UV-resistant amorphous fluorinated coating for anodized titanium surfaces

In this work, a high molecular weight copolymer of tetrafluoroethylene and perfluoro-4-trifluoromethoxy-1,3-dioxole (HYFLON^® AD60) and two perfluoropolyethers (PFPEs) containing ammonium phosphate or triethoxysilane functionalities, FLUOROLINK^® F10 and FLUOROLINK^® S10 respectively, have been evaluated as protective coatings that can be easily applied on anodized titanium surfaces. Water and n-dodecane contact angle measurements have been recorded by using the sessile drop method for bare and coated surfaces in order to determine the hydrophobic and oleophobic properties of the coatings. The UV-stability of coatings have been studied by Fourier transform infrared spectroscopy (FT-IR) analyses and by observing the variation of water contact angles on coated substrates before and after UV irradiation at regular time intervals. The thickness of the fluorinated films has been measured by ellipsometry and by weight evaluation. Preliminary tests of the adhesion between films and substrate have been conducted.     

Morphology,Composition, and Bioactivity of Strontium-Doped Brushite Coatings Deposited on Titanium Implants via Electrochemical Deposition

Surface modification techniques have been applied to generate titanium implant surfaces that promote osseointegration for use in dental applications. In this study, strontium-doped brushite coatings were deposited on titanium by electrochemical deposition. The phase composition of the coating was investigated by energy dispersive X-ray spectroscopy and X-ray diffraction. The surface morphologies of the coatings were studied through scanning electron microscopy, and the cytocompatibility and bioactivity of the strontium-doped brushite coatings were evaluated using cultured osteoblasts. Osteoblast proliferation was enhanced by the addition of strontium, suggesting a possible mechanism by which strontium incorporation in brushite coatings increased bone formation surrounding the implants. Cell growth was also strongly influenced by the composition of the deposited coatings, with a 10% Sr-doped brushite coating inducing the greatest amount of bone formation among the tested materials.     

Corrosion behavior of electrochemically assembled nanoporous titania for biomedical applications

Corrosion resistance of nanoporous titania was investigated in Hank’s solution using potentiodynamic polarization and electrochemical impedance spectroscopic techniques. The phase structure, surface morphology and elemental composition of the untreated, anodized heat treated and anodized heat treated titanium specimens immersed in Hank’s solution for seven days were characterized using X-ray diffraction, atomic force microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy techniques, respectively. The X-ray diffraction technique revealed that the anodized heat treated titanium exhibited anatase structure. The atomic force microscopic and scanning electron microscopic results showed that the titanium surface has transformed from a smooth to nanoporous surface depending on the anodization conditions. The energy dispersive X-ray spectroscopy results confirmed the formation of hydroxyapatite over the anodized titanium after immersion for seven days in Hank’s solution. The electrochemical results revealed that the anodized heat treated titanium after seven day immersion in Hank’s solution showed nobler shift in corrosion potential compared to untreated and anodized titanium. Hence, the results suggested that the nanoporous titania layer developed on titanium is a promising material for application as orthopaedic implants.     

Hydroxyapatite coating on titanium surface with titania nanotube layer and its bond strength to substrate

A vertically aligned titania nanotube layer on titanium surface was prepared by electrochemical anodic oxidation in an F⁻-containing electrolyte, followed by annealing at 450 °C. Bioactive hydroxyapatite (HA) coatings on as anodized titania nanotube layer were obtained by a biomimetic method without other surface treatment. The morphology, crystal structure, and components of the titania nanotube layer and bioactive coatings were examined by scanning electron microscopy, thin film X-ray diffraction, and Fourier transform infrared spectroscopy. The bond strength between the HA coatings and substrates was tested using a mechanical tester. The diameter of the titania nanotubes was about 100 nm, the wall thickness about 19 nm and the height about 1 μm. HA rapidly deposited on the as anodized nanotube surface after immersion in a biomineral solution only for 1 day. The HA coatings were carbonated apatite and composed of a number of column-like crystals with nanometer size. Tensile test shows that the bond strength between the HA coating and the nanotube layer was larger than 15.3 MPa.     

