Preparation,Morphology and Properties of Waterborne-Polyurethane/Silica

A series of waterborne-polyurethane/silica (WPU/SiO₂) were prepared from isophoronediisocyanate, polyester polyol, dimethylolpropionic acid, tetraethoxysilane and 3-glycidyloxypropyl trimethoxysilane. The WPU/SiO₂ dispersion had narrower particle size distribution than the pure WPU. The mechanical properties of WPU/SiO₂ films were improved than the pure WPU. WPU/SiO₂ films were characterized by FT-IR spectroscopy, SEM, TEM, AFM, XRD and UV-Vis spectroscopy. The results showed that WPU/ SiO₂ hybrid films were found to be smooth morphology, and had good thermal stability and tunable transparence with the silica fraction in the film. Through suitable adjustment of silica content, some thin films have potential applications as the specialty materials.     

Texture effect on the electrochemical properties of LiCoO2 thin films prepared by PLD

LiCoO₂ thin films were prepared by pulsed laser deposition (PLD) on Pt/Ti/SiO₂/Si (Pt) and Au/MgO/Si (Au) substrates, respectively. Crystal structures and surface morphologies of thin films were investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The LiCoO₂ thin films deposited on the Pt substrates exhibited a preferred (0 0 3) texture with smooth surfaces while the LiCoO₂ thin films deposited on the Au substrates exhibited a preferred (1 0 4) texture with rough surfaces. The electrochemical properties of the LiCoO₂ films with different textures were compared with charge-discharge, dQ/dV, and Li diffusion measurements (PITT). Compared with the (1 0 4)-textured LiCoO₂ thin films, the (0 0 3)-textured thin films exhibited relatively lower electrochemical activity. However, the advantage of the (1 0 4)-textured film only remained for a small number of cycles due to the relatively faster capacity fade. Li diffusion measurements showed that the Li diffusivity in the (0 0 3)-textured film is one order of magnitude lower than that in the (1 0 4)-textured film. As discussed in this paper, we believe that Li diffusion through grain boundaries is comparable to or even faster than Li diffusion through the grains.     

Effect of rapid thermal annealing on the structural and electrical properties of TiO2 thin films prepared by plasma enhanced CVD

Titanium oxide thin films were deposited on p-type Si(100), SiO₂/Si, and Pt/Si substrates by plasma enhanced chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄ and oxygen. As-deposited amorphous TiO₂ thin films were treated by rapid thermal annealing (RTA) in oxygen ambient, and the effects of RTA conditions on the structural and electrical properties of TiO₂ films were studied in terms of crystallinity, microstructure, current leakage, and dielectric constant. The dominant crystalline structures after 600 and 800 ‡C annealing were an anatase phase for the TiO₂ film on SiO₂/Si and a rutile phase for the film on a Pt/Si substrate. The dielectric constant of the as-grown and annealed TiO₂ thin films increased depending on the substrate in the order of Si, SiO₂/Si, and Pt/ Si. The SiO₂ thin layer was effective in preventing the formation of titanium silicide at the interface and current leakage of the film. TEM photographs showed an additional growth of SiO_x from oxygen supplied from both SiO₂ and TiO₂ films when the films were annealed at 1000 ‡C in an oxygen ambient. Intensity analysis of Raman peaks also indicated that optimizing the oxygen concentration and the annealing time is critical for growing a TiO₂ film having high dielectric and low current leakage characteristics.     

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

Chemical anchoring of silica nanoparticles onto polyaniline chains via electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of SiO2

Chemical anchoring of silica nanoparticles onto polyaniline (PANI) chains was conducted through electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of silica nanoparticles. The grafting of N-substituted aniline on surfaces of silica nanoparticles were realized through hydrolysis of triethoxysilylmethyl N-substituted aniline (ND42) and the following condensation reaction with silanol groups on surfaces of SiO₂. Organic-inorganic interactions between PANI and SiO₂ involved in electro-co-polymerization process pushed the polymer chains apart and so facilitated the 1D growth of the polymer. Hence, the obtained hybrid film PANI/ND42-SiO₂ displayed nano-fibrous morphologies (ca. 50 nm in diameter). Consequently, PANI/ND42-SiO₂ exhibited an average specific capacitance of 380 F g⁻¹, ca. 40% higher than that of PANI/SiO₂ (276 F g⁻¹). The hybrid film also showed improved cyclic stability.     

