlled morphology. Here, we report for the first time on highly scalable, ultrathin CNT films, to be employed as conductometric sensors for NO2 and NH3 detection at room temperature. The sensing films are produced by dip coating using dissolved CNTs in chlorosulfonic acid as a working solution. This surfactant-free approach does not require any post-treatment for the removal of dispersants or any CNTs functionalization, thus promising high quality CNTs for better sensitivity and low production costs. The effect of CNT film thickness and defect density on the gas sensing properties has been investigated. Detection limits of 1 ppm for NO2 and 7 ppm for NH3 have been achieved at room temperature. The experimental results reveal that defect density and film thickness can be controlled to optimize the sensing response. Gas desorption has been accelerated by continuous in-situ UV irradiation.

Ultrastructure of Biofilms Formed by Bacteria from Industrial Processes

Microorganisms exist predominantly as sessile multispecies communities in natural habitats. Most bacterial species can form these matrix-enclosed microbial communities called biofilms. Biofilms occur in a wide range of environments, on every surface with sufficient moisture and nutrients, also on surfaces in industrial settings and engineered water systems. This unwanted biofilm formation on equipment surfaces is called biofouling. Biofouling can significantly decrease equipment performance and lifetime and cause contamination and impaired quality of the industrial product. In this thesis we studied bacterial adherence to abiotic surfaces by using coupons of stainless steel coated or not coated with fluoropolymer or diamond like carbon (DLC). As model organisms we used bacterial isolates from paper machines (Meiothermus silvanus, Pseudoxanthomonas taiwanensis and Deinococcus geothermalis) and also well characterised species isolated from medical implants (Staphylococcus epidermidis). We found that coating of steel surface with these materials reduced its tendency towards biofouling: Fluoropolymer and DLC coatings repelled all four biofilm formers on steel. We found great differences between bacterial species in their preference of surfaces to adhere as well as their ultrastructural details, like number and thickness of adhesion organelles they expressed. These details responded differently towards the different surfaces they adhered to. We further found that biofilms of D. geothermalis formed on titanium dioxide coated coupons of glass, steel and titanium, were effectively removed by photocatalytic action in response to irradiation at 360 nm. However, on non-coated glass or steel surfaces irradiation had no detectable effect on the amount of bacterial biomass. We showed that the adhesion organelles of bacteria on illuminated TiO2 coated coupons were complety destroyed whereas on non-coated coupons they looked intact when observed by microscope. Stainless steel is the most widely used material for industrial process equipments and surfaces. The results in this thesis showed that stainless steel is prone to biofouling by phylogenetically distant bacterial species and that coating of the steel may offer a tool for reduced biofouling of industrial equipment. Photocatalysis, on the other hand, is a potential technique for biofilm removal from surfaces in locations where high level of hygiene is required. Our study of natural biofilms on barley kernel surfaces showed that also there the microbes possessed adhesion organelles visible with electronmicroscope both before and after steeping. The microbial community of dry barley kernels turned into a dense biofilm covered with slimy extracellular polymeric substance (EPS) in the kernels after steeping in water. Steeping is the first step in malting. We also presented evidence showing that certain strains of Lactobacillus plantarum and Wickerhamomyces anomalus, when used as starter cultures in the steeping water, could enter the barley kernel and colonise the tissues of the barley kernel. By use of a starter culture it was possible to reduce the extensive production of EPS, which resulted in a faster filtration of the mash.

Evaluation of the Interfacial Adhesion between Brittle Coating and Ductile Substrate by Cross-Secitional Indention

The cross-sectional indentation method is extended to evaluate the interfacial adhesion between brittle coating and ductile substrate. The experimental results on electroplated chromium coating/steel substrate show that the interfacial separation occurs due to the edge chipping of brittle coating. The corresponding models are established to elucidate interfacial separation processes. This work further highlights the advantages and potential of this novel indentation method.

Evaluation of the Interfacial Adhesion between Brittle Coating and Ductile Substrate by Cross-Secitional Indention

The cross-sectional indentation method is extended to evaluate the interfacial adhesion between brittle coating and ductile substrate. The experimental results on electroplated chromium coating/steel substrate show that the interfacial separation occurs due to the edge chipping of brittle coating. The corresponding models are established to elucidate interfacial separation processes. This work further highlights the advantages and potential of this novel indentation method

Control of wettability of carbon nanotube array by reversible dry oxidation for superhydrophobic coating and supercapacitor applications