Effects of pigmentation on siloxane–polyurethane coatings and their performance as fouling-release marine coatings

Siloxane–polyurethane paints were formulated and characterized for coating properties and performance as fouling-release (FR) marine coatings. Paints were formulated at 20 and 30 pigment volume concentrations with titanium dioxide, and aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) loadings were varied from 0 to 30% based on binder mass. The coatings were characterized for water contact angle, surface energy (SE), gloss, and pseudobarnacle (PB) adhesion. The assessment of the FR performance compared with polyurethane (PU) and silicone standards through the use of laboratory biological assays was also performed. Biofilm retention and adhesion were conducted with the marine bacterium Cellulophaga lytica, and the microalgae diatom Navicula incerta. Live adult barnacle reattachment using Amphibalanus amphitrite was also performed. The pigmented coatings were found to have properties and FR performance similar to those prepared without pigment. However, a higher loading of PDMS was required, in some cases, to obtain the same properties as coatings prepared without pigment. These coatings rely on a self-stratification mechanism to bring the PDMS to the coating surface. The slight reduction in water contact angle (WCA) and increase in pseudobarnacle release force with pigmentation suggests that pigmentation slowed or interfered with the self-stratification mechanism. However, increasing the PDMS loading is an apparent method for overcoming this issue, allowing for coatings having similar properties as those of clear coatings and FR performance similar to those of silicone standard coatings.     

Synthesis of sulfonyl fluorinated macro emulsifier for low surface energy emulsion polymerization application

Fluorinated acrylate emulsions have been extensively applied for hydrophobic surface coatings. To obtain fluorinated emulsions of low surface energy, amphiphilic sulfonyl macro emulsifiers consisting of 2‐(perfluorohexyl) ethyl acrylate (PFHEA) and 2‐acrylanmido‐2‐methylpropanesulfonic acid (AMPS) were designed via radical polymerization and subsequently used for the emulsion copolymerization of PFHEA, methyl methacrylate (MMA), and methyl butyl acrylate (MBA). Under optimum synthesis conditions, the emulsifier displayed superior emulsification properties such as high monomer conversion, small particle size, and excellent stability compared with conventional emulsifiers. The corresponding emulsions with sulfonyl macro emulsifiers exhibited extreme low surface energy (9.8 mN/m) and outstanding hydrophobicity due to high contents of fluorinated chains, as well as thimbleful hydrophilic sulfonyl groups, which shows the great potential in water repellent modification application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44921.     

Synthesis of fluoroalkyl‐modified polyester and its application in improving the hydrophobicity and oleophobicity of cured polyester coatings

The fluoroalkyl‐modified polyester (PE‐F_n) was synthesized by the reaction of polyester resin (PE) and fluorinated isocyanate, and the structure of the synthesized product was characterized by proton nuclear magnetic resonance (¹H‐NMR) and fluorine nuclear magnetic resonance (¹⁹F‐NMR). The water and oil wettability of the cured PE coatings with PE‐F_n as additives was investigated by contact angle meter. The results showed that the introduction of an extremely low concentration of PE‐F_n into PE led to the increase in contact angle of water and diiodomethane on cured PE coatings, and the decrease in the surface free energy. The X‐ray photoelectron spectroscopic (XPS) analysis showed that the F/C molar ratio in the outer few nanometers was significantly higher than that in the bulk, indicating that the fluoroalkyl groups in PE‐F_n had enriched on the coating surface. It was also found that longer fluoroalkyl groups and fluoroalkyl groups with ? CF₃ at its end had the higher tendency to aggregate on the coating surface. The topological structures of the cured coatings were recorded by an atomic force microscope under tapping mode and the results revealed that there was a strong surface segregation of fluorinated species. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39812.     

Fabrication of superhydrophobic titanium surfaces by anodization and surface mechanical attrition treatment

A superhydrophobic surface of titanium was fabricated by anodization in sodium chloride solution followed by immersion in perfluorodecyltriethoxysilane. The surface characteristics of the anodic film (morphology, composition, microstructure, and adhesion) were investigated by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and scratch testing. The anodic film was comprised of TiO₂ and TiCl₃ with a thickness of 50 nm. The anodized titanium surface exhibited a hierarchical structure, which consisted of a microscale horn structure with a nanoscale strip-overlay. This structure provided superhydrophobicity (water contact angle: 151.9° and sliding angle: 3°) following the immersion process. Furthermore, coverage of the hierarchical structure on the anodized titanium surface was improved by performing surface mechanical attrition treatment (SMAT) to grain-refine titanium surface which was then anodized and it enhanced a slightly increased water contact angle. The thickness (200 nm) of the anodic film on the SMAT-pretreated titanium surface was much higher than that on the titanium surface (50 nm). This resulted from a large number of grain boundaries on the surface serving as a fast diffusion path during anodization. However, the adhesion of the SMAT-and-anodized film was worse than that formed by anodization only. This is due to a large number of pores within the SMAT-and-anodized film.     

