TEM,XPS and thermo-mechanical properties of novel sustainable hybrid coatings

This work contributes to the development of a new generation of protective coatings composed of organic–inorganic materials. A silica based hybrid film was used in this work as high performance materials. The silica sol–gel film reveals enhanced thermo-mechanical properties in comparison with the pure polymer film. Herein, we demonstrate the possibility of employing cheap SiO₂ as prospective nano-fillers for hybrid coatings with active thermo-mechanical properties. Organic–inorganic hybrid coatings based on polyimide and silica were synthesized through a simple physical mixing technique. 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA), benzene-1,3-diamine (BDA), 3,3′-oxydianiline (ODA) and SiO₂, were used as precursors for the hybrid coatings. These hybrid coatings were deposited via spin coating onto a galvanized iron, aluminum and copper in order to study the adhesive strength. The effects induced by the silica content on the mechanical properties of the coated samples were investigated. The mechanical properties of hybrid composite were found to be enhanced compared to polyimide coating. The main objective was to observe potential improvements in the mechanical and thermal properties of PI–silica hybrid films. Morphology, and structural changes in the composite films were studied as well as adhesion and impact strength and these characteristics were compared with those of unreinforced polyimide films.     

Effects of indenter angle on micro‐scale fracture toughness measurement by pillar splitting

We present improvements to a recently developed pillar splitting technique that can be used to characterize the fracture toughness of materials at the micrometer scale. Micro‐pillars with different aspect ratios were milled from bulk Si (100) and TiN and CrN thin films, and pillar splitting tests were carried out using four different triangular pyramidal indenters with centerline‐to‐face angles varying from 35.3° to 65.3°. Cohesive zone finite element modeling (CZ‐FEM) was used to evaluate the effect of different material parameters and indenter geometries on the splitting behavior. Pillar splitting experiments revealed a linear relationship between the splitting load and the indenter angle, while CZ‐FEM simulations provided the dimensionless coefficients needed to estimate the fracture toughness from the splitting load. The results provide novel insights into the fracture toughness of materials at small‐scales using the pillar spitting technique and provide a simple and reliable way to measure fracture toughness over a broad range of material properties.     

Transformation of polymers in a stream of low-temperature arc discharge plasma

Spraying of polymer materials in a low-temperature plasma stream is a very efficient way of depositing polymer coatings on large surfaces. The deposition of powdered polymers by an arc discharge plasma flow and spraying from the bulk have been compared. The properties of powdered polymers do not change considerably during transportation by the stream because of the short residence of the particles in the plasma. When spraying from the bulk, polymers are transported in the form of melt droplets (polyethylene, polycarbonate) or in gaseous phase (polytetrafluoroethylene); autohesion of the droplets or secondary polymerization occurs, respectively, on the substrate surface. This process offers high-quality thin films and coatings whose structure depends significantly on the characteristics of the substrate as well as on the structure of the source polymer. Obtained polymer coatings contain nitrogen and oxygen entrapped from the atmosphere as well as (on the glass surface) the products of glass etching. This fact enables one to vary widely the properties of the coatings. Furthermore, the problem of obtaining combined protective coatings in which polymer melt fills the pores between metal particles can be solved successfully in a united technological cycle including plasma spraying of the polymer and the metal. © 1995 John Wiley & Sons, Inc.     

Plasma enhanced aerosol–gel deposition of Al2O3 coatings

The new plasma enhanced aerosol–gel technique has been used for alumina films preparation, in this work. This process integrates aerosol–gel deposition of films and their plasma treatment in one reactor. The alumina films deposited by aerosol–gel method on Si substrate were plasma or thermally treated. The influence of deposition and condensation conditions on properties of the films was studied. Produced coatings were characterized in terms of surface morphology (SEM, AFM) as well as crystalline and chemical structure (FTIR, XRD). Plasma discharge used for modification of the substrates prior to the deposition process improved homogeneity of produced coatings. Coatings obtained at room temperature exhibit boehmite structure which was transformed into γ-Al₂O₃ after annealing. A similar transformation was induced by low temperature oxide plasma discharge treatment for sufficiently thin coatings.     

Antireflective coatings prepared by sol–gel processing: Principles and applications

Sol–gel processing is a powerful tool to prepare antireflective (AR) coatings on optical surfaces. In this paper the different strategies to obtain antireflective properties are reviewed: porous λ/4 layers, multilayer interference-type films and index-gradient materials such as “moth eye” structures. The processing of the respective films is described and evaluated; references to respective commercial products on glass substrates are given.AR coatings may have a particularly high importance for transparent ceramics as their index of refraction is significantly higher than that of common glass types. Reflective losses therefore are higher which is especially unpleasant for materials with a yet improvable intrinsic transparency.Recent studies indicate that specific porous λ/4 layers may exhibit pronounced anti-soiling features. Laboratory experiments as well as outdoor exposure tests were used to demonstrate the dust-repellant properties.     

Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys

Inorganic–organic hybrid materials are attracting a strong scientific interest mainly for their outstanding inherent mechanical and thermal properties, which can be traced back to the intimate coupling of both inorganic and organic components. By carefully choosing the experimental parameters used for their synthesis, chemically and thermally stable acrylate-based hybrid material embedding the zirconium oxocluster Zr₄O₄(OMc)₁₂, where OMcCH₂C(CH₃)C(O)O, can be deposited as UV-cured films on aluminium alloys.

In particular, the molar ratios between the oxocluster and the monomer, the polymerisation time, the amount of photo-initiator and the deposition conditions, by using an home-made spray-coating equipment, were optimised in order to obtain the best performing layers in terms of transparency and hardness to coat aluminium alloy (AA1050, AA6060 and AA2024) sheets. Furthermore, it was also evaluated whether the hybrid coatings behave as barrier to corrosion.

Several coated samples were prepared and characterised. Environmental scanning electronic microscopy (ESEM) and scratch test were used to investigate the morphology of the films and to evaluate their scratch resistance, respectively. Electrochemical impedance spectroscopy (EIS) was performed in order to evaluate if the coatings actually protect the metallic substrate from corrosion.

In order to measure shear storage modulus (G′) and loss modulus (G″) of the materials used for coatings, bulk samples were also obtained by UV-curing of the precursors solution. Dynamical mechanical thermal analysis (DMTA) was performed in shear mode on cured disks of both the hybrid materials and pristine polymer for comparison. The values of T_g were read off as the temperatures of peak of loss modulus. The length and mass of all the samples were measured before and after the DMTA analysis, so that the shrinkage of the materials in that temperature range was exactly evaluated.     

Electrochemical synthesis: a novel technique for processing multi-functional coatings

Electrochemical synthesis is a powerful tool for surface modification, substrate cleaning and formulation of thin films and bulk materials. It is especially suited for surface modification of fibers, metals and films. In the past decade electrochemical method has become the preferred technique for in situ passivation, and coating of commodity metals such as aluminum, zinc, copper and steel.

We have successfully synthesized different kinds of conducting polymers, including polypyrrole (PPy)–polyaniline (PANi) composites. The processability and corrosion performance of PPy/PANi, composite coatings are significantly better than those for either PPy or PANi, coatings.

In this paper, we will discuss the use of electrochemical technique in the synthesis and characterization of multi-functional corrosion resistant conducting polymer coatings for aerospace and automotive applications.     

Surface properties of cationic ultraviolet‐curable coatings containing a siloxane structure

A polysiloxane diglycidyl ether was used as a comonomer of epoxy resins to obtain coatings through the ultraviolet curing technique. Notwithstanding its very low concentration (<1 wt %), the siloxane monomer caused a change in the surface properties of the films. Selective surface stratification was evidenced by X‐ray photoelectron spectroscopy analysis, and an interesting surface modification was achieved without changing the bulk properties of the films or the rate of polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 584–589, 2004     

A study on the elastic modulus of silicone duplex or bi-layer coatings using micro-indentation

A Fischerscope continuous microindenter with a spherical indenter was used to obtain maximum indentation load and depth data for a 2.2 mm sheet of RTV11 (a silicone elastomer), a 1.6 mm sheet of J501 (an elastomer containing 60% silicone and 40% butyl acrylate styrene) as well as six duplex elastomeric coatings. The duplex coatings consisted of RTV11 top coat and J501 bond coat. The Waters’s empirical relationship was used to determine the modulus of elasticity E for the RTV11 and J501 sheets. The Waters’s relationship was then used to determine the equivalent modulus, E_c, for duplex coatings from maximum indentation load versus elastic indentation depth data. The values of E_c as determined from the Waters’s model (and experimental data) were in good agreement with the values obtained by an equivalent stiffness method. By being able to determine E_c from the equivalent stiffness method and using this value in the Waters’s model, one may determine the load versus elastic depth of indentation for duplex coatings.     

