Panagiotis N. Manoudis

Superhydrophobic Composite Films Produced on Various Substrates

Hydrophilic silica (SiO2) nanoparticles were dispersed in solutions of poly(methyl methacrylate) (PMMA) and in solutions of a commercial poly(alkyl siloxane) (Rhodorsil 224), and the suspensions were sprayed on glass surfaces. The effect of the particle concentration on the hydrophobic character of PMMA-SiO2 and Rhodorsil-SiO2 films was investigated and showed the following: (i) Static contact angles (theta s), measured on surfaces that were prepared from dilute dispersions (particle concentration <1% w/v), increase rapidly with particle concentration and reach maximum values (154 and 164 degrees for PMMA-SiO2 and siloxane-SiO2, respectively). Further increases in particle concentration do not have any effect on theta s. (ii) The effect of particle concentration on the contact angle hysteresis (thetaAlpha - thetaR) is more complicated: as the particle concentration increases, we first notice an increase in hysteresis, which then decreases and finally becomes constant at elevated particle concentrations. The lowest thetaAlpha - thetaR values were 5 degrees for PMMA-SiO2 and 3 degrees for siloxane-SiO2, respectively. (iii) SEM and AFM images show that a two-length-scale hierarchical structure is formed on the surface of the superhydrophobic films. It is demonstrated that superhydrophobicity can be achieved using various hydrophilic nanoparticles (alumina and tin oxide nanoparticles were successfully tested) and that the substrate has almost no effect on the hydrophobic character of the applied coatings, which were produced on silicon, concrete, aluminum, silk, wood, marble, and of course glass. The results are discussed in light of Wenzel and Cassie-Baxter models.

Polymer-Silica nanoparticles composite films as protective coatings for stone-based monuments

The decrease of surface energy of mineral substrates similar to those used in many stone monuments of cultural heritage by the application of protective polymer coatings along with the simultaneous increase of their surface roughness can increase their ability to repel water substantially. In this work, the effect of artificially induced roughness on the water repellency of mineral substrates coated with protective polymer films was investigated. Natural marble samples or home made calcium carbonate blocks were tried as the mineral substrates. The roughness increase was achieved by mineral chemical etching or by creation of nanoscale binary composition film on the substrate surface. PMMA and PFPE were the polymers used, while different-sized silica nanoparticles were employed for the production of the nanocomposite films. Examination of the coated and uncoated surfaces with profilometry and AFM and measurements of water contact angles reveal a pronounced effect of the surface roughness on water repellency. Especially in the case of nanocomposite coatings, the surfaces become super-hydrophobic. This result indicates that the nanoscale binary composition film scheme, which is characterized by its simplicity and low cost, is a suitable candidate for the water protection of stone-based monuments on large scale.

From hydrophobic to superhydrophobic and superhydrophilic siloxanes by thermal treatment.

The cross-influence effects of treatment temperature and time on the wettability of a siloxane elastomer is investigated in detail, through static and tilt contact angle measurements. The material is heated at 400, 500, 600, 650, 700, and 800 °C for various periods, ranging from 1 to 300 s. The siloxane surface is subjected to multiple wettability transitions with treatment time: from intrinsic hydrophobicity to superhydrophobicity (and water repellency) and then through intermediate stages (hydrophobicity and hydrophilicity) to superhydrophilicity. For the time scale used herein (1-300 s), this scenario is recorded for treatment at 650, 700, and 800 °C. For treatment at lower temperatures (400, 500, and 600 °C) only the first transition, from intrinsic hydrophobicity to superhydrophobicity, is recorded. Scanning electron microscopy, micro-Fourier transform infrared (micro-FTIR), and micro-Raman spectroscopies are employed to correlate the aforementioned wettability transitions with structural and chemical changes of the siloxane surface, developed during thermal treatment. It is shown that the first transition from intrinsic hydrophobicity to superhydrophobicity is accompanied by a severe surface-structure evolution that increases surface roughness. Once superhydrophobicity is achieved, the surface structure reaches a saturation point and it is not subjected to any other change with further thermal treatment. FTIR spectroscopy shows that the intensity of the O-H/C-H peaks increases/decreases with treatment time, and Raman measurements show that the C-Si-C vibrations gradually disappear with treatment time. The evaporation of a droplet resting on a superhydrophobic, water-repellent siloxane surface, which was produced after appropriate thermal treatment, is monitored. It is shown that droplet evaporation initially follows the constant contact area mode. At later evaporation stages, a transition to the constant contact angle mode is recorded. Finally, it is demonstrated that the superhydrophobic and water-repellent siloxane surfaces exhibit self-cleaning properties, good durability, and furthermore do not practically affect the optical transparency of glass substrates.

Surface Properties of Superhydrophobic Coatings for Stone Protection

Superhydrophobic films are produced by a simple and low cost method. Silica (SiO2) nanoparticles are dispersed in solutions of Rhodorsil 224, a commercial poly(alkyl siloxane) which is used for the protection of outdoor cultural heritage objects, and the suspensions are sprayed on glass surfaces. It is shown that the siloxane-nanoparticle composite films prepared from dispersions of high particle concentrations (≥ 0.5% w/v) exhibit superydrophobic properties (high static contact angle and small hysteresis) which can be rationalized by the Cassie-Baxter model, according to quantitative measurements obtained by SEM images. Siloxane-nanoparticle films are then deposited (sprayed) on “Opuka”, a fine-grained argillite which was used for the restoration of the castle of Prague. It is shown that the treated stone surfaces exhibit superydrophobic properties, similar to the treated glass surfaces. The efficacy of the superhydrophobic films to protect Opuka is evaluated by performing water contact angle, water capillary absorption, water vapor permeability and colorimetric measurements. It is shown that the use of nanoparticles in the protective coating has a positive effect on the results of the aforementioned tests, except for the colorimetric measurements.

Superhydrophobic and Water-Repellent Polymer-Nanoparticle Composite Films

The wetting properties of the surfaces of polymer films changed dramatically from the usual inherent hydrophobicity (or slight hydrophilicity) to superhydrophobicity (contact angle, CA > 150°) by embedding oxide nanoparticles into the polymer matrices. The desired hierarchical roughness at the micrometer and nanometer scale was induced in poly(methyl methacrylate), polystyrene, and four poly(alkyl siloxane) films enriched with silica, tin oxide, alumina, and zinc oxide nanoparticles, ranging from 7 to 70 nm in mean diameter. Particles were added in the polymer solutions which were afterward sprayed on various substrates, such as glass, silicon, concrete, aluminum, silk, paper, wood, marble (white), sandstone, and mortar. It is stressed that superhydrophobicity was accompanied by water repellency, as evidenced by the low contact angle hysteresis (CAH < 10°). Consequently, it is demonstrated that the simple suggested method for transforming the wetting properties of polymer films to achieve extreme nonwetting is flexible as it can be effectively applied using different materials, including polymers and nanoparticles of low cost. Moreover, the method can be easily used for the surface treatment of large and various substrates. The effects of the (1) concentration and size of the nanoparticles, (2) chemical nature of the polymer matrix, and (3) treated substrate on the wetting properties of the films were investigated and interpreted using scanning electron microscopy (SEM). Finally, it is shown that depending on the color of the underlying substrate, the superhydrophobic water-repellent polymer-nanoparticle films may have a negligible effect on the aesthetic appearance of the treated substrate.