Compositional effects on the fouling resistance of fluorourethane coatings

Conclusions  A series of fluorinated polyurethane polymers have been prepared and characterized. Immersion experiments have been performed to determine the fouling-release effectiveness of the coatings. The surface energies of the films are between 12 mJ m⁻² to 33 mJ m⁻² and are controlled by the fluorine content of the polymer. These surface energies are well below the values shown by conventional alkyd, epoxy, vinyl, polyester, and polyurethane coatings (39 mJ m⁻² and 50 mJ m⁻²). Surface energy is not the dominant factor in determining the fouling- release behaviour of these coatings. Instead, measurements of the coating modulus, hardness, and glass transition temperature indicate that supple, soft polymers, with a high degree of mobility may display more effective fouling-release characteristics than more rigid, harder polymers below their glass transition temperatures. Surface roughness also appears to be a major factor in determining coating fouling-release behaviour. This work has demonstrated that marine organisms bind to fluorinated polyurethanes with significantly less strength than to the unfluorinated epoxy, vinyl and urethane resins which are now used with toxicants in marine coatings. However, this work has shown that these fluorinated polyurethanes are not sufficiently promising to merit further attention as non-toxic anti-fouling coatings for ship hulls. Fluorinated polyurethanes remain very attractive coatings for exterior and anti-corrosive service, especially in application requiring easy cleanability and resistance to sunlight, weather, and chemicals.     

Preparation and characterization of UV‐cured hybrid coatings by triethoxysilane‐modified dimethacrylate based on bisphenol‐s epoxy

Novel hybrid oligomers based on a UV‐curable bisphenol‐S epoxy dimethacrylate (DBSMA) were synthetized. DBSMA was modified with various amount of (3‐isocyanatopropyl)triethoxysilane coupling agent. The modification degree of the hybrid oligomer was varied from 0 to70 wt %. The photopolymerization kinetics was monitored by a real‐time infrared spectroscopy. The conversion and rate of hybrid coatings increased with the increase in modification degree. UV‐curable, hard, and transparent organic–inorganic hybrid coatings were prepared. They were performed by the analyses of various properties such as surface and mechanical properties. Results from the mechanical measurements showed that the properties of hybrid coatings improved with the increase in modification degree. The thermal behavior of coatings was also investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Plasma-Sprayed Aluminum and Titanium Adherends: II. Durability Studies for Wedge Specimens Bonded with Polyimide Adhesive

The durability of plasma-sprayed metals bonded with a polyimide adhesive has been studied. Metal adherend surfaces were prepared for adhesive bonding by plasma-spraying inorganic powders on aluminum and titanium. The plasma-sprayed materials included Al₂O₃, AlPO₄. MgO, and SiO₂ on aluminum, and TiO₂, TiSi₂, MgO, and SiO₂ on titanium. The coatings were sprayed at two different thicknesses. Durability studies of samples prepared in a wedge-type geometry were carried out. Bonded specimens were maintained in an environmental cycle that included exposure to the conditions; low temperature, - 20°C; relative humidity at elevated temperature, 70% RH at 66°C; elevated temperature (160°C) in air, high temperature (160°C) in vacuum (130 torr, 0.2 atm.), and room temperature. Crack growth rate and mode of failure were determined. The results of the durability tests indicate that thin coatings (25 μm) of plasma-sprayed materials perform better than thicker (150 μm) coatings. The crack growth rate for thin coatings (25 μm) of Al₂O₃, AlPO₄, SiO₂, and MgO plasma-sprayed on aluminum was equivalent to that for phosphoric acid anodized aluminum. Similarly, the durability performance for titanium samples prepared with a 25 μm-thick TiO₂, TiSi₂, and SiO₂ plasma-sprayed coatings was equivalent to that for a Turco®-prepared titanium surface. Although the evaluation of durability as a function of surface chemistry was an objective of the study, it was not possible to evaluate the effect, since most failures occurred within the adhesive (cohesive failure) during the environmental tests. That failure occurred in the adhesive indicates that the coating-adherend and the coating-adhesive interactions are sufficiently robust to prevent interfacial failure under the experimental conditions investigated.     

The Use of AFM and Surface Energy Measurements to Investigate Drug-Canister Material Interactions in a Model Pressurized Metered Dose Inhaler Formulation

The aim of the project was to investigate the interactions between micronized salbutamol sulphate, budesonide, and formoterol fumarate dihydrate and different canister surfaces materials (Aluminium, anodized aluminium, perfluoroalkoxy, fluorinated ethylene propylene—polyether sulphone, and polytetrafluoroethylene) used in pressurized metered dose inhalers (pMDIs).