In this thesis, dry chemical modification methods involving UV/ozone, oxygen plasma, and vacuum annealing treatments are explored to precisely control the wettability of CNT arrays. By varying the exposure time of these treatments the surface concentration of oxygenated groups adsorbed on the CNT arrays can be controlled. CNT arrays with very low amount of oxygenated groups exhibit a superhydrophobic behavior. In addition to their extremely high static contact angle, they cannot be dispersed in DI water and their impedance in aqueous electrolytes is extremely high. These arrays have an extreme water repellency capability such that a water droplet will bounce off of their surface upon impact and a thin film of air is formed on their surface as they are immersed in a deep pool of water. In contrast, CNT arrays with very high surface concentration of oxygenated functional groups exhibit an extreme hydrophilic behavior. In addition to their extremely low static contact angle, they can be dispersed easily in DI water and their impedance in aqueous electrolytes is tremendously low. Since the bulk structure of the CNT arrays are preserved during the UV/ozone, oxygen plasma, and vacuum annealing treatments, all CNT arrays can be repeatedly switched between superhydrophilic and superhydrophobic, as long as their O/C ratio is kept below 18%.

The effect of oxidation using UV/ozone and oxygen plasma treatments is highly reversible as long as the O/C ratio of the CNT arrays is kept below 18%. At O/C ratios higher than 18%, the effect of oxidation is no longer reversible. This irreversible oxidation is caused by irreversible changes to the CNT atomic structure during the oxidation process. During the oxidation process, CNT arrays undergo three different processes. For CNT arrays with O/C ratios lower than 40%, the oxidation process results in the functionalization of CNT outer walls by oxygenated groups. Although this functionalization process introduces defects, vacancies and micropores opening, the graphitic structure of the CNT is still largely intact. For CNT arrays with O/C ratios between 40% and 45%, the oxidation process results in the etching of CNT outer walls. This etching process introduces large scale defects and holes that can be obviously seen under TEM at high magnification. Most of these holes are found to be several layers deep and, in some cases, a large portion of the CNT side walls are cut open. For CNT arrays with O/C ratios higher than 45%, the oxidation process results in the exfoliation of the CNT walls and amorphization of the remaining CNT structure. This amorphization process can be implied from the disappearance of C-C sp2 peak in the XPS spectra associated with the pi-bond network.

The impact behavior of water droplet impinging on superhydrophobic CNT arrays in a low viscosity regime is investigated for the first time. Here, the experimental data are presented in the form of several important impact behavior characteristics including critical Weber number, volume ratio, restitution coefficient, and maximum spreading diameter. As observed experimentally, three different impact regimes are identified while another impact regime is proposed. These regimes are partitioned by three critical Weber numbers, two of which are experimentally observed. The volume ratio between the primary and the secondary droplets is found to decrease with the increase of Weber number in all impact regimes other than the first one. In the first impact regime, this is found to be independent of Weber number since the droplet remains intact during and subsequent to the impingement. Experimental data show that the coefficient of restitution decreases with the increase of Weber number in all impact regimes. The rate of decrease of the coefficient of restitution in the high Weber number regime is found to be higher than that in the low and moderate Weber number. Experimental data also show that the maximum spreading factor increases with the increase of Weber number in all impact regimes. The rate of increase of the maximum spreading factor in the high Weber number regime is found to be higher than that in the low and moderate Weber number. Phenomenological approximations and interpretations of the experimental data, as well as brief comparisons to the previously proposed scaling laws, are shown here.

Dry oxidation methods are used for the first time to characterize the influence of oxidation on the capacitive behavior of CNT array EDLCs. The capacitive behavior of CNT array EDLCs can be tailored by varying their oxygen content, represented by their O/C ratio. The specific capacitance of these CNT arrays increases with the increase of their oxygen content in both KOH and Et4NBF4/PC electrolytes. As a result, their gravimetric energy density increases with the increase of their oxygen content. However, their gravimetric power density decreases with the increase of their oxygen content. The optimally oxidized CNT arrays are able to withstand more than 35,000 charge/discharge cycles in Et4NBF4/PC at a current density of 5 A/g while only losing 10% of their original capacitance.

Thin catalytic coatings on microreactor walls A way to make industrial processes more efficient

Current trends in the development of microstructured reactors with thin catalytic films (from 100 nm up to several microns) that have self-assembled nanostructures are discussed. A major technique that is used to prepare such films is sol-gel processing. This involves depositing a complex fluid on a microstructured substrate by dip, spin, or spray coating, followed by surfactant removal to form the porous nanostructures. A novel methodology has been developed by which a uniform coating containing controlled amounts of (poly) metallic nanoparticles can be obtained. This elegant strategy is based on the condensation of metal oxide species by self-assembly in the presence of metallic colloids. The potential microreactor applications brought forth by this innovative protocol are placed in perspective in the light of its versatility.

