Formation and Depth Profiling Analysis of Multilayers Derived from Sol-Gel Processing Using Dynamic SIMS, RBS, and TEM

Silica sol-gel single layer AR coatings are used in high peak power pulsed lasers due to their high laser induced damage threshold (LIDT) and their low refractive index (1.22). We have used sol-gel processing to spin and dip coat multilayers of alternating high index (zirconia/hafnia) and low index (base catalysed silica) sol-gels on to fused silica substrates. When tailored at the correct thickness these stacks have shown >95% reflectivity at 355 nm and normal incidence whilst retaining a high LIDT. Depth profiling using Dynamic Secondary Ion Mass Spectrometry (DSIMS) and Rutherford back scattering (RBS) through these multilayer coatings has revealed the effect of increasing the number of layers in the stack. Results are presented for both spin and dip coated multilayers and a significant difference in the interfacial boundary is seen between the two coating processes. These differences are related to changes in the LIDT of the coatings. Individual layer thicknesses were estimated using this technique and compared to values gained from UV-Visible spectroscopy. TEM analysis of an ion-milled cross-section of the multilayers was performed showing the colloidal silica coatings and the depth of interpenetration of the interfaces.     

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].     

Surface synthesization of magnesium alloys for improving corrosion resistance and implant applications

In the field of biodegradable material, a new research area has emerged for magnesium (Mg) and its alloys because of its high biocompatibility and biomechanical compatibility. This review summarizes many important types of research that have been done on degradable coatings on magnesium and its alloys for various implant applications. When magnesium alloys come into contact with other metals, they have a low open circuit potential and are consequently prone to galvanic corrosion. When exposed to air or a humid environment, magnesium may rapidly oxidize and generate a thin layer of loose MgO. Its applications were limited due to these drawbacks. Different types of corrosion have been studied in relation to magnesium and its alloys. Several coating methods are described, split into conversion and deposition coatings based on the individual processing procedures employed. This paper covers the most recent advancements in the development of biodegradable Mg alloy coatings over the last decade, revealing that the corrosion resistance of Mg and its alloys increases in most of circumstances due to coatings. Corrosion rate, coating morphology, adhesion, and surface chemistry were identified and explored as significant elements affecting coating performance. Calcium phosphate coatings made by deposition or conversion processes established for orthopedic purposes are the focus of many investigations according to a review of the literature. More research is needed on organic-based biodegradable coatings to improve corrosion resistance. Improved mechanical qualities are also crucial for coating materials. Developing adequate methodologies for studying the corrosion process in depth and over time is still a hot topic of research.     

Planar step-index waveguides obtained via sol–gel synthesis from organometallic precursors

Inorganic and hybrid sols obtained from Si, Ti, Zr and Ce organometallic precursors were used to prepare single and multilayer coatings with different thicknesses. Planar step-index waveguides with different refractive indices were thus prepared by dip-coating the above sols onto commercial soda-lime glass substrates, followed by appropriate thermal annealing. The resultant coatings were characterized by transmission electron microscopy and energy dispersive X-ray spectrometry to elucidate the interface and bonding between the sol–gel derived coatings and the glass substrates. Diffusion of alkali and alkaline earth elements from the glass into the coating layer was confirmed and proposed to play a role in the coating-substrate bonding, inducing excellent optical quality planar interfaces. Optical waveguide characterization performed on a 4.15 μm thick hybrid SiO₂:CeO₂ (95:5) step-index waveguide yielded losses of 1.50 dB/cm.     

