Parameters influencing the templated growth of colloidal crystals on chemically patterned surfaces

The influence of various experimental parameters on the vertical deposition and structure formation of colloidal crystals on chemically patterned surfaces, with hydrophilic and hydrophobic areas, was investigated. The pattern dimensions range from about 4 to 400 microm, which is much larger than the individual particle size (255 nm), to control the microscopic crystal shape rather than influencing the crystal lattice geometry (as achieved in colloidal epitaxy). The deposition resolution and selectivity were tested by varying the particle concentration in the suspension, the substrate withdrawing speed, pattern size and orientation, and wetting contrast between the hydrophilic and hydrophobic regions. The evolution of colloidal crystal thickness with respect to the pattern dimensions and deposition parameters was further studied. Our results show that the pattern size has a rather strong influence on the deposited number of colloid layers and on the crystal quality. Better results are obtained when the lines of a stripe pattern are oriented parallel to the withdrawing direction rather than perpendicular. The deposition resolution (defined as the minimum feature size on which particles can be deposited) depends on the wetting contrast and increases with lower average hydrophobicity of the substrate.     

The Application of Nano-SiOx Coatings as Migration Resistance Layer by Plasma Enhanced Chemical Vapor Deposition

Accumulative intake of plasticizers that are generally used to produce flexibility of webs in plastics has been proven to cause reproductive system problems and women??s infertility, and long-term consumption may even cause cancer. Hence a nano-scale layer, named as functional barrier layer, was deposited on the plastic surface to prevent plasticizer diethylhexyl phthalate (DEHP) migration from food-contact materials to foods. The feasibility of a functional barrier layer, i.e. SiO_x coating through plasma enhanced chemical vapor deposition process was then described in this paper. In this research we used Fourier transform infrared spectroscope to analyze the chemical composition of the coatings, scanning electron microscope to explore the topography of the coating surfaces, surface profilemeter to measure coating thickness in plastics, and high-performance liquid chromatography to evaluate the barrier properties of coatings. The results have clearly shown that the coatings can perfectly block the migration of the DEHP from plastics to their containers. It is to be noted that process parameters had a critical influence on the block properties of coatings. When the deposition conditions of SiO_x coatings were optimized, i.e. the discharge power of 50?W, 4:1 of O₂: HMDSO ratio and the thickness of 100?nm, the 71.2?% DEHP was effectively blocked in the plastic film.     

Plasma enhanced aerosol–gel method: a new way of preparing ceramic coatings

The sol–gel process is widely used for the production of powders, coatings and bulk materials. However, being a wet-chemical technique, it has certain limitations related to properties of aqueous colloidal solution, especially when applied as a coating. The most frequently used methods, such as dip- and spin-coating, are difficult to apply onto more complex substrates. In these cases, the aerosol–gel deposition method can be regarded as the solution of this problem. In the present article, a novel plasma enhanced aerosol–gel method of coatings production is presented. A novelty of this method is based on an integration of the aerosol–gel deposition of thin films and their low temperature plasma treatment. Owing to the above, all stages of the coatings production process—substrate preparation, film deposition, and its plasma treatment, can be carried out in a single reactor. The design and operational scheme of such device is presented in this work. Using this device, thin coatings were first deposited on substrates and then plasma treated. The effect of deposition and plasma discharge conditions on morphology and chemical structure of the films has been studied. It was found that plasma treatment had a substantial influence on all the examined properties of the aerosol–gel deposited coatings.     

Slow vertical deposition of colloidal crystals: a Langmuir-Blodgett process?

For an evaporating colloidal suspension in which the evaporation velocity exceeds the sedimentation velocity, particles will accumulate at the solvent-air interface. If neither diffusion nor convection can disperse this accumulation, it is expected to grow into a colloidal multilayer several microns thick. We observe that the thickness of colloidal crystals vertically deposited from 1 mum diameter polystyrene latex suspensions of 0.002 < or = phi < or = 0.008 increases linearly with distance in the growth direction and that these thickness profiles are consistent with their growth from a horizontal colloidal layer accumulated beneath the solvent-air interface. We describe a means for performing vertical deposition at growth rates slower than the evaporation rate by adding solvent to the bottom of the colloidal suspension and observe that halving the growth rate of vertical deposition increases both the thickness and the reflectivity of the resulting colloidal crystals, effects indistinguishable from those of doubling the concentration of the colloidal suspension, data also consistent with the colloidal crystals' growth from a horizontal layer of particles beneath the interface. If sufficiently little reorganization is involved as particles move from this horizontal layer to the vertically deposited colloidal crystal, slow vertical deposition of polymer microspheres might be thought of as the Langmuir-Blodgett transfer of a horizontal colloidal crystal onto a vertical substrate. Colloidal crystals deposited using both high concentration and slowed growth can have peak IR reflectance in excess of 80%, exceeding most published values. These observations provide a conceptual framework for engineering vertically deposited colloidal crystals that combine thickness with good optical performance.     

