Organic-inorganic hybrid sol-gelcoatings for metal corrosion protection: a review of recent progress

This paper is a review of the most recent and relevant achievements (from 2001 to 2013) on the development of organic–inorganic hybrid (OIH) coatings produced by sol–gel-derivedmethods to improve resistance to oxidation/corrosion of different metallic substrates and their alloys. This review is focused on the research of OIH coatings based on siloxanes using the sol–gel process conducted at an academic level and aims to summarize the materials developed and identify perspectives for further research. The fundamentals of sol–gel are described, including OIH classification, the interaction with the substrate, their advantages, and limitations. The main precursors used in the synthesis ofOIHsol–gel coatings for corrosion protection are also discussed, according to the metallic substrate used. Finally, a multilayer system to improve the resistance to corrosion is proposed, based on OIH coatings produced by the sol–gel process, and the future research challenges are debated.

Organic-inorganic nanostructured multilayers for calcium phosphate biomineralization

The weak fixation of biomaterials within the bone structure is one of the major reasons of implants failures. Calcium phosphate (CaP) coatings are used in bone tissue engineering to improve implant osseointegration by enhancing cellular adhesion, proliferation and differentiation, leading to a tight and stable junction between implant and host bone. It has also been observed that materials compatible with bone tissue either have a CaP coating or develop such a calcified surface upon implantation. Thus, the development of bioactive coatings becomes essential for further improvement of integration with the surrounding tissue. However, most of current applied CaP coatings methods (e.g. physical vapor deposition), cannot be applied to complex shapes and porous implants, provide poor structural control over the coating and prevent incorporation of bioactive organic compounds (e.g. antibiotics, growth factors) because of the used harsh processing conditions. Layer-by-layer (LbL) is a versatile technology that permits the building-up of multilayered polyelectrolyte films in mild conditions based on the alternate adsorption of cationic and anionic elements that can integrate bioactive compounds. As it is recognized in natureâ s biomineralization process the presence of an organic template to induce mineral deposition, this work investigate a ion based biomimetic method where all the process is based on LbL methodology made of weak natural-origin polyelectrolytes. A nanostructured multilayer component, with 5 or 10 bilayers, was produced initially using chitosan and chondroitin sulphate polyelectrolyte biopolymers, which possess similarities with the extracellular matrix and good biocompatibility. The multilayers are then rinsed with a sequential passing of solutions containing Ca2+ and PO43- ions. The formation of CaP over the polyelectrolyte multilayers was confirmed by QCM-D, SEM and EDX. The outcomes show that 10 polyelectrolyte bilayer condition behaved as a  better site for initiating the formation of CaP as the precipitation occur at earlier stages than in 5 polyelectrolyte bilayers one. This denotes that higher number of bilayers could hold the CaP crystals more efficiently. This work achieved uniform coatings that can be applied to any surface with access to the liquid media in a low-temperature method, which potentiates the manufacture of effective bioactive biomaterials with great potential in orthopedic applications.

Hot-dip galvanized steel dip-coatedwith ureasilicate hybrid in simulated concrete pore solution: Assessment of coating morphology and corrosion protection efficiency

The barrier effect and the performance of an organic–inorganic hybrid (OIH) sol–gel coating are highlydependent on the coating deposition method as well as processing conditions. In this work, studies onthe influence of experimental parameters using the dip coating method were performed. Factors suchas residence time (Rt), a curing step between each dip step and the number of layers of sol–gel OIHfilms deposited on HDGS to prevent corrosion in highly alkaline environments were studied. These OIHcoatings were obtained using a functionalized siloxane, 3-isociantepropyltriethoxysilane that reactedwith a diamino-functionalized oligopolymer (Jeffamine®D-230). The barrier efficiency of OIH coatings insimulated concrete pore solutions (SCPS) was assessed in the first moments of contact, by electrochemicalimpedance spectroscopy and potentiodynamic methods. The durability and stability of the OIH coatings inSCPS was monitored during eight days by macrocell current density. The morphological characterizationof the surface was performed by scanning electronic microscopy before and after exposure to SCPS.Glow discharge optical emission spectroscopy was used to obtain quantitative composition profiles toinvestigate the thickness of the OIH coatings as a function of the number of layers deposited and theinfluence of the Rt in the coating thickness.