Properties of alkoxysilane castor oil synthesized via thiol-ene and its polyurethane/siloxane hybrid coating films

We developed a new silanized castor oil (MSCO) composed of castor oil and 3-mercaptopropyl trimethoxy silane via thiol-ene coupling (TEC). This MSCO was used as a functional polyol in the preparation of a series of bio-based polyurethane/siloxane (SiPU) hybrid coatings through reactions with different castor-oil-and-isophorone-diisocyanate (IPDI) ratios. The SiPU films exhibited better mechanical and thermal properties than castor oil-based coatings without MSCO. The cross-linked structure of the obtained hybrid materials was confirmed by Fourier transform infrared (FTIR) spectroscopy, whereas the morphologies and surface roughness of the hybrid-coating films were observed by scanning electron microscopy (SEM). A slight phase separation was observed in the obtained hybrid materials. The introduction of a silica network can reduce the surface energy of the obtained hybrid materials. The thermal stability of the obtained hybrid materials increases with increasing Si content. The obtained hybrid materials can be applied in coatings as a result of these characteristics, and this study provides an alternative method of preparing hybrid materials from renewable sources.     

Preparation and corrosion protective properties of nanostructured titania-containing hybrid sol–gel coatings on AA2024

Titania-containing organic–inorganic hybrid sol–gel films have been developed as an alternative to chromate-based coatings for surface pretreatment of aluminium alloys. Stable hybrid sols were prepared by hydrolysis of 3-glycidoxypropyltrimethoxysilane and different titanium organic compounds in 2-propanol solution in the presence of small amounts of acidified water. Different diketones were used as complexing agents in this synthesis for controllable hydrolysis of titanium organics. The properties of the obtained coatings were compared with those of zirconia-containing films. Electrochemical impedance spectroscopy (EIS) measurements and standard salt spray tests were performed to investigate the corrosion protection performance of the hybrid coatings. It was revealed that their protective properties depend significantly on the nature of metalorganic precursors and complexing agents used in the process of sol preparation. The best anticorrosive protection of AA2024 in chloride solutions is provided by the titania-containing sol–gel films prepared with titanium(IV) tetrapropoxide and acetylacetone as starting materials. In the case of zirconia-containing films, better protective properties were found when applying ethylacetoacetate as a complexing agent.     

Characterisation of indentation microstructures for porous SOFC cathodes

In this study, high-resolution focused ion beam sectioning assisted with SEM imaging was used to study the indentation microstructures of porous bulks and films of a solid oxide fuel cell cathode material (La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ) sintered at different temperatures. The crack morphologies and pore-filling densification caused by crushing of particle networks were studied in details. Analysis showed distinct permanent deformation mechanisms of the indentation microstructures between porous bulks and films. Whilst remarkable porosity gradient was found for the porous films under both Berkovich and spherical indenters, the porous bulks were found to behave more like dense materials. Results also showed that radial cracks induced by Berkovich indentation on the bulks could not generate observable pop-in/pop-out events in the loading-unloading curves. However, when indenting with the spherical indenter on a thick film, the shear sliding of the particle networks immediately under the indenter could cause phenomenal disruption in the loading unloading curves shown.     

Effectiveness of polymer coatings on reducing indention damage in glass

Polymer coatings are widely used to protect glass from indentation damage. A model for the strength degradation that occurs when a sharp indenter penetrates through the coating is developed by accounting for the indentation load shared by the coating and substrate. This model accounts for the additional load supported by the coating due to the pile-up of coating material underneath the indenter. The model predicts the strength degradation as a function of indentation load, coating and substrate hardnesses, and coating thickness. Comparison of the model to experimental data for a wide range of polymer coatings (two epoxies, epoxy acrylate, and urethane acrylate) on soda-lime glass substrates shows good agreement.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

Preparation,mechanical properties and surface morphologies of waterborne fluorinated polyurethane-acrylate

A series of waterborne fluorinated polyurethane-acrylate (WFPUA) materials were prepared from polyester polyol (NJ-330), isophorone diisocyanate (IPDI), dimethylol propionic acid (DMPA) and different content of hexafluorobutyl acrylate (FA). The chemical structure was characterized with FT-IR, ¹H and ¹³C NMR; and the result confirmed that the FA monomer had been introduced into the chain of the WPUA polymer. The physical properties of WFPUA dispersions, mechanical properties and thermal properties of WFPUA films were measured. When the content of FA monomer was 3.0 wt.%, the film exhibited the highest tensile strength, hardness and excellent chemical resistance. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used for characterization of cross and surface sections of the WFPUA films to verify the results. The obtained WFPUA materials have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings and wood finishes.     