Effects of liquid bridge between colloidal spheres and evaporation temperature on fabrication of colloidal multilayers

For the application of colloidal crystal films as "photonic band gap" materials, their domain size and thickness are significant. The substrate withdrawing speed, the colloidal suspension volume fraction, and the colloidal suspension temperature have been studied for the domain size and thickness controls of colloidal crystals in this study. Stable dispersions of monodispersed polystyrene spheres with a diameter of 245 nm were synthesized according to a general emulsion polymerization for colloidal crystal films. By experimental results and the theoretical relationship between the number of layers and other parameters, we could know that the water bridge between colloidal spheres (which is formed by capillary force) influences the number of colloidal crystal layers significantly.     

Colloid surface engineering via deposition of multilayered thin films from polyelectrolyte blend solutions

Multilayer thin films were constructed on polystyrene colloidal particles by depositing alternating layers of poly(allylamine hydrochloride) (PAH) at pH 7.5 and varying composition blends of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS) at pH 3.5. Following the deposition of each layer, microelectrophoresis experiments showed alternating zeta-potentials, suggesting the formation of multilayered films on the particles. Scanning and transmission electron microscopy were used to examine the surface morphology of the colloidal particles, with homogeneous surface coatings apparent for films deposited from PAA/PSS blend solutions containing up to 90 wt % PAA. The colloidal stability of these particles is greater than those coated with individual PAH and PAA layers. In the case of the blend PAA/PSS = 25:75 wt %, up to 20 layers were assembled without compromising the colloidal stability of the dispersion. The results demonstrate that the deposition of layers from PE blend solutions containing a strong and weak PE can be used as a facile method for controlling the surface properties and hence the colloidal stability of core-shell particles, as well as the thickness and morphology of the coatings. Control of these parameters is important for subsequent processing and application of these particles in controlled delivery, photonics, catalytic, and separation applications.     

Hybrid silica coatings on polycarbonate: enhanced properties

Hybrid silica coatings based on 3- glycidoxypropyltriethoxysilane (GPTES), tetraethylorthosilicate (TEOS) and colloidal silica were deposited on polycarbonate (PC) by the sol–gel method, in order to obtain a material with enhanced properties with respect to raw PC (mainly scratch resistance, hydrophobicity and density), and consequently reach increased durability. The necessity of performing a N₂-plasma treatment on PC (before coating deposition) was highlighted in order to obtain a good adherence between the coating and the substrate: XPS measurements showed that after treatment, nitrogenous radicals had formed on the PC surface and were able to link covalently with the sol during its deposition. Adherence was also higher when young sols (<8-day-old) were used. Different alkoxysilanes/colloidal silica ratios were tested to optimize the coating resistance: crack resistance of the coatings was found to be greater when the ratio was high. Scratch resistance of raw PC was enhanced as soon as PC was coated, irrespective of the alkoxysilanes/colloidal silica ratio or the sol ageing time. The density of the coatings was assessed by environmental ellipsometric porosimetry and found to be very high. Water contact angle measurements showed that the hydrophobicity of the coatings was inferior to raw PC. The addition in the sol of a small wt% of octyltriethoxysilane (OTES), 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FTES) and silicone surface additive (BYK-306) allowed a significant increase in hydrophobicity of the samples.     

Biomaterial coatings by stepwise deposition of silk fibroin

A completely aqueous, stepwise deposition process with Bombyx mori silk fibroin for the assembly of nanoscale thin film coatings is reported the first time. The focus of this work was to develop an understanding of the control of this deposition process and to characterize the films formed from a physicochemical perspective. The deposition process was monitored by UV spectrophotometry and research quartz crystal microbalance. Both absorbance and film thickness correlated linearly with the number of silk fibroin layers deposited, analogous to multilayered materials fabricated from conventional polyelectrolytes. The polymer adsorption process was stable and reproducible, with control of a single layer thickness ranging from a few to tens of nanometers, determined by the concentrations of silk fibroin, salt concentration in the dipping solution, and method of rinsing. The driving force for the assembly of silk fibroin onto the substrate was primarily hydrophobic interactions, while some electrostatic interactions were also involved. The difference with this approach from traditional polyelectrolyte layer-by-layer techniques is that an intervening drying step is used to control the structure and stability of the self-assembled silk fibroin. The assembled films were stable under physiological conditions and supported human bone marrow stem cell adhesion, growth, and differentiation. This approach offers new options to engineer biomaterial coatings as well as bulk materials with control of both interfacial properties conducive to specific cellular or tissue responses and the potential to entrap and deliver labile molecules or other components due to the all-aqueous process described.     