Stability of capillaries coated with highly charged polyelectrolyte monolayers and multilayers under various analytical conditions--application to protein analysis

The stability of capillaries coated with highly charged polyelectrolytes under various analytical conditions was studied, as well as their performance for the analysis of proteins by Capillary Electrophoreis (CE) over a wide range of pH (2.5-9.3). In this study, fused silica capillaries were modified either with a poly(diallyldimethylammonium) chloride (PDADMAC) monolayer or PDADMAC/poly(sodium 4-styrenesulfonate) (PSS) multilayer coatings, using optimal coating conditions previously determined. Results show that the coated capillaries are remarkably stable and efficient to limit protein adsorption under a variety of extreme electrophoretic conditions even in the absence of the coating agent in the background electrolyte which is exceptional for non-covalent coatings. Monolayer coated capillaries were demonstrated for the first time to be stable to acidic rinses and to organic solvents which proves that the stability of the capillaries is highly dependent on the coating procedure used. In addition, PDADMAC/PSS multilayer coatings were found to be stable to alkaline treatments. PDADMAC/PSS coated capillaries gave excellent performances for the analysis of proteins covering a large range of pI (4-11) and of molecular weight (14-65 kDa) over a wide pH range (i.e. 2.5-9.3). Even at high pH 9.3, protein analysis was possible with very good repeatabilities (RSD(tm)<1% and RSD(CPA)<2.6% (n ≥ 8)) and high peak efficiencies in the order of 700,000.     

Electric-field-induced fabrication of covalently linked second-order nonlinear optical multilayer films on nonconductive substrates

A highly stable second-order nonlinear optical multilayer film was constructed on insulating substrates using the electric-field-induced layer-by-layer assembly technique. The substrates used in this method could be arbitrary. In another, the substrates could be modified with polyanion solution by spin coating as cladding layer. Then, the nonlinear optical multilayer films were assembled on the cladding layer directly by the electric-field-induced layer-by-layer assembly technique. The resulting cross-linked multilayer films fabricated by this method displayed high optical transparency, good thermal stability, and excellent nonlinear optical properties which can be made into waveguide devices directly.     

Influence of polyelectrolyte coating conditions on capillary coating stability and separation efficiency in capillary electrophoresis

Polyelectrolytes are widely used in capillary electrophoresis as coating agents of silica capillaries to prevent adsorption phenomena and improve the repeatability of peptide and protein analysis. A systematic study of the coating experimental conditions has been carried out to optimize coating stability and performance. The main experimental parameters studied were the type and concentration of polyelectrolytes used in several monolayer and multilayer coatings, the ionic strength of coating and stabilizing solutions, and the procedures used for coating and capillary storage. Electroosmotic flow magnitude, direction and repeatability were used to monitor coating stability. Coating ability to limit adsorption was investigated by monitoring variations of migration times, time-corrected peak areas and separation efficiency of test peptides. Capillary-to-capillary and batch-to-batch reproducibility was also studied. In addition, the separation performance of polyelectrolyte coatings were compared to those obtained with bare silica capillaries.     

Influence of polyelectrolyte capillary coating conditions on protein analysis in CE

CE of biomolecules is limited by analyte adsorption on the capillary wall. To prevent this, monolayer or successive multiple ionic‐polymer layers (SMILs) of highly charged polyelectrolytes can be physically adsorbed on the inner capillary surface. Although these coatings have become commonly used in CE, no systematic investigation of their performance under different coating conditions has been carried out so far. In a previous study (Nehmé, R., Perrin, C., Cottet, H., Blanchin, M. D., Fabre, H., Electrophoresis 2008, 29, 3013–3023), we investigated the influence of different experimental parameters on coating stability, repeatability and peptide peak efficiency. Optimal coating conditions for monolayer and multilayer (SMILs) poly(diallyldimethylammonium) chloride/ poly(sodium 4‐styrenesulfonate) coated capillaries were determined. In this study, the influence of polyelectrolyte concentration and ionic strength of the coating solutions, and the number of coating layers on coating stability and performance in limiting protein adsorption was carried out. EOF magnitude and repeatability were used to monitor coating stability. Coating ability to limit protein adsorption was investigated by monitoring variations of migration times, time‐corrected peak areas and separation efficiency of test proteins. The separation performance of polyelectrolyte coatings were compared with those obtained with bare silica capillaries.     

