Materials

Research

14 pages, 3350 KiB

Open AccessArticle

Field Test of Self-Cleaning Zr-Modified-TiO₂-SiO₂ Films on Glass with a Demonstration of Their Anti-Fogging Effect

by Andraž Šuligoj, Olena Pliekhova, Nives Vodišek, Mohor Mihelčič, Angelja K. Surca, Roman Kunič, Barbara Šubic, Jernej Starman, Aleš Ugovšek and Urška Lavrenčič Štangar

Materials 2019, 12(13), 2196; https://doi.org/10.3390/ma12132196 - 8 Jul 2019

Cited by 9 | Viewed by 3632

Abstract

The number of commercial products claiming self-cleaning properties is rising and testing of long-term activity and durability of such coatings needs to be addressed more. The time-dependent changes of different characteristics like haze, transparency, and color are essential for transparent glazing materials. Herein, [...] Read more.

The number of commercial products claiming self-cleaning properties is rising and testing of long-term activity and durability of such coatings needs to be addressed more. The time-dependent changes of different characteristics like haze, transparency, and color are essential for transparent glazing materials. Herein, we aimed to examine whether the laboratory results obtained on the Zr-modified-titania-silica (TiZr) self-cleaning materials would translate to larger-scale outdoor-exposed testing. TiZr thin films were deposited via spraying onto float glass window surfaces and exposed into three different environments for 20 months. For comparison, a commercially available active SGG BIOCLEAN^TM glass and standard float glass were simultaneously exposed in the same conditions. It was shown that the self-cleaning property of either a commercial product or TiZr-coated float glass was not considerably effective in real field test conditions, although the previous laboratory tests showed pronounced photocatalytic activity of TiZr thin films. The inclination angle; however, was shown to have a considerable effect on the self-cleaning ability of samples, as did the rain patterns during the testing period. On the other hand, the anti-fogging effect of our TiZr material was very well expressed in controlled laboratory conditions (measuring droplet formation time) as well as in the real outdoor environment. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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16 pages, 4113 KiB

Open AccessArticle

Characterization of Photoactive Fe-TiO₂ Lime Coatings for Building Protection: The Role of Iron Content

by Chrysi Kapridaki, Nikolaos Xynidis, Eleftheria Vazgiouraki, Nikolaos Kallithrakas-Kontos and Pagona Maravelaki-Kalaitzaki

Materials 2019, 12(11), 1847; https://doi.org/10.3390/ma12111847 - 6 Jun 2019

Cited by 20 | Viewed by 3290

Abstract

Iron-doped TiO₂ nanoparticles, ranging in Fe concentrations from 0.05 up to 1.00% w/w, were synthesized through a simple sol-gel method. Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), Ultraviolet-Visible (UV-Vis) spectroscopy, nitrogen adsorption−desorption isotherms, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near-edge [...] Read more.

Iron-doped TiO₂ nanoparticles, ranging in Fe concentrations from 0.05 up to 1.00% w/w, were synthesized through a simple sol-gel method. Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), Ultraviolet-Visible (UV-Vis) spectroscopy, nitrogen adsorption−desorption isotherms, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near-edge structure spectroscopy (XANES) were used to characterize the synthesized nanoparticles. The characterization of the Fe-doped TiO₂ nanoparticles revealed the predominant presence of anatase crystalline form, as well as the incorporation of the Fe³⁺ ions into the crystal lattice of TiO₂. The photocatalytic assessment of the Fe-doped TiO₂ nanoparticles indicated that the low iron doping titania (0.05 and 0.10% w/w) have a positive effect on the photocatalytic degradation of Methyl Orange under visible radiation. Moreover, FTIR monitoring of calcium hydroxide pastes enriched with low Fe-doped TiO₂ revealed enhancement of carbonation at both early and later stages. Improved photocatalytic performance and increased lime carbonation, observed in lime coatings with low Fe-doped TiO₂ admixtures, established them as invaluable contributors to the protection of the built environment. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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16 pages, 10859 KiB

Open AccessArticle

Amphiphobic Nanostructured Coatings for Industrial Applications

by Federico Veronesi, Giulio Boveri and Mariarosa Raimondo

Materials 2019, 12(5), 787; https://doi.org/10.3390/ma12050787 - 7 Mar 2019

Cited by 8 | Viewed by 3796

Abstract

The search for surfaces with non-wetting behavior towards water and low-surface tension liquids affects a wide range of industries. Surface wetting is regulated by morphological and chemical features interacting with liquid phases under different ambient conditions. Most of the approaches to the fabrication [...] Read more.