Colloidal crystal layers of hexagonal nanoplates by convective assembly

Particles of the zeolite ZSM-2 prepared as nearly hexagonal nanoplatelets were coated onto flat substrates by a convective assembly technique. On the submillimeter scale, coatings ranged in patterns from striped to continuous. Particles were preferentially oriented out-of-plane, as supported by X-ray diffractometry. The novel observation is that where the particle coating was only a monolayer thick, particles were locally close-packed and uniformly oriented both in and out of plane in a hexagonal colloidal crystalline arrangement that may be described as being tiled (observations by scanning electron microscopy). This is the first documented demonstration of convective assembly applied to anisometric nanoparticles that resulted in particulate coatings with locally ordered microstructure, i.e., colloidal crystallinity.     

Mechanism and kinetics of the formation of zinc pack coatings

A zinc deposition method that could be used instead hot-dip galvanizing is pack cementation, where the substrate is heated immersed in a powder mixture containing Zn and a halide activator (NH₄Cl). In the present work the mechanism of this process is examined, along with the effect of temperature and heating time on the coating thickness and structure. For this purpose the coating was deposited and characterized with SEM, while the deposition mechanism was investigated with DSC. From the above examination it was deduced that the deposition of Zn takes place with a multiple-step mechanism, which involves several reactions in the gaseous phase including the formation of volatile zinc halides and finally the diffusion of zinc in the crystal lattice of the ferrous substrate. This procedure is accomplished at about 300°C and leads to the growth of a coating composed by two layers referring to Γ and δ phase of the Fe-Zn system. The coating deposition rate seems to be controlled by the zinc diffusion as its determination at 300 and 350°C showed, where it was deduced that the coating thickness is a linear function of the square root of heating time. However the coating structure is not affected by the heating time and temperature.     

Versatile multilayer thin film preparation using hydrophobic interactions, crystallization, and chemical modification of poly(vinyl alcohol)

Multilayer thin film coatings were prepared on silicon substrates. Poly(vinyl alcohol) was adsorbed from aqueous solution to propyldimethylsilyl-modified silicon wafers. This thin semicrystalline coating was chemically modified using acid chlorides to form thicker, hydrophobic coatings. The products of the modification reactions allowed adsorption of a subsequent layer of poly(vinyl alcohol) that could subsequently be hydrophobized. This two-step process (adsorption/chemical modification) allows layer-by-layer deposition to prepare coatings with thickness, chemical structure, and wettability control.     

Synthesis and crystallization of hybrid spherical colloids composed of polystyrene cores and silica shells

The St?ber method has been adopted to prepare hybrid core-shell particles by coating the surfaces of monodisperse polystyrene beads with uniform silica shells. Polystyrene beads with diameters in the range of 0.1-1.0 microm have been successfully demonstrated for use with this process, and the thickness of the silica coating could be controlled in the range of 50-150 nm by adjusting the concentration of tetraethoxysilane, the deposition time, or both. The morphology and surface smoothness of the deposited silica were found to strongly depend on a number of parameters such as the surface functional groups on the polymer beads, the pH value of the medium, and the deposition time. Hollow spheres made of silica could be obtained by selectively removing the polymer cores via calcination in air at an elevated temperature or by wet etching with toluene. These core-shell colloids were also explored as building blocks to fabricate long-range ordered lattices (or colloidal crystals) that exhibited stop bands different from those assembled from spherical colloids purely made of either polystyrene or silica.     