The Structural Stability of Graphene Anticorrosion Coating Materials is Compromised at Low Potentials

Corrosion of engineered structures is a major problem causing an estimated economic loss of more than 2 trillion US dollars annually worldwide. Graphene has recently emerged as highly promising, low‐cost, and transparent anticorrosion coating material. Herein, it is shown that a multilayer graphene film grown on Ni by chemical vapor deposition undergoes abrupt stability failure under galvanic‐corrosion conditions. The multilayer graphene coating was examined by optical microscopy, SEM, energy dispersive X‐ray spectroscopy, Raman spectroscopy, and cyclic voltammetry after exposure to potentials between 600 and 1300 mV in alkaline solution. A fast and simple electrochemical method is proposed to sensitively quantify the damage caused by the applied potential bias. It is based on quantification of the oxidation signals generated by the underlying Ni‐metal catalyst that is exposed by damage to the graphene film. It is shown that film damage can start at potentials as low as 900 mV and that macroscopic and extensive damage can be caused at potentials above 1000 mV. In addition, once the graphene film has been damaged, the corrosion rate of the underlying metal is significantly increased. These findings are of great importance for potential applications of multilayer graphene films in coating metal structures with huge industrial and economic implications.     

Surface-treatment of Alkaline Earth Sulfides Based Phosphor

A series of alkaline earth sulfides based phosphors Ca0.8Sr0.2S : Eu^2 , Tm^3 were covered with a layerof protective coating with alkaline earth fluorides by heating the mixture of phosphor and NH4HF2 at elevatedtemperatures. The coatings were characterized by means of XRD and SEM. The optical properties of thecoated phosphors and the influences of the coating on their properties have been discussed extensively. Thestabilities of the coated and uncoated phosphors have been compared.     

聚合物层状组装膜

介绍了近几年来我们研究组在层状组装膜的构筑以及功能化研究方面取得的一些最新进展.包括结合表面溶胶-凝胶技术与静电层状组装技术,实现了二阶非线性基团在层状组装多层膜中的非对称排列,制备了具有二阶非线性效应的膜材料;采用室温压印技术,发展了一种简便、经济和具有普适性的层状组装聚合物膜图案化方法;以轻度交联的聚合物微凝胶为构筑基元,制备了具有高负载量的聚合物层状组装膜;发展了一种基于离子剥离技术的层状组装自支持膜制备方法;基于层状组装技术,制备了具有超疏水和抗反射功能的涂层.     

Deposition of protective-decorative coatings onto aluminum alloys

Technique for deposition of a nickel coating onto various aluminum alloys was developed. This coating can be used both independently and as a sublayer under multilayer coatings and, in particular, under those of nickel, tin–bismuth, lustrous nickel, and lustrous chromium. The technique includes anodization, chemical treatment, and electrodeposition of nickel in a special solution. The working modes of the anodization electrolyte were chosen and the necessity for a preliminary chemical treatment of the oxide film being formed was substantiated. A composition of the acid electrolyte for the subsequent nickel plating was developed with buffer and improving additives. The thus deposited electroplated nickel coatings exhibit a high adhesion to the aluminum base without additional thermal treatment. This makes it possible not only to reduce the technological time for deposition of the subsequent multilayer coatings, but also to fully automate the whole process.     

The electrodeposition of composite coatings: Diversity,applications and challenges

A wide range of coatings can be produced by incorporating particles into an electrodeposit. The matrix may be a metal, conductive polymer or conductive ceramic, whereas the particle can be metallic, polymeric, ceramic or combinations of spheroidal, irregular or layered inclusions. Nanostructured, gradient, multilayer and sandwich layer deposit further widen possibilities. Electrochemical approaches to the deposition of composite coatings offer the benefits of good control over deposition rate (hence thickness), coating composition and deposit properties. Both faradaic electrodeposition and electrophoresis are usually involved. This review focuses on nanosized inclusions in a metal matrix over the last two decades. Interactions between bath composition, particle dispersion, operational variables and resultant deposit properties are poorly documented in the literature. Our understanding of the mechanism of composite deposition remains patchy, despite progress and computer models are scarce. Electrode geometry, electrolyte hydrodynamics and current distribution remain poorly treated. Markets in electronics, surface engineering, aerospace, corrosion protection and electrochemical energy conversion have been stimulated by newer uses for self-cleaning, superhydrophobic and biocompatible surfaces. Challenges to be met by further research and development are prioritised.     