Ureasilicate hybrid coatings for corrosion protection of galvanized steel in chloride-contaminated simulated concrete pore solution

Organic-inorganic hybrid (OIH) sol-gel coatings based on ureasilicates (U(X)) have promising properties for use as eco-friendly coatings on hot dip galvanized steel (HDGS) and may be considered potential substitutes for pre-treatment systems containing Cr(VI). These OIH coatings reduce corrosion activity during the initial stages of contact of the HDGS samples with highly alkaline environments (cementitious media) and allow the mitigation of harmful effects of an initial excessive reaction between cement pastes and the zinc layer. However, the behavior of HDGS coated with U(X) in the presence of chloride ions has never been reported. In this paper, the performance of HDGS coated with five different U(X) coatings was assessed by electrochemical measurements in chloride-contaminated simulated concrete pore solution (SCPS). U(X) sol-gel coatings were produced and deposited on HDGS by a dip coating method. The coatings performance was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization curves measurements, macrocell current density and polarization resistance in contact with chloride-contaminated SCPS. The SEM/EDS analyses of the coatings before and after the tests were also performed. The results showed that the HDGS samples coated with the OIH coatings exhibited enhanced corrosion resistance to chloride ions when compared to uncoated galvanized steel.

Flexible organic–inorganic hybrid layer encapsulation for organic opto-electronic devices

In this work we produce and study the flexible organic–inorganic hybrid moisture barrier layers for the protection of air sensitive organic opto-electronic devices. The inorganic amorphous silicon nitride layer (SiNx:H) and the organic PMMA [poly (methyl methacrylate)] layer are deposited alternatingly by using hot wire chemical vapor deposition (HW-CVD) and spin-coating techniques, respectively. The effect of organic–inorganic hybrid interfaces is analyzed for increasing number of interfaces. We produce highly transparent (∼80% in the visible region) hybrid structures. The morphological properties are analysed providing a good basis for understanding the variation of the water vapor transmission rate (WVTR) values. A minimum WVTR of 4.5 × 10−5g/m2day is reported at the ambient atmospheric conditions for 7 organic/inorganic interfaces. The hybrid barriers show superb mechanical flexibility which confirms their high potential for flexible applications.

Eco-friendly luminescent hybrid materials based on EuIII and LiI co-doped chitosan

Biopolymer-based materials have been of particular interest as alternatives do synthetic polymers due to their low toxicity, biodegradability and biocompatibility. Among them, chitosan is one of the most studied ones and has recently been investigated for the application as solid state polymer electrolytes. Furthermore, it can serve as a host for luminescent species such as rare earth ions, giving rise to materials with increased functionality, of particular interest for electrochemical devices. In this study, we investigate chitosan based luminescent materials doped wit Eu3+ and Li+ triflate salts from the structural, photophysical and conductivity points of view. Because the host presents a broad emission band in the blue to green, while Eu3+ emits in the red, fine tuning of emission colour and/or generation of white light is possible by optimizing composition and excitation scheme. Europium lifetimes (5D0) are in the range 270 – 350 µs and quantum yields are as high as 2%. Although Li+ does not interfere with the luminescent properties, it grants ion-conducting properties to the material suggesting that a combination of both properties could be further explored in multifunctional device.

Silk fibroin based multifunctional materials

Silk fibroin is a commonly available natural biopolymer produced in specialized glands of arthropods, such as silkworms or spiders, scorpions, mites, bees and flies. This biopolymer has a long history of use in textile production and also as sutures or treatment of skin wounds. Silk fibroin has been increasingly explored in other areas of biomedical science where we can find a higher morphological diversification of silk biomaterials like films, electrospun fibers, 3D porous scaffolds or nanoparticles. In recent years it has been demonstrated that fibroin is an excellent material for active components in optical devices. This new application opens the way towards the development of multifunctional optoelectronic devices, which in perspective can be made fully biocompatible and eventually bioresorbable. Moreover, fibroin can be added to other biocomponents in order to modify the biomaterial properties leading to optimized and total different functions. These improvements can go from higher cell adhesion in tissue engineering or enhanced optical transparency, smoothness or flexibility in optoelectronic devices. The tuning and completely understanding of silk fibers physicochemical properties and interaction with other elements are of crucial importance for the improvement of already existent silk-based materials and the basis for the development of new products.