Facile preparation and characterization of low-gloss waterborne polyurethane coatings using amine-based chain extenders

A novel waterborne polyurethane (WPU) coating with a self-roughed surface is prepared using a general prepolymer emulsion polymerization method. A rough surface is formed by crosslinking the WPU particles through the introduction of a polyfunctional amine-based chain extender. Ethylenediamine, diethylenetriamine (DETA) and triethylenetetramine (TETA) with different functional groups are used as chain extenders, and their effect on the surface morphology and gloss of WPU films is investigated. DETA and TETA form a rough surface on the WPU film by crosslinking the polymer chains and promoting phase separation between soft and hard segments. A rough surface reflects light diffusely, resulting in a decrease in the gloss of the film. Overall, the chain extension improves the thermal stability and tensile strength of the WPU film. In particular, the WPU film with DETA, exhibiting the highest chain extension effect, shows the lowest gloss value, the highest tensile strength and thermal stability. The present series of WPU materials, prepared without matting agents and special treatment processes, can be an effective alternative for producing low-gloss coatings. © 2022 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.     

Deposition of high fluorine content macromolecular thin layers under continuous-flow-system corona discharge conditions

Summary High fluorine content macromolecular layers were deposited on polyethylene (PE) film surfaces under an originally designed, continuos-flow-system plasma reactor conditions. Survey and angle resolution, ESCA data and ATR-FTIR results indicate that the plasma-created films are thin and have a fairly uniform structure. The fluorinated layers have a 60% relative fluorine atomic concentration, and are mainly composed of CF₂-CF, and C-CF₃ groups. AFM images collected from virgin and plasma-exposed PE surfaces show a significantly rougher surface of the plasma-treated substrates. Applications can be envisaged for creating Teflon-like coatings on various polymeric film surfaces using a continuous plasma process. Received: 1 June 1999/Revised version: 1 September 1999/Accepted: 1 September 1999     

Preparation of siloxane–silsesquioxane hybrid thin films for large‐scale‐integration interlayer dielectrics with excellent mechanical properties and low dielectric constants

Several kinds of homogeneous organic–inorganic hybrid polymer thin films were designed with improved mechanical properties and low dielectric constants (<3.0). Novel soluble siloxane–silsesquioxane hybrid polymers were synthesized with cyclic and/or cage silane monomers, which had triorganosiloxy (R₃Si_1/2), diorganosiloxane (R₂SiO_2/2), and organosilsesquioxane (RSiO_3/2) moieties with ethylene bridges at the molecular level, by the hydrolysis and condensation of 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane (a cyclic monomer). The electrical properties of these films, including the dielectric constant (～2.51), leakage current (6.4 × 10^?11 A/cm² at 0.5 MV/cm), and breakdown voltage (～5.4 MV/cm) were fairly good. Moreover, the mechanical properties of the hybrid films, including the hardness (～7 GPa), modulus (～1.2 GPa), and crack‐free thickness (<2 μm), were excellent in comparison with those of previous spin‐on‐glass materials with low dielectric constants. The excellent mechanical properties were proposed to be due to the high contents of Si? OH groups (>30%) and the existence of ethylene bridge and siloxane moieties in the hybrid polymer precursors. In addition, the mechanical properties of the hybrid films were affected by the contents of the cagelike structures. The more cagelike structures a hybrid film contained, the worse its mechanical properties were. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 626–634, 2003     