A new room-temperature deposition technique for optical coatings

We describe a new coating method Laminar Flow Coating (LFC) technique developed to obtain highly reflective (HR) laser damage resistant sol-gel multidielectric coatings. Such coatings are used in high-power lasers for inertial confinement fusion experiments (ICF). This technique uses substrates in an upside-down position and a travelling wave of coating solution is transported with a laminar motion under the substrate surface with a tubular dispense unit. This creates a thin-film coating by solvent evaporation. Satisfactory results have been obtained on 20-cm square glass substrates regarding the optical performances, the thickness uniformity, the edge-effects and the laser damage resistance. This deposition technique combines the advantages of both classical techniques: the non-exclusive substrate geometry such as in dip-coating and the small solution consumption such as in spin-coating.The association of sol-gel colloidal suspensions and LFC coating process has been demonstrated as a promising way to produce inexpensive specific optical coatings [1].     

Correlation Between the Electrical and Optical Properties of an Atmospheric Pressure Plasma During Siloxane Coating Deposition

The effect of varying process parameters on atmospheric plasma characteristics and properties of nanometre thick siloxane coatings is investigated in a reel-to-reel deposition process. Varying plasma operation modes were observed with increasing applied power for helium and helium/oxygen plasmas. The electrical and optical behaviour of the dielectric barrier discharge were determined from current/voltage, emission spectroscopy and time resolved light emission measurements. As applied power increased, multiple discharge events occurred, producing a uniform multi-peak pseudoglow discharge, resulting in an increase in the discharge gas temperature. The effects of different operating modes on coating oxidation and growth rates were examined by injecting hexamethyldisiloxane liquid precursor into the chamber under varying operating conditions. A quenching effect on the plasma was observed, causing a decrease in plasma input power and emission intensity. Siloxane coatings deposited in helium plasmas had a higher organic component and higher growth rates than those deposited in helium/oxygen plasmas.     

Deposition of oriented zeolite A films: in situ and secondary growth

Zeolite A suspensions with a monomodal, narrow particle size distribution have been prepared. The suspended particles in a TMAOH water solution at pH 9 are negatively charged with a zeta potential of −43 mV. Modification of the external surface of the zeolite particles by a silylation reaction produces particles that, when they are suspended in water, are positively charged and have a zeta potential of +40 mV.The suspensions of the negatively or positively charged particles can be used for the preparation of adsorbed layers of particles on oppositely charged substrates by electrostatic attraction. This deposition process leads to a high coverage of the substrate with well-adhered particles. The cubic morphology of the zeolite particles results in preferential orientation after deposition. The particles are oriented with their {h 0 0} planes (cube faces) parallel and perpendicular to the substrate (out-of-plane orientation). The particles are randomly oriented with respect to the direction perpendicular to the substrate (in-plane orientation). Although, under optimized conditions, the coverage is high and only one adsorption cycle is necessary, the particles are not closely packed.Alternately, the zeolite particle suspensions can be used to deposit close-packed arrays of particles by convective particle transport during dip coating on substrates bearing the same charge as the zeolite particles. Using monodispersed zeolite A suspensions and slow speed dip coating close-packed hexagonal colloidal crystals were prepared. The type of colloidal crystal deposits formed range from continuous sublayers, monolayers, or multilayers to isolated discoidal clusters consisting of few zeolite particles. Factors affecting the deposited layer(s) structure are particle concentration of the suspension and withdrawal speed. In addition to close packing, the layers prepared by dip coating exhibit preferred orientation with the particle faces lying parallel and perpendicular to the substrate surface. Moreover, this second route of precursor film formation by colloidal crystallization leads to domains of well-aligned zeolite particles in three dimensions, i.e. with their faces parallel to each other. The oriented domains span the length of several particles; however, low angle boundaries and other defects during colloidal crystallization prevent the formation of macroscopically three-dimensionally ordered zeolite particles.The precursor layers were subjected to secondary growth in order to prepare continuous intergrown films. Secondary growth proceeds initially by local epitaxy on the deposited particles. Later in the process, deposition proceeds by incorporation of particles from solution along with re-nucleation on the growing film. The intergrown films have predominately [h 0 0] out-of-plane orientation; however, after extended secondary growth treatment a population of [h h h] grains appears on the surface of the regrown films.     