The search for surfaces with non-wetting behavior towards water and low-surface tension liquids affects a wide range of industries. Surface wetting is regulated by morphological and chemical features interacting with liquid phases under different ambient conditions. Most of the approaches to the fabrication of liquid-repellent surfaces are inspired by living organisms and require the fabrication of hierarchically organized structures, coupled with low surface energy chemical composition. This paper deals with the design of amphiphobic metals (AM) and alloys by deposition of nano-oxides suspensions in alcoholic or aqueous media, coupled with perfluorinated compounds and optional infused lubricant liquids resulting in, respectively, solid–liquid–air and solid–liquid–liquid working interfaces. Nanostructured organic/inorganic hybrid coatings with contact angles against water above 170°, contact angle with n-hexadecane (surface tension γ = 27 mN/m at 20 °C) in the 140–150° range and contact angle hysteresis lower than 5° have been produced. A full characterization of surface chemistry has been undertaken by X-ray photoelectron spectroscopy (XPS) analyses, while field-emission scanning electron microscope (FE-SEM) observations allowed the estimation of coatings thicknesses (300–400 nm) and their morphological features. The durability of fabricated amphiphobic surfaces was also assessed with a wide range of tests that showed their remarkable resistance to chemically aggressive environments, mechanical stresses and ultraviolet (UV) radiation. Moreover, this work analyzes the behavior of amphiphobic surfaces in terms of anti-soiling, snow-repellent and friction-reduction properties—all originated from their non-wetting behavior. The achieved results make AM materials viable solutions to be applied in different sectors answering several and pressing technical needs. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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19 pages, 2352 KiB

Open AccessFeature PaperArticle

Hydrothermal Synthesis of Rare-Earth Modified Titania: Influence on Phase Composition, Optical Properties, and Photocatalytic Activity

by Nejc Rozman, David M. Tobaldi, Uroš Cvelbar, Harinarayanan Puliyalil, João A. Labrincha, Andraž Legat and Andrijana Sever Škapin

Materials 2019, 12(5), 713; https://doi.org/10.3390/ma12050713 - 28 Feb 2019

Cited by 39 | Viewed by 3867

Abstract

In order to expand the use of titania indoor as well as to increase its overall performance, narrowing the band gap is one of the possibilities to achieve this. Modifying with rare earths (REs) has been relatively unexplored, especially the modification of rutile [...] Read more.

In order to expand the use of titania indoor as well as to increase its overall performance, narrowing the band gap is one of the possibilities to achieve this. Modifying with rare earths (REs) has been relatively unexplored, especially the modification of rutile with rare earth cations. The aim of this study was to find the influence of the modification of TiO₂ with rare earths on its structural, optical, morphological, and photocatalytic properties. Titania was synthesized using TiOSO₄ as the source of titanium via hydrothermal synthesis procedure at low temperature (200 °C) and modified with selected rare earth elements, namely, Ce, La, and Gd. Structural properties of samples were determined by X-ray powder diffraction (XRD), and the phase ratio was calculated using the Rietveld method. Optical properties were analyzed by ultraviolet and visible light (UV-Vis) spectroscopy. Field emission scanning electron microscope (FE-SEM) was used to determine the morphological properties of samples and to estimate the size of primary crystals. X-ray photoelectron spectroscopy (XPS) was used to determine the chemical bonding properties of samples. Photocatalytic activity of the prepared photocatalysts as well as the titania available on the market (P25) was measured in three different setups, assessing volatile organic compound (VOC) degradation, NO_x abatement, and water purification. It was found out that modification with rare earth elements slows down the transformation of anatase and brookite to rutile. Whereas the unmodified sample was composed of only rutile, La- and Gd-modified samples contained anatase and rutile, and Ce-modified samples consisted of anatase, brookite, and rutile. Modification with rare earth metals has turned out to be detrimental to photocatalytic activity. In all cases, pure TiO₂ outperformed the modified samples. Cerium-modified TiO₂ was the least active sample, despite having a light absorption tail up to 585 nm wavelength. La- and Gd-modified samples did not show a significant shift in light absorption when compared to the pure TiO₂ sample. The reason for the lower activity of modified samples was attributed to a greater Ti³⁺/Ti⁴⁺ ratio and a large amount of hydroxyl oxygen found in pure TiO₂. All the modified samples had a smaller Ti³⁺/Ti⁴⁺ ratio and less hydroxyl oxygen. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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13 pages, 2427 KiB

Open AccessFeature PaperArticle

Use of Steel Industry Wastes for the Preparation of Self-Cleaning Mortars

by José Balbuena, Luis Sánchez and Manuel Cruz-Yusta

Materials 2019, 12(4), 621; https://doi.org/10.3390/ma12040621 - 19 Feb 2019

Cited by 11 | Viewed by 2954

Abstract

An important problem, which must be solved, is the accumulation of industrial waste in landfills. Science has an obligation to transform this waste into new products and, if possible, with high added value. In this sense, we propose the valorization of the waste [...] Read more.