The surface component approach for polar and apolar interfacial interactions was used to predict the adhesion behavior of micronized drugs with the inner surfaces of pMDI canisters. This was achieved using a combination of in situ colloid probe atomic force microscopy (AFM) measurements and theoretical treatment of the surface free energy measurements, via a contact angle–based technique of the interacting surfaces.

All three drugs exhibited similar dispersive surface energy free values. A greater variation was, however, found in the polar component of the surface free energy measurements. These results were also reflected in the dispersive and polar components of the canister materials. Moreover, the linear relationship between the work of adhesion and AFM measured adhesion was shown to be correlated on the polar contributions of the surface free energies of the interacting materials. AFM measurements indicated that salbutamol sulphate was found to have the strongest adhesive forces with respect to the canister surface materials while budesonide and formoterol fumarate dihydrate appeared to have similar adhesive characteristics. The present study suggests that investigations into the design and characterization of pMDI formulations would benefit from considerations of the polar contribution of the surface free energy and relative work of adhesion of the drug and various components of a pMDI system.     

Surface properties of fluorinated hybrid coatings

A commercial perfluoropolyether containing alkoxysilane functionalities was employed to prepare organic–inorganic hybrid coatings by using the sol‐gel process in the presence of tetraethoxysilane. Contact angle analysis revealed a strong hydrophobic and oleophobic character of the coatings almost independently from the molecular weight of the starting fluorinated oligomer. Surface tension values were in the range of 14–16 mN/m, suggesting a preferential segregation of fluorinated segments onto the surface of the coating. Atomic force microscopy showed the presence very smooth surfaces permitting to neglect the contribution of the surface roughness to wettability. Friction coefficient values were markedly lower with respect to the value of uncoated glass substrate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1483–1488, 2006     

A novel mono‐methacryloyloxy terminated fluorinated macromonomer used for the modification of UV curable acrylic copolymers

A novel macromonomer containing fluorinated units (PHFBMA‐GMA) was synthesized through a two‐step procedure: firstly, hexafluoro‐butyl methacrylate (HFBMA) was polymerized in the presence of functional chain transfer agent 3‐mercaptopropionic acid (MPA) and then the carboxyl acid group terminated polymer was end‐capped with glycidyl methacrylate (GMA). Chemical structures of PHFBMA‐GMA were characterized by gel permeation chromatography, fourier transform infrared spectroscopy (FTIR), and ¹H nuclear magnetic resonance (NMR). Subsequently, PHFBMA‐GMA was employed as reactive surface additives added into UV‐cured polyacrylate to modify UV‐curable coatings. It is convenient to control the tail length of the fluorinated segments in this study by adjusting the ratio of initiator and chain transfer agent. The influence of both the concentration and the molecular weight of PHFBMA‐GMA on the surface properties of UV‐cured films was investigated. With increasing both the concentration and the molecular weight of PHFBMA‐GMA, the surface energy of the UV‐cured films decreased. X‐ray photoelectron spectroscopy was employed to characterize and quantify the surface composition and the results confirm the enrichment of fluorinate atoms on the surface. Moreover, the physical properties of UV‐cured films, such as gel content, water absorption, pencil hardness, adhesion, chemical resistance, mechanical properties, optical transmittance, and thermal properties, were also investigated in detail. The novel macromonomer was economical but effective to modify the properties of the UV‐curable coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43116.     

Synthesis and characterization of poly(fluorinated acrylate)/silica hybrid nanocomposites

The nanocomposite particles (NPs) with inorganic silica as core and fluorinated polymer shell have been in situ synthesized via emulsion polymerization. The chemical composition and core‐shell structure were characterized by Fourier‐transform infrared spectrometry and transmission electron microscopy. The results showed that silica nanoparticles were encapsulated in latex particles, with single‐ and multicore morphologies coexisting. Thermal gravimetric analysis also suggested the successful encapsulation of silica into NPs with enhanced thermal stability. The surface properties of the latex films produced from the core‐shell particles were also investigated by contact angle method and water absorption measurement. Both fluorinated polymer and silica contributed to less water absorption ratio and lower surface‐free energy, which was composed of larger polar component and smaller disperse component, just reversed as usual. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

在改性模拟体液中电沉积羟基磷灰石涂层

Hydroxyapatite coatings were directly prepared on anodized titanium by electro-deposition method in a modified simulated body fluid. The configuration, structure and bioactivity of the coating were investigated with scanning electron microscopy (SEM), X-ray diffraction analyzer (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The results demonstrated that pure and homogeneous hydroxyapatite coating can be obtained without any post-treatment. The prepared coating showed good bioactivity in simulated body fluid (SBF). The time required for a fully covered dense hydroxyapatite coatings was 4 days immersion in SBF.     