Effect of acid or alkaline catalyst and of different capping agents on the optical properties of CdS nanoparticles incorporated within a diureasil hybrid matrix

CdS nanoparticles (NPs) were synthesized using colloidal methods and incorporated within a diureasil hybrid matrix. The surface capping of the CdS NPs by 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) organic ligands during the incorporation of the NPs within the hybrid matrix has been investigated. The matrix is based on poly(ethylene oxide)/poly(propylene oxide) chains grafted to a siliceous skeleton through urea bonds and was produced by sol–gel process. Both alkaline and acidic catalysis of the sol–gel reaction were used to evaluate the effect of each organic ligand on the optical properties of the CdS NPs. The hybrid materials were characterized by absorption, steady-state and time-resolved photoluminescence spectroscopy and High Resolution Transmission Electron Microscopy (HR-TEM). The preservation of the optical properties of the CdS NPs within the diureasil hybrids was dependent on the experimental conditions used. Both organic ligands (APTMS and MPTMS) demonstrated to be crucial in avoiding the increase of size distribution and clustering of the NPs within the hybrid matrix. The use of organic ligands was also shown to influence the level of interaction between the hybrid host and the CdS NPs. The CdS NPs showed large Stokes shifts and long average lifetimes, both in colloidal solution and in the xerogels, due to the origin of the PL emission in surface states. The CdS NPs capped with MPTMS have lower PL lifetimes compared to the other xerogel samples but still larger than the CdS NPs in the original colloidal solution. An increase in PL lifetimes of the NPs after their incorporation within the hybrid matrix is related to interaction between the NPs and the hybrid host matrix.

Polymer electrolytes for electrochromic devices

Polymer electrolytes are currently the focus of much attention as potential electrolytes in electrochemical devices such as batteries, display devices and sensors. Generically, solid polymer electrolytes (SPEs) are mixtures of salts with soft polar polymers. SPEs have many advantages including high energy density, no risk of leakage, no issues related to the presence of solvent, wide electrochemical stability windows, simplified processability and light weight. With the goal of developing a new family of environmentally friendly multifunctional biohybrid materials displaying high ionic conductivity we have produced in the present work, flexible films based on different polymers or hybrids incorporating different salts. The polymer electrolytes studied here have been characterized by means of Differential Scanning Calorimetry, Thermogravimetric Analysis, X-ray diffraction, Polarized Optical Microscopy, complex impedance spectroscopy and cyclic voltammetry. An evaluation of the performance of the sample with the highest conductivity as electrolyte in all solid-state ECDs was performed.

Lithium-doped silk fibroin films for application in electrochromic devices

Silk fibroin (SF) is a commonly available natural biopolymer produced in specialized glands of arthropods, with a long history of use in textile production and also in health cares. The exceptional intrinsic properties of these fibers, such as self-assembly, machinability, biocompatibility, biodegradation or non-toxicity, offer a wide range of exciting opportunities [1]. It has long been recognized that silk can be a rich source of inspiration for designing new materials with tailored properties, enhanced performance and high added value for targeted applications, opening exciting new prospects in the domain of materials science and related technological fields, including bio-friendly integration, miniaturization and multifunctionalization. In recent years it has been demonstrated that fibroin is an excellent material for active components in optics and photonics devices. Progress in new technological fields such as optics, photonics and electronics are emerging [2,3]. The incorporation of polymer electrolytes as components of various devices (advanced batteries, smart windows, displays and supercapacitors) offers significant advantages with respect to traditional electrolytes, including enhanced reliability and improved safety. SF films are particularly attractive in this context. They have near-perfect transparency across the VIS range, surface flatness (together with outstanding mechanical robustness), ability to replicate patterned substrates and their thickness may be easily tailored from a few nanometers to hundreds of micrometers through spin-casting of a silk solution into subtract. Moreover, fibroin can be added to other biocomponents or salts in order to modify the biomaterial properties leading to optimized and total different functions. Preliminary tests performed with a prototype electrochromic device (ECD) incorporating SF films doped with lithium triflate and lithium tetrafluoroborate (LiTFSI and LiBF4, respectively) as electrolyte and WO3 as cathodic electrochromic layer, are extremely encouraging. Aiming to evaluate the performance of the ion conducting SF membranes doped with LiTFSI and LiBF4 (SF-Li), small ECDs with glass/ITO/WO3/SF-Li/CeO2-TiO2/ITO/glass configuration were assembled and characterized. The device exhibited, after 4500 cycles, the insertion of charge at -3.0 V reached –1.1 mC.cm-2 in 15 s. After 4500 cycles the window glass-staining, glass/ITO/WO3/Fibrin-Li salts electrolyte/CeO2-TiO2/ITO/glass configuration was reversible and featured a T  8 % at λ = 686 nm

Degradation of all-inkjet-printed organic thin-film transistors with TIPS-pentacene under processes applied in textile manufacturing