Oxidation-induced Cu coating on steel surface

Copper is accumulated in recycled steels and is difficult to be removed during steelmaking processes when steel scrap is used as steel sources. Meanwhile, copper characteristic properties are of importance both to human beings and to animals and plants. In this paper, integrated copper coating was observed on the surface of copper-containing steels when the steels were heated at around 1150°C. However, the copper was separately scattered after heating at 1000°C. The forming mechanisms of copper coating will be discussed in detail. By choosing proper descaling reagent, self-generated oxidation-induced copper coating appeared on the steel surface. The method proposed in this work is environmentally friendly for nontoxic chemicals being used. In addition, this provides a new concept for producing protective composite by oxidizing from the substrate directly and there is no binding problem.

Oxidation-induced Cu coating on steel surface

Copper is accumulated in recycled steels and is difficult to be removed during steelmaking processes when steel scrap is used as steel sources. Meanwhile, copper characteristics are of importance both to human beings and to animals and plants. In this paper, integrated copper coating was observed on the surface of copper-containing steels when the steels were heated at around 1150°C. However, the copper was separately scattered in and under the surface rust after heating at 1000°C. The forming mechanisms of copper coating are discussed in detail. By choosing a proper descaling reagent, self-generated oxidation-induced copper coating appeared on the steel surface. The method proposed in this work is environmentally friendly for nontoxic chemicals being used. In addition, this provides a new concept for producing protective composite by oxidizing from the substrate directly and there is no bonding problem.

Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations

Novel acid-terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by 1H and 13C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl3, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white-spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans-esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol-functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins.

Enhanced MALDI MS sensitivity by weak base additives and glycerol sample coating

The concept of rationally designing MALDI matrices has been extended to the next “whole sample” level. These studies have revealed some unexpected and exploitable insights in improving MALDI sensitivity. It is shown that (i) additives which only provide additional laser energy absorption are best to be avoided; (ii) the addition of proton donors in the form of protonated weak bases can be highly beneficial; (iii) the addition of glycerol for coating crystalline samples is highly recommended. Overall, analytical sensitivity has been significantly increased compared to the current “gold” standards in MALDI MS, and new insights into the mechanisms and processes of MALDI have been gained.

Crosslinking of Poly(N-vinyl-2-pyrrolidone) in the Coating of Cotton Yarn

Coating of cotton yarn is employed in the textile industry to increase the mechanical resistance of the yarns and resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study is to investigate the usage of a synthetic hydrophilic polymer, poly(N-vinyl-2-pyrrolidone) (PVP), to coat 100% cotton textile yarn, aiming to give the yarn a temporary mechanical resistance. For the improvement of the mechanical resistance of the yarn, the following crosslinking processes of PVP were investigated: UV-C (ultraviolet) radiation, the Fenton and photo-Fenton reactions, and sensitized UV-C radiation. The influence of each crosslinking process was determined through tensile testing of the coated yarns. The results indicated that the best crosslinking process employed was UV-C radiation; increasing the mechanical resistance of the yarn up to 44% if compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. POLYM. ENG. SCI., 51:445-453, 2011. (C) 2010 Society of Plastics Engineers

Fluidized bed CrN coating formation on prenitrocarburized plain carbon steel

CrN coatings were formed on plain carbon steel by prenitrocarburizing, followed by thermoreactive deposition and diffusion (TRD) in a fluidized bed furnace at 570 °C. During TRD, Cr was transferred from Cr powder in the fluidized bed to the nitrocarburized substrates by gas-phase reactions initiated by reaction of HCl gas with the Cr. The microstructural processes occurring in the white layer, caused by N diffusion toward the surface during this stage were studied. This study compares TRD atmospheres employing inert gas and HCl or inert gas, H2, and HCl. Surface characterization was performed by scanning electron microscopy (SEM), x-ray diffraction (XRD), and glow-discharge optical-emission spectroscopy (GDOES).

Cr(N,C) diffusion coating formation on pre-nitrocarburised H13 tool steel

The microstructural processes of Cr(N,C) coating formation by thermoreactive deposition and diffusion (TRD) on pre-nitrocarburised H13 tool steel were studied. Both nitrocarburising and TRD were performed in fluidized bed furnaces at 570 °C. During TRD, chromium was transferred from chromium powder in the fluidized bed, to the nitrocarburised substrates by gas-phase reactions initiated by reaction of HCl gas with the chromium. Addition of 30% H2 to the input inert gas was found to increase the rate of coating formation, although hydrogen reduction resulted in rapid loss of nitrogen to the surface. The reason for the increased rate of coating formation could not be established without further investigation, although several possible explanations have been proposed. It was found that porosity and the formation of an iron nitride ‘cover layer’ during nitrocarburising were the biggest influences on the microstructure of the Cr(N,C) coating. Microstructural characterization of the coatings was performed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and glow discharge optical emission spectroscopy (GDOES).

COATING COMPOSITION AND PROCESS FOR THE PREPARATION THEREOF

The invention relates to coating compositions and processes for the preparation thereof. The coating composition is used for the formation of hydrophobic coatings on a substrate. The coating composition may be used for the formation of hydrophobic particulate coatings.