Cerium-doped hydroxyapatite/collagen coatings on titanium for bone implants

The novelty of the present research consists in the possibility of obtaining cerium-doped hydroxyapatite/collagen coatings on the titanium support, to improve the performance of the bone implants. These coatings were deposited on the titanium surface by biomimetic method using a modified supersaturated calcification solution (SCS) additionally containing a cerium source and collagen. Prior to the deposition of the apatite layer, an alkali ÷ thermal oxidation pretreatment has been applied to ensure an increase in the bioactivity of the titanium surface. The coatings were examined by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy. The EDX and XRD investigations of the coatings indicated that cerium was incorporated in the hydroxyapatite lattice. The collagen presence in the coatings was confirmed by FTIR analysis. The cerium-doped hydroxyapatite/collagen coatings showed good antibacterial efficacy against Escherichia coli and Staphylococcus aureus bacteria, being more effective against Escherichia coli. These coatings have a significant potential to be used in the dental and orthopedic implants, as the osseointegration depends on much more factors than simple formation of hydroxyapatite.     

Development of an environmentally friendly protective coating for the depleted uranium-0.75 wt.% titanium alloy: Part IV. Vibrational spectroscopy of the coating

Molybdenum oxide based conversion coatings have been formed on the surface of the depleted uranium-0.75 wt.% titanium alloy and the coating structure was found to undergo changes as it ages. Raman and Fourier transform infrared (FT-IR) spectroscopies have been performed to examine these changes. Raman spectroscopic measurements indicate that the coating is based on an octamolybdate structure and FT-IR experiments show that uranyl hydroxide is present in the as-made coating but no longer apparent in the aged coatings, supporting the proposed mechanism describing the aging of the coating. Both techniques show that none of the molybdenum is in the form of tetrahedral molybdates.     

Effectiveness of PANI/Cu/TiO2 ternary nanocomposite on antibacterial and antistatic behaviors in polyurethane coatings

Surfaces with antibacterial and antistatic functionalities are one of the new demands of todays' industry. Therefore, a facile method for the preparation of multifunctional polyaniline/copper/TiO₂ (PANI/Cu/TiO₂) ternary nanocomposite based on in situ polymerization is presented. This nanocomposite was characterized through the different techniques and was utilized for induction of antibacterial and antistatic properties in polyurethane coatings. Measurement of the conductivity of PANI/Cu/TiO₂ ternary nanocomposite indicated higher electrical conductivity of this nanocomposite compared to pure PANI. The antibacterial activity of the modified polyurethane coatings was tested against Gram-positive and Gram-negative bacteria which led to remarkable reduction in bacterial growth. Besides, it was observed that polyurethane coating with 2 wt % content of ternary nanocomposite has a surface electrical resistance equal 4 × 10⁸ Ω/sq which acquires surface electrical resistance of standard antistatic coatings. The final coatings were also characterized in terms of thermal and mechanical properties to investigate the effect of the ternary nanocomposite on improvement of these properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48825.     

Bioinspired metal–polymer thin films with varying hydrophobic properties

Nanocomposites involve the inclusion of one material into the layers of another material at a nanoscale level. Inspired by nature, nanocomposites material systems offer functionalities over their bulk forms which in some cases have evolved over millions of years. Here, thin film coatings have been fabricated by PVD sputtering, comprising a soft PTFE phase which is combined with a hard metallic NiTi phase. A series of coatings with PTFE ranging from 10 to 75 vol% have been prepared, and their surface energies and microstructures investigated. The surface energy of the nanocomposite films changes with the PTFE content, falling in the range between PTFE and NiTi with water contact angles between 80° and 102° for a thin film with 25 and 75 vol% of PTFE, respectively. Here, both TEM and EDX reveal PTFE forming along NiTi column boundaries. Coatings with PTFE content greater than 50 vol% failed due to a build-up of intrinsic stress. The degree of hybridization between NiTi and PTFE was found to be dependent on the PTFE layer thickness. SEM analysis of this coating reveals PTFE at the surface embedded within the NiTi matrix.