An important problem, which must be solved, is the accumulation of industrial waste in landfills. Science has an obligation to transform this waste into new products and, if possible, with high added value. In this sense, we propose the valorization of the waste which is generated in the steel lamination process (HSL) through its conversion into a new material with photocatalytic activity which is suitable for use as an additive to obtain a self-cleaning construction material. The valorization of steel husk lamination waste is achieved through a grinding process, which allows the sample to be homogenized, in size, without altering its phase composition, and a thermal treatment that turns it into iron oxide, which acts as a photocatalyst. These residues, before and after treatment, were characterized by different techniques such as PXRD (Powder X-Ray Diffraction), TGA (Thermogravimetric Analysis), SBET (Specific surface area, Brunauer-Emmett-Teller), SEM (Scanning Electron Microscopy) and Diffuse reflectance (DR). MB and RhB tests show that this material is capable of self-cleaning, both of the material itself and when it is incorporated into a construction material (mortar). In addition, the NO_x gas elimination test shows that it is also capable of acting on greenhouse gases such as NO_x. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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15 pages, 2537 KiB

Open AccessArticle

Efficiency of Novel Photocatalytic Coating and Consolidants for Protection of Valuable Mineral Substrates

by Andreja Pondelak, Sabina Kramar, Jonjaua Ranogajec, Luka Škrlep, Snežana Vucetic, Vilma Ducman and Andrijana Sever Škapin

Materials 2019, 12(3), 521; https://doi.org/10.3390/ma12030521 - 9 Feb 2019

Cited by 3 | Viewed by 3592

Abstract

In the process of protection and consolidation of valuable materials, the efficiency is the crucial property that needs to be considered. TiO₂/ZnAl layered double hydroxide (LDH) coating and silicate- and carbonate-based consolidants were synthesized and proposed to be used for protection [...] Read more.

In the process of protection and consolidation of valuable materials, the efficiency is the crucial property that needs to be considered. TiO₂/ZnAl layered double hydroxide (LDH) coating and silicate- and carbonate-based consolidants were synthesized and proposed to be used for protection and consolidation of four porous mineral substrates: brick, stone, render and mortar. The photocatalytic efficiency of TiO₂/ZnAl LDH coating, as well as consolidation efficiency of two consolidants, both applied on model substrates, were studied. The photocatalytic coating showed significant activity and performed well after the durability tests involving rinsing and freezing/thawing procedures. After treatment with both consolidants, a serious enhancement of consolidation of the used substrates was found. On the other hand, the application of TiO₂/ZnAl LDH, as well as consolidants, caused negligible changes in the water vapour permeability values and in appearance of the porous mineral substrates, indicating a high level of compatibility. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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15 pages, 1730 KiB

Open AccessArticle

Quantification of the Photocatalytic Self-Cleaning Ability of Non-Transparent Materials

by Marco Minella and Claudio Minero

Materials 2019, 12(3), 508; https://doi.org/10.3390/ma12030508 - 8 Feb 2019

Cited by 8 | Viewed by 3229

Abstract

The photo-induced reactivity of compounds at the surface of photocatalytic materials is used to maintain the cleanliness of the surface of glass, concretes and paints. A standard method to quantify the photocatalytic self-cleaning (SC) properties of non-transparent materials was recently published. It is [...] Read more.

The photo-induced reactivity of compounds at the surface of photocatalytic materials is used to maintain the cleanliness of the surface of glass, concretes and paints. A standard method to quantify the photocatalytic self-cleaning (SC) properties of non-transparent materials was recently published. It is based on the covering of the sample surface with a defined amount of dye and on the evaluation of the reflectance spectra of the coloured surface under irradiation. The calibration of the spectral changes allowed the quantification of the surface residual dye and the evaluation of the self-cleaning kinetics. The method was tested on seven white and coloured photocatalytic materials using methylene blue (MB), rhodamine B (RhB) and metanil yellow (MY). The main by-products of the MB photocatalytic degradation at the solid/solid interface were identified, showing that MB degradation in solution follows a path quite different from that at the solid/solid interface. Also MY showed a different order of photoreactivity. Furthermore, experiments at the solid/solid interface are more trustworthy than tests in solution for evaluating the self-cleaning ability. The differences of the photocatalytic phenomena at the solid/solid interface in comparison with the most studied photoactivated processes at the solid/liquid interface are outlined. Furthermore, photocatalytic materials showed selectivity toward some specific dyes. This encourages the use of more than one dye for the evaluation of the self-cleaning ability of a photocatalytic material. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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15 pages, 4849 KiB

Open AccessArticle

Improved Self-Cleaning Properties of Photocatalytic Gypsum Plaster Enriched with Glass Fiber

by Kamila Zając, Magdalena Janus and Antoni W. Morawski

Materials 2019, 12(3), 357; https://doi.org/10.3390/ma12030357 - 24 Jan 2019

Cited by 11 | Viewed by 3547

Abstract

In the study the self-cleaning properties of photoactive gypsum plasters are presented. The modified gypsum plasters were obtained by addition of 1 and 3 wt.% of nitrogen-modified titanium dioxide (TiO₂/N) and 0.1, 0.3, and 0.5 wt.% of glass fiber. The self-cleaning [...] Read more.

In the study the self-cleaning properties of photoactive gypsum plasters are presented. The modified gypsum plasters were obtained by addition of 1 and 3 wt.% of nitrogen-modified titanium dioxide (TiO₂/N) and 0.1, 0.3, and 0.5 wt.% of glass fiber. The self-cleaning ability of the obtained materials was tested during two dyes decomposition: Methylene Blue (MB) and Reactive Orange (RO). It was found that presence of glass fiber increased photocatalytic activity of modified gypsum plasters, which may be due to the fact glass fiber may act as ducts for light and transport it to sites screened by TiO₂ or glass fiber can retard