Stimuli-responsive self-healing anticorrosion coatings: from single triggering behavior to synergetic multiple protections

As a notorious and ubiquitous destructive phenomenon, metal corrosion can cause huge economic losses, infrastructure failures, and even industrial disasters. Tremendous efforts have been dedicated to intelligent self-healing coatings for corrosion inhibition at damaged sites, targeting for enhanced longevity, extensive adaptability of metallic materials. Anticorrosion coating performing self-healing activities, by either healing coating defects or forming protective layer on corrosive parts, is quite attractive in metal-relevant applications. In this review, we mainly focus on stimuli-feedback anticorrosion coatings (SFACs), based on different triggering mechanisms to initiate self-healing behaviors. Stimuli-responsive smart systems, from single stimulus-response to synergetic multistimuli-response, act as a core concept both in controllable healing agent diffusion and increased availability of payloads for corroded area. Multifunctional stimuli-responsive self-healing coatings integrating with non-wettable property are also explored, which provide synergistic and diversified metal protections that are hard to actualize with a single action. Not only research progress of SFACs over the past few decades is reviewed in this article, but also perspectives on future development of this field are presented.     

Polyelectrolyte templating strategy for the fabrication of multilayer hemicyanine Langmuir-Blodgett films showing enhanced and stable second harmonic generation

Polyelectrolyte templating effectively suppresses the aggregation of cationic hemicyanine-based amphiphiles in monolayer Langmuir-Blodgett (LB) films leading to enhanced and stable optical second harmonic generation (SHG). The current study explores the impact of different polyelectrolytes (salts of poly(4-styrenesulfonic acid), deoxyribonucleic acid, and carboxymethylcellulose) on the mode of formation of multilayer LB films of the hemicyanine amphiphile and their SHG response. Pressure-area isotherms and Brewster angle microscopy reveal the impact of the polyelectrolyte complexation on the Langmuir films. Transfer ratios observed during film deposition, supported by electronic absorption spectra and atomic force microscope images of the multilayer LB films, suggest that the polyanions influence the deposition sequence, leading to significant variations in the SHG. Carboxymethylcellulose is identified as an optimal template that induces favorable z-type deposition, leading to the formation of stable multilayer films. These films exhibit the expected quadratic increase of SHG with the extent of deposition; significantly the film response is very stable under extended laser irradiation. It is proposed that structural adjustments of the sandwiched polymer layer lead to the observed deposition sequence and film stability. Polyelectrolyte templating is demonstrated to be a simple and effective strategy for the fabrication of multilayer LB films to elicit efficient quadratic nonlinear optical response.     

离子液体和聚离子液体固相微萃取涂层制备及应用进展

固相微萃取(Solid-phase microextraction,SPME)技术因其具有操作简单、萃取时间短、无需有机溶剂、易于自动化操作等优点,成为近年来发展起来的一种新型样品前处理技术。涂层是SPME技术的核心,决定了涂层萃取的选择性和容量。离子液体和聚离子液体因具有环境友好、蒸汽压低、热稳定性好、设计灵活、粘度大等特点,已作为一类新的涂层材料广泛应用于SPME,并对各种分析物均展现出良好的萃取效果和选择性。本文从制备技术、形貌、选择性、稳定性、寿命、应用等方面综述了近年来离子液体和聚离子液体基SPME涂层的研究进展,对它们的优缺点进行了对比讨论,并对其未来发展方向进行了展望。     

Investigation of the stability of polyelectrolyte multilayer coatings in open-tubular capillary electrochromatography using laser scanning confocal microscopy