Synthesis and Properties of Cerium and Titanium Oxide Thin Coatings for Corrosion Protection of 304 Stainless Steel

Powders and thin coatings of ceria and titania were synthesized from aqueous and solvent-based precursors. Thin coatings were deposited on polished 304 stainless steel coupons by dipping them in the appropriate sol-gel oxide precursors. The coatings were subsequently densified and crystallized at several hundreds of degrees. It was possible to obtain dense titania coatings by applying thin coatings of cerium dioxide prior to titania on stainless steel substrates. Underlayer ceria coatings proved to be pivotal in obtaining dense titania coatings and preserving the integrity of the stainless steel while going through the high temperature treatments. The effect of processing parameters such as the atmosphere of heat-treatment, and temperature on the microstructure and crystal structure of the films and powders of ceria and titania was investigated. X-ray diffraction was used to identify the crystal structure of films and powders upon heat-treatment. Electrochemical measurements in NaCl, and analytical techniques such as SEM and EDX were used to evaluate the corrosion performance and pitting morphology of coated samples. A composite coating of ceria and titania was able to prevent crevice corrosion and increase the pitting resistance of the 304 stainless steel relative to the uncoated substrate.     

Numerical Modeling of Thin Film Deposition in Expanding Thermal Plasma

Expanding thermal plasma (ETP) is a widely used technique for deposition of a thin layer of ceramic materials and metal oxide on a substrate for a wide range of applications including abrasion resistance, UV absorption, as well as conductive and optical coatings. The coating quality is found to be dependent on operating parameters as well as reactor designs. In this article, we have presented a CFD based model of the ETP process to simulate the deposition of silica-like coatings on a polycarbonate substrate. Along with the flow-thermal model of plasma jet expansion process, the study also reports the development of a simplified gas phase and surface reaction model to simulate the coating phenomena. The model has been used further to study the effect of various operating conditions on the coating thickness, viz. reactor pressure, reagent flow rate, distance of the substrate from the arc and substrate alignment.     

Facile synthesis of TiO2 inverse opal electrodes for dye-sensitized solar cells

Engineering of TiO(2) electrode layers is critical to guaranteeing the photoconversion efficiency of dye-sensitized solar cells (DSSCs). Recently, a novel approach has been introduced for producing TiO(2) electrodes using the inverted structures of colloidal crystals. This paper describes a facile route to producing ordered macroporous electrodes from colloidal crystal templates for DSSCs. Using concentrated colloids dispersed in a volatile medium, the colloidal crystal templates were obtained within a few minutes, and the thickness of the template was easily controlled by changing the quantity of colloidal solution deposited. Here, the effects of the structural properties of the inverse opal TiO(2) electrodes on the photovoltaic parameters of DSSCs were investigated. The photovoltaic parameters were measured as a function of pore ordering and electrode film thickness. Moreover, DSSC applications that used either liquid or viscous polymer electrolyte solutions were investigated to reveal the effects of pore size on performance of an inverse opal TiO(2) electrode.     

电化学方法在钛表面制备Co-YSZ/HAp纳米复合涂层

采用复合电沉积和电泳沉积两步法在钛基体上制备了Co-YSZ/HAp纳米复合涂层, 与只采用电泳沉积法在钛基体上制备纳米HAp单一涂层进行了比较研究.采用场发射扫描电镜、X 射线衍射和能量散射谱对复合涂层的微观形貌, 纳米HAp外层表面形貌, 晶相, 复合涂层的断面形貌及元素组成分布进行分析研究. 通过粘结-拉伸实验测定了涂层与基体的结合强度, 结果表明, Co-YSZ/HAp 纳米复合涂层与钛基体的结合强度明显高于纳米HAp 单一涂层与钛基体的结合强度, 说明复合涂层具有更好的力学性能.     

Electrochemical Processing of Reaction-bonded Ceramic Composite Coatings

Ceramic matrix composite coatings are currently of much interest for application in high-temperature and highly corrosive environments. Formation of ceramic coatings by electrochemical processing is a relatively new mean^[1-2]. It presents several advantages over alternative coating techniques, the thickness and morphology of the deposit can be controlled by the electrochemical parameters, relatively uniform deposits are obtainable on complex shapes, the deposition rate is higher than that using most other methods and the equipment required is of low cost Recently we developed a novel fabrication technique for the production of ceramic/ceramic and ceramic/metal composite coatings by electrochemical processing^[3]. The technique combined two electrochemical deposition methods, electrophoretic deposition (EPD) and electrolytic deposition (ELD), which can produce uniform composite layers of closely controlled thickness on both metallic and ceramic substrates at ambient temperature with inexpensive equipment. However, the main problem associated with electrochemical processing is the difficulty in sintering of the coatings. First, high temperature is required for sintering of the coatings. Secondly, the volume shrinkage of the coatings during sintering leads to the formation of cracks in coatings bonded to metal substrates. So a reaction forming technique, reaction bonding process, also has been developed to produce near net-shape ceramic coatings, which overcome problems caused by the shrinkage of ceramics during sintering.