Qualitative and Semiquantitative Determination of the Atomic and Molecular Tungsten Distributions in Hybrid Hydroxyurethanes-Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW12O40]3-).

In this study, hybrid poly(dimethylsiloxane)-derived hydroxyurethanes films (PDMSUr-PWA) containing phosphotungstic acid (H3PW12O40/PWA) were characterized using field emission gun scanning electron microscopy (FEG-SEM), in attenuated total reflectance Fourier transform mid-infrared mode (ATR FT-MIR), and analyzed using synchrotron radiation micro-X-ray fluorescence (SR-µXRF), synchrotron radiation grazing incidence X-ray fluorescence (SR-GIXRF), laser-induced breakdown spectroscopy (LIBS), and instrumental neutron activation analysis (NAA) in order to correlate the distribution patterns of tungsten and properties of PDMSUr-PWA films. PDMS constitute elastomers with good mechanical, thermal, and chemical (hydrophobicity/non-hygroscopy) resistance. Currently, products based on urethanes (e.g., polyurethanes) are widely used in many applications as plastics, fiber-reinforced polymers, high-performance adhesives, corrosion-resistant coatings, photochromic films, among others. The possibility to combine inorganic and organic components can produce a hybrid material with unique properties. PWA has an important role as agent against the corrosion of steel surfaces in different media, besides exhibiting amazing catalytic and photochromic properties in these films. PWA kept its structure inside of these hybrid films through interactions between the organic matrix of PDMSUr and silanol from the inorganic part (organically modified silica), as was shown using ATR FT-MIR spectra. The FEG-SEM/SR-µXRF/wide-angle X-ray scattering (WAXS)/X-ray diffraction (XRD)/energy dispersive X-ray results proved the presence of PWA in the composition of domains of PDMSUr-PWA films. At PWA concentrations higher than 50 wt%/wt, tungsten segregation across the thickness is predominant, while that at PWA concentrations lower than 35 wt%/wt, tungsten segregation at surface is predominant. Inhomogeneities in the tungsten distribution patterns (at micrometric and millimetric level) may play an important role in the mechanical properties of these films (elastic modulus and hardness).

Preparation of Polyurethane Monolithic Resins and Modification with a Condensed Tannin-Yielding Self-Healing Property.

Resins of polyurethane were prepared from vegetable oils (crambe and castor) and modified by adding green corrosion inhibitor (condensed tannin). The oils were characterized by gas chromatography with flame-ionization detection (GC-FID), attenuated total reflectance Fourier transform infrared spectroscopy (FTIR-ATR) and thermogravimetric analysis (TGA). The reaction was monitored by characterizing the intermediate products (polyester and prepolymer). The polyester was characterized by solubility in methanol, acidity index, hydroxyl groups and FTIR-ATR, and the prepolymer was characterized by solid content, solvent content, isocyanate (NCO) groups and FTIR-ATR. The formation of PU resins was confirmed by FTIR-ATR and TGA, and the presence of tannin particles incorporated in the coating can be observed by optical microscopy (OM). The absence of the band attributed to NCO in FTIR-ATR spectra of the resins confirmed the complete reaction between polyester and prepolymer. The OM observation and a video demonstrate that Polyurethane (PU)-modified with condensed tannin resin presents self-healing effect, probably through the formation of new hydrogen bonds when in contact with deionized water. Therefore, these results open possibilities for new synthetic routes aiming at improving the very important self-healing property for protecting metals and their alloys against corrosion, extending significantly the metallic materials lifetime as previously demonstrated by our group.

Role of Polymeric Coating on the Phosphate Availability as a Fertilizer: Insight from Phosphate Release by Castor Polyurethane Coatings.

The coating of fertilizers with polymers is an acknowledged strategy for controlling the release of nutrients and their availability in soil. However, its effectiveness in the case of soluble phosphate fertilizers is still uncertain, and information is lacking concerning the chemical properties and structures of such coatings. Here, an oil-based hydrophobic polymer system (polyurethane) is proposed for the control of the release of phosphorus from diammonium phosphate (DAP) granules. This material was systematically characterized, with evaluation of the delivery mechanism and the availability of phosphate in an acid soil. The results indicated that thicker coatings can change the maximum nutrient availability toward longer periods, such as 4.5-7.5 wt % DAP coated, that presented the highest concentrations at 336 h, as compared to 168 h for uncoated DAP. In contrast, DAP treated with 9.0 wt % began to increase the concentration after 168 h until it results in maximum release at 672 h. These effects could be attributed to the homogeneity of the polymer and the porosity. The strategy successfully provided long-term availability of a phosphate source.