A simple polyelectrolyte multilayer (PEM) coating procedure was used for the development of stable modified capillaries. PEM coatings were constructed in fused-silica capillaries using alternating rinses of cationic and anionic polyelectrolytes. The multilayer coatings investigated in this study consisted of two and twenty layer pairs, or bilayers. A bilayer is one layer of a cationic polymer and one layer of an anionic polymer. Poly(diallyldimethylammonium chloride) was used as the cationic polymer, and the polymeric surfactant poly(sodium N-undecanoyl-L-leucylvalinate) was used as the anionic polymer. Previous studies for both chiral and achiral separations have shown that PEM-coated capillaries have excellent reproducibilities, remarkable endurance, and strong stabilities against extreme pH values when used in open-tubular capillary electrochromatography (OT-CEC). In this study, the stability of the coatings was further investigated after exposure to 0.1 M and 1.0 M NaOH. Structural changes of these coatings were monitored using laser scanning confocal microscopy (LSCM) after flushing the capillaries with NaOH. This technique allowed observation of the degradation of the coatings. Observations are discussed in terms of separations using OT-CEC. Electropherograms obtained from the chiral separation of 1,1'-binaphthyl-2,2'-dihydrogenphosphate in OT-CEC showed a decrease in selectivity and an increase in electroosmotic mobility after long exposure to NaOH. The ability to recover the capillaries by exposure to NaOH was also demonstrated. Measurements of electroosmotic mobility and selectivity showed that 2-bilayer and 20-bilayer PEM coatings could be completely removed from the capillary surface after approximately 3.5 and 9.5 h, respectively, of continuous exposure to 1 M NaOH.     

Layer-by-layer fabrication of broad-band superhydrophobic antireflection coatings in near-infrared region

Broad-band superhydrophobic antireflective (AR) coatings in near infrared (NIR) region were readily fabricated on silicon or quartz substrates by a layer-by-layer (LbL) assembly technique. First, a porous poly(diallyldimethylammonium chloride) (PDDA)/SiO2 nanoparticle multilayer coating with AR property was prepared by LbL deposition of PDDA and 200 nm SiO2 nanoparticles. PDDA was then alternately assembled with sodium silicate on the PDDA/SiO2 nanoparticle coating to prepare a two-level hierarchical surface. Superhydrophobic AR coating with a water contact angle of 154 degrees was finally obtained after chemical vapor deposition of a layer of fluoroalkylsilane on the hierarchical surface. Quartz substrate with the as-fabricated superhydrophobic AR coating has a maximal transmittance above 98% of incidence light in the NIR region, which is increased by five percent compared with bare quartz substrate. Simultaneously, the superhydrophobic property endows the AR coating with water-repellent ability. Such superhydrophobic AR coatings can effectively avoid the disturbance of water vapor on their AR property and are expected to be applicable under humid environments.     

Ultrafine grain formation and coating mechanism arising from a blast coating process: A transmission electron microscopy analysis

This article examines the substrate/coating interface of a coating deposited onto mild steel and stainless steel substrates using an ambient temperature blast coating technique known as CoBlast. The process uses a coincident stream of an abrasive blast medium and coating medium particles to modify the substrate surface. The hypothesis for the high bond strength is that the abrasive medium roughens the surface while simultaneously disrupting the passivating oxide layer of the substrate, thereby exposing the reactive metal that then reacts with the coating medium. The aim of this study is to provide greater insight into the coating/substrate bonding mechanism by analysing the interface between a hydroxyapatite coating on both mild and stainless steel substrates. The coating adhesion was measured via a tensile test, and bond strengths of approximately 45 MPa were measured. The substrate/coating interface was examined using transmission electron microscopy and selected area diffraction. The analysis of the substrate/coating interface revealed the presence of ultrafine grains in both the coating and substrate at interface associated with deformation at the interface caused by particle impaction during deposition. The chemical reactivity resulting from the creation of these ultrafine grains is proposed to explain the high adhesive strength of CoBlast coatings.