Incorporation of carbon nanotubes into the biomedical polymer poly(styrene-β-isobutylene-β-styrene)

Poly(styrene-β-isobutylene-β-styrene) (SIBS) is a block copolymer that has been used extensively as a coating for medical devices in which it acts as a carrier for therapeutics. In this study the incorporation of carbon nanotubes (CNTs) into SIBS coatings was investigated as a means of modifying both the electrical conductivity and the surface characteristics of the SIBS coatings in order to affect the cell adhesion and proliferation characteristics of the coatings. SIBS was found to aid in the dispersion of CNTs in toluene. The conductivity of films cast from these dispersions increased with increased single wall carbon nanotube (SWNT) content in the range 0.05% to 0.30% (w/v). The surface morphology of these cast films was found to depend on the concentration of incorporated SWNTs. Growth of L-929 (mouse fibroblast) cells on the coatings was visualised by light microscopy and by calcein staining and fluorescence microscopy. The cytotoxicity of the coatings was assessed by quantitation of growth of L-929 cells on the coatings over 72 h using lactate dehydrogenase assay (LDH). L-929 cells were found to grow logarithmically on SIBS coatings and on SIBS incorporating SWNTs. SWNT/SIBS dispersions may therefore be used to form suitable coating materials for biomedical applications, and are worthy of further investigation.     

Fabrication of super water repellent silver flake/copolymer blend films and their potential as smart fabrics

A facile technique is demonstrated for the fabrication of super water repellent co‐polymer blend‐silver composite films from fatty acid surface functionalized fine silver flakes. Initially, high concentrations of surface functionalized silver flakes were dispersed in poly(vinyl chloride‐co‐vinyl acetate‐co‐vinyl alcohol) copolymer in solution to form electrically conducting adhesives/paints (ECAs) with a bulk resistivity of ∼3 × 10⁻⁵ Ω cm. The solvent‐borne ECAs were then blended with a water‐dispersed perfluoromethacrylate copolymer (Zonyl 8740) using a simple solvent‐inversion process to obtain super water‐repellent colloidal copolymer blend‐silver emulsions. The colloidal emulsions could be spray‐deposited on a number of fibrous substrates including fabrics and paper. A particular example is demonstrated herein by spray‐depositing these emulsions onto molten paraffin wax‐based laminates (60°C), which were partially impregnated into fabrics to fabricate highly water repellent, flexible, and thermoresponsive fabrics. A paraffin wax/polyolefin blend base film was used for the purpose. The surface topology of the superhydrophobic copolymer/silver composite films displayed fractal‐like hierarchical structures ideal for self‐cleaning hydrophobicity. On relatively low‐absorbent permeable porous surfaces such as cellulosic films (paper) impregnated with wax/polyolefin films, self‐cleaning ability of the coatings was maintained even for temperatures at which paraffin wax component of the laminated film was molten indicated by low‐water roll‐off angles. Hence, the composites have excellent compatibility with organic phase change materials such as paraffin wax and wax/polyolefin blends, and they can be used to fabricate nonwetting, thermoregulated, and electroactive fabrics. Antimicrobial properties of silver offer additional advantages for potential biomedical applications. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

氧化锆涂层(薄膜)的应用与研究

重点归纳了氧化锆(Zr02)作为热障涂层材料的应用和研究内容，并对Zr02功能薄膜材料和生物涂层材料的研究进行了简单总结。对纳米氧化锆涂层的研究现状进行初步介绍。     

Indentation behavior of polymer coatings on glass

For relatively soft polymer coatings on soda-lime glass substrates the indentation load increases substantially when the indenter penetrates into the glass substrate since the glass can now directly support some of the indenter load. A model for the indentation load-depth behavior is developed by accounting for the indentation load shared by the coating and substrate. This model accounts for the additional load supported by the coating due to the pile-up of coating material underneath the indenter. The model predicts the indentation behavior as a function of coating and substrate hardnesses and coating thickness. Comparison of the model to experimental data for a wide range of polymer coatings (two epoxies, epoxy acrylate, and urethane acrylate) on soda-lime glass substrates shows good agreement.     

Processing–structure–adhesion relationship in CVD diamond films on titanium substrates

The hardness and adhesion properties of diamond films deposited on pure Ti and Ti–6Al–4V alloy are related to the structural characteristics of the films and of the intermediate layers formed at the film/substrate interface. Deposition experiments were performed by hot-filament CVD systematically varying the deposition temperature (650–850 °C) and time (60–360 min). The morphology and structure of the coatings and interfaces were investigated by optical and electron microscopy (SEM) and by the combined use of reflection diffraction (RHEED) and X-ray powder diffraction (XRPD), used also in the GID (Grazing Incidence Diffraction) mode. Hardness measurements (HV) of the deposits were made at a constant loading of 25 g on specifically prepared transversal sections of the specimen. Only small differences concerning the mechanical properties have been found for films grown on pure Ti and Ti–6Al–4V substrates. Adhesion of diamond on the substrate has been determined by the scratch test. The analysis of the micrographs of the indenter scratches and of the fracture-correlated acoustic emissions clearly indicates the occurrence of a multi-step detachment process, leading progressively to effective delamination of the diamond coatings.