Printed electronics represent an alternative solution for the manufacturing of low-temperature and large area flexible electronics. The use of inkjet printing is showing major advantages when compared to other established printing technologies such as, gravure, screen or offset printing, allowing the reduction of manufacturing costs due to its efficient material usage and the direct-writing approach without requirement of any masks. However, several technological restrictions for printed electronics can hinder its application potential, e.g. the device stability under atmospheric or even more stringent conditions. Here, we study the influence of specific mechanical, chemical, and temperature treatments usually appearing in manufacturing processes for textiles on the electrical performance of all-inkjet-printed organic thin-film transistors (OTFTs). Therefore, OTFTs where manufactured with silver electrodes, a UV curable dielectric, and 6,13-bis(triisopropylsilylethynyl) pentance (TIPS-pentacene) as the active semiconductor layer. All the layers were deposited using inkjet printing. After electrical characterization of the printed OTFTs, a simple encapsulation method was applied followed by the degradation study allowing a comparison of the electrical performance of treated and not treated OTFTs. Industrial calendering, dyeing, washing and stentering were selected as typical textile processes and treatment methods for the printed OTFTs. It is shown that the all-inkjet-printed OTFTs fabricated in this work are functional after their submission to the textiles processes but with degradation in the electrical performance, exhibiting higher degradation in the OTFTs with shorter channel lengths (L=10 μm).

Electrochromic devices incorporating biohybrid electrolytes doped with a lithium salt, an ionic liquid or a mixture of both

The sol-gel method was employed in the synthesis of di-urethane cross-linked poly( caprolactone) (PCL(530)/siloxane biohybrid ormolytes incorporating either a mixture of lithium triflate (LiCF3SO3) and the ionic liquid (IL) 1-ethyl-3-methyl imidazolium tetrafluoroborate ([Emim]BF4), or solely with [Emim]BF4 or LiCF3SO3. The ormolyte doped with [Emim]BF4 is thermally more stable and exhibits higher ionic conductivity (4 x 10-4 and 2 x 10-3 S cm-1 at 36 and 98 ºC, respectively) than those containing the LiCF3SO3/[Emim]BF4 mixture or just LiCF3SO3. The three ormolytes were employed in the production of glass/ITO/ormolyte/WO3/ITO/glass electrochromic devices (ECDs) designated as ECD@Y with Y = Li-[Emim]BF4, [Emim]BF4 and Li. The three ECDs displayed fast switching speed (ca. 30 s). ECD@Li-[Emim]BF4 exhibited an electrochromic contrast of 18.4 % and an optical density change of 0.11 in the visible region, the coloration efficiency attained at 555 nm was 159 and 80.2 cm-2 C-1 in the “on” and “off” states, respectively, and the open circuit memory was 48 hours. In the “on” state the CIE 1931 color space coordinates were x = 0.29 and y = 0.30, corresponding to blue color.

Controlled aggregation of gold nanoparticles in a di-ureasilmatrix. Optical and micro indentation investigation

Nanocomposite materials with an organic-inorganic urea-silicate (di-ureasil) based matrix containing gold nanoparticles (NPs) were synthesized and characterized by optical (UV/Vis) spectroscopy and indentation measurement. The urea silicate gels were obtained by reaction between silicon alkoxyde modified by isocyanate group and polyethylene glycol oligomer with amine terminal groups in presence of catalyst. The latter ensures the successful incorporation of citrate-stabilized gold NPs in the matrix. It is shown that using a convenient destabilizing agent (AgNO3) and governing the preparative conditions, the aggregation degree of gold NPs can be controlled. The developed synthesis procedure significantly simplifies the preparative procedure of gold/urea silicate nanocomposites, compared to the procedure using gold NPs, preliminary covered with silica shells. Mechanical properties of the prepared sample were characterised using depth sensing indentation methods (DSI) and an idea about the type of aggregation structures was suggested.

Polymer electrolyte based on DNA and N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium bis(trifluoromethylsulfonyl)imide

Combining ionic liquids (ILs) with polymers offers the prospect of new applications, where they surpass the performance of conventional media, such as organic solvents, giving advantages in terms of improved safety and a higher operating temperature range. In this work we have investigated the morphology, thermal and electrochemical properties of polymer electrolytes prepared through the addition of con- trolled quantities of the cholinium based IL N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium bis(trifluo- romethylsulfonyl)imide ([N1 1 1 2(OH)] [NTf2]) to a deoxyribonucleic acid (DNA) host network. These novel IL-based electrolytes have been analyzed aiming at applications in electrochemical devices. An optimized sample showed good thermal stability up to 155 °C and a wide electrochemical window of ~3.5 V. The highest conductivity was registered for the DNA[N1 1 1 2(OH)][NTf2] (1:1) (2.82 × 10-5 and 1.09 × 10-3 S cm-1 at 30 and 100 °C, respectively).

Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C2mim][CnSO3], [C2mim][CnSO4] and [C2mim][diCnPO4]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes (SPE) membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10−4 S cm−1 and a wide electrochemical window of ∼ 4.0 V.