Studies on metal/benzocyclobutene (BCB) interface and adhesion

Interfacial characteristics such as chemical reaction, metal diffusion, and morphology were investigated for Cu/BCB, Cr/BCB and Ti/BCB structures. Using Auger and XPS depth profiling, the formation of titanium carbide and chromium oxide was confirmed at the metal/BCB interface. Annealing at 250°C for extended periods resulted in the diffusion of Cu, Cr and Ti into the BCB and subsequent formation of Cu-Si, CrSi₂ and Ti-Si compound precipitates. The reaction is a thermal diffusion controlled process which is dependent on time and temperature. Ar sputtering treatment of BCB film before metallization was found to roughen the surface, resulting in metal spikes which penetrate into the roughened BCB film. However, the peel strength of metals on BCB was only about 177 g cm^_1presumably due to the brittleness of the BCB film. The etch rates of the BCB film in a reactive ion etcher (RIE) and a plasma etcher were measured using Ar, O₂, O₂ + CF₄, and O₂ + SF₆ gas mixtures. Faster etch rates were obtained when CF₄ and SF₆ were added to oxygen, since the presence of atomic fluorine enhances the etch rate of organics, while also etching Si and SiO₂ formed by exposure of Si-containing BCB film to oxygen gas. Surface compositional changes on the BCB film were observed by XPS after plasma modification. Pure O₂ and O₂ + CF₄ plasmas oxidized the carbo-siloxane linkage (C_—Si_—O) of the BCB, resulting in the formation of SiO₂ on the surface. The O₂ + SF₆ plasma, however, did not produce the surface SiO₂, because of its faster Si and SiO₂ etch rates.     

The chain extender content and NCO/OH ratio flexibly tune the properties of natural rubber‐based waterborne polyurethanes

The effects of chain extender content (ethylene diamine, EDA) and NCO/OH ratio on the properties of natural rubber‐based waterborne polyurethanes (WPUs) were investigated experimentally. The particle size of WPU increased significantly with the NCO/OH ratio, in the presence of the EDA chain extender, while it was unaffected by the EDA content. The water uptake of WPU film increased with the EDA content, while the swelling in various solvents decreased. In a thermal analysis, the second decomposition stage of a WPU film increased with the EDA content and with the NCO/OH ratio that also positively affected the dynamic mechanical and mechanical properties. These factors in WPU films had no the effect on the T_g. The stress–strain curves clearly showed the change in WPU films from soft elastomeric materials to ductile and hard plastics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42505.     

Influence of interface structure on microstructure and dielectric properties of bismuth magnesium niobate thin films

Bismuth magnesium niobate (Bi_3/2MgNb_3/2O₇, BMN) thin films were prepared on bare SiO₂/HR-Si and Pt/TiO₂/SiO₂/HR-Si substrates by using sol-gel spin coating technique followed by rapid thermal annealing process. The influence of the interface on crystalline structure and tunable dielectric properties of the two types of BMN films were investigated. It was found that the BMN films prepared on SiO₂/Si substrate with a BMN/SiO₂ interface structure had higher orientation and better crystallinity. The deposited BMN thin films with a BMN/SiO₂ interface structure exhibited superior tunability of 52.5%, while it showed a relative small tunability value of the film with BMN/Pt interface structure. It suggests that the interface state between the films and substrates, electric field distribution, and orientation degree are responsible for the impacts on the microstructure and tunable dielectric properties of the BMN thin films.     

Multi-Directional Growth of Aligned Carbon Nanotubes Over Catalyst Film Prepared by Atomic Layer Deposition

The structure of vertically aligned carbon nanotubes (CNTs) severely depends on the properties of pre-prepared catalyst films. Aiming for the preparation of precisely controlled catalyst film, atomic layer deposition (ALD) was employed to deposit uniform Fe₂O₃ film for the growth of CNT arrays on planar substrate surfaces as well as the curved ones. Iron acetylacetonate and ozone were introduced into the reactor alternately as precursors to realize the formation of catalyst films. By varying the deposition cycles, uniform and smooth Fe₂O₃ catalyst films with different thicknesses were obtained on Si/SiO₂ substrate, which supported the growth of highly oriented few-walled CNT arrays. Utilizing the advantage of ALD process in coating non-planar surfaces, uniform catalyst films can also be successfully deposited onto quartz fibers. Aligned few-walled CNTs can be grafted on the quartz fibers, and they self-organized into a leaf-shaped structure due to the curved surface morphology. The growth of aligned CNTs on non-planar surfaces holds promise in constructing hierarchical CNT architectures in future.     

Facile construction of silica-based surface coating onto polypropylene microporous film through dopamine-assisted hydrolysis of tetraethoxysilane

Surface modification with silica-based coating is widely used to attain high performance and construct special functions for thin films. In this paper, dopamine (DA) and tetraethoxysilane (TEOS) were used as initial building blocks to construct a biomimetic hydrophilic and mechanical robust silica-based coating onto polypropylene (PP) microporous film. It was found that the final DA/TEOS coating can be steadily immobilized onto PP film and greatly improve the hydrophilic property of PP film as evidenced by the decreased contact angle. Furthermore, the coating structures were comparatively investigated through one-step synthesis and two-step synthesis of DA and TEOS with a fixed ratio. Interestingly, the one-step synthesized coating possesses a loosely-packed layer with dispersed SiO₂ nanoparticles within polydopamine matrix while the two-step synthesized coating shows a high loading of SiO₂ nanoparticles. As a result, the two-step approach leads to a continuous SiO₂ layer with abundant hydroxyl groups, indicating a better lyophilic property and depressed thermal shrinkage. In addition, the concentric SiO₂ layer results in a significant increase of the tensile strength of PP films.     

Dielectric and conduction properties of polyimide/silica nano‐hybrid films

Dielectric and conduction properties of polyimide/silica nano‐hybrid films were investigated with the silica content and the testing frequency, using a small electrode system. The hybrid films were prepared through sol‐gel process and thermal imidization, by using pyromellitic dianhydride and 4,4′‐oxydianiline as polyimide precursors, and tetraethoxysilane and methyltriethoxysilane as silica precursors. The dielectric coefficient of PI/SiO₂ films was monotonically increased with increasing silica content, and decreased with increasing testing frequency. The dielectric loss of PI/SiO₂ films had no obvious changes with increasing silica content, but monotonically increased with increasing testing frequency. These can be contributed to the different quantity and migration chunnels of current carriers, which were mainly influenced by a few of complicated factors. There were remarkable differences between conduction property of PI/TEOS‐SiO₂ films and PI/MTEOS‐SiO₂ films because of the different size and dispersion status of silica particles in the polyimide matrix. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Development of the scratch resistance on acrylic sheet with basic colloidal silica (SiO2)—methyltrimethoxysilane (MTMS) nanocomposite films by sol–gel technique

The formation of scratch‐resistant coating film prepared from colloidal silica and a polysiloxane matrix was investigated. Methyltrimethoxysilane (MTMS) was hydrolysed and mixed with silica sol (SiO₂) at various compositions to form the hybrid hard‐coating nanocomposite film. The hydrolysed MTMS (polysiloxane) acts as the polymeric binder that is covalently linked to the colloidal silica surface and provides adhesion for the scratch resistant coating film to the substrate. The ratio between the polymeric matrix and the SiO₂ nanoparticles was found to play a major role in controlling the coating film appearance and its resistance to scratching. At a SiO₂ content < 30 wt.%, the agglomeration of the hydrolysed polysiloxane was observed and caused the opacity of the coating film. At a SiO₂ content >70 wt.%, there was not enough polysiloxane to act as a binder for the SiO₂, therefore a shrinkage upon solidification of the coating film caused cracking within the nanocomposite film. The optimum ratio was found to be at 40 wt.% ≤SiO₂ ≤60 wt.%, where the films had a transparent, crack free hard coating, with excellent scratch resistance, good adhesion and very good environmental resistance. The nanoindentation revealed that the nanocomposite film, at the optimum loading, possessed a higher strength with a higher SiO₂ loading. Film properties, including hardness, scratch resistance, adhesion and environmental resistance were also examined. The morphology of nanocomposite films was identified by atomic force microscopy (AFM) and scanning electron microscopy (SEM). © 2011 Canadian Society for Chemical Engineering     

Preparation, characterization and properties of UV-curable waterborne polyurethane acrylate/SiO2 coating

The UV-curable waterborne polyurethane acrylate (UV-WPUA) oligomer was first prepared based on isophorone diisocyanate (IPDI), polyether polyol (NJ-220), dimethylol propionic acid (DMPA), and hydroxyethyl methyl acrylate (HEMA) via an in situ method. With the different content tetraethoxysilane (TEOS) and 3-glycidyloxypropyltrimethoxysilane (GLYMO) as coupling agents, a series of waterborne UV-WPUA/SiO₂ oligomers were prepared by the sol?Cgel process. The physical and mechanical properties of the UV-WPUA and UV-WPUA/SiO₂ hybrid coating materials were measured. The UV-WPUA and WPUA/SiO₂ hybrid materials were characterized using FTIR spectra, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD) measuring apparatuses to determine their structures, thermal properties, surface morphologies, etc. The results showed the SiO₂ particles of the hybrid materials had wide dispersion, forming a good interfacial bonding layer on surfaces. The tensile strength, water resistance, and thermal properties of the hybrid materials were better than those of the UV-WPUA. The resulting UV-WPUA/SiO₂ hybrids are promising for a number of applications, e.g., for high-performance water-based UV-curable coatings.     

Effect of chemical interaction on morphology and mechanical properties of CPI‐OH/SiO2 hybrid films with coupling agent

A novel hybrid film composed of copolyimide with hydroxyl group, silica and γ‐glycidyloxypropyltrimethoxysilane (CPI‐OH/SiO₂/GOTMS) was prepared by the sol–gel process based on hydrolyzed tetraethoxysilane (TEOS) under acidic condition. GOTMS, as the coupling agent, and hydroxyl group in PI chain were used to improve the compatibility between the PI and SiO₂. The components, morphologies, and mechanical properties of the hybrids were investigated by FTIR, UV–vis, SEM, stress–strain tests, and DMA. The results showed that SiO₂ particle size significantly decreased, fractured cross sections of hybrid were rougher, and the surfaces of spherical SiO₂ particles were more widely covered by PI component. The tensile mechanical properties of hybrids increased when adding GOTMS. The critical points of maximum tensile strength and elongation at break move from 11 to 16 wt % SiO₂ content. DMA results showed that the storage moduli of hybrids with GOTMS, when above 260°C, were obviously higher than those without GOTMS; the tan δ transition temperature of hybrid films went up from 317 to 337°C. It suggests that chemical interaction between CPI‐OH and SiO₂ is formed and the PI molecular mobility is restricted by the chemical interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3530–3538, 2007     

Wear,thermal, and physical properties of fluorine-containing polyimide/silica hybrid nanocomposite coatings

This study prepared fluorine and SiO₂ particles containing organic–inorganic hybrid polyimide nanocomposite coatings (PISFs) with inorganic content in the range of 5–20% in pure polyimide solutions via the sol–gel process. Polyimide hybrid structures containing fluorine and SiO₂ particles were synthesized by using perfluorooctyltriethoxysilane and tetraethyl orthosilicate. These formulations were applied on aluminum sheets by using a 75 μm wire wound applicator, and the coatings were cured for 8 h at room temperature and then 24 h at 100 °C. Increased inorganic contents caused slight decreases in the initial decomposition temperatures, but the char yield values increased for PISF15 and PISF20. All samples exhibited hydrophobic properties. When all samples were compared, PISF5 and PISF10 exhibited hydrophobicity, high wear resistance and thermal properties. Additionally, PISF5 and PISF10 showed high adhesion, hardness, and methyl ethyl ketone solvent resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47399.     

Properties of films obtained by UV-curing 4,4'-hexafluoroisopropylidenediphenoldihydroxyethylether diacrylate and its mixtures with the hydrogenated homologue

A new ultraviolet (UV)-curable acrylic monomer, 4,4'-hexafluoroisopropylidene-diphenoldihydroxyethylether diacrylate, was synthesized: it was cured as a film and its properties compared with those of its fully hydrogenated homologue. The introduction of two CF₃groups into the monomer did not change its reactivity in the UV-curing reaction, but increased the glass transition temperature (T_g) of the cured polymeric film, decreased its refractive index (n), and lowered its surface tension. The fluorinated and the hydrogenated monomers were completely miscible and give homogeneous films: the T_g and n values were found linearly dependent on the fluorinated monomer content. The surface properties were deeply influenced by the presence of fluorine; a surface enrichment of the fluorinated monomer was evidenced by X-ray photoelectron spectroscopy analyses on the surfaces of the films obtained from mixtures of the two monomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 979–983, 1997     

Patterning Si by using surface functionalization and microcontact printing with a polymeric ink

This paper describes a simple procedure for patterning Si substrate using a combination of surface functionalization and microcontact printing(ΜCP). The Si/SiO₂ surfaces were chemically modified to present self-assembled monolayers (SAMs) of siloxanes terminating in reactive carboxylic anhydride groups and then patterned with poly(ethylene imine) (PEI) by, ΜCP We used the patterned thin films of PEI as etch resists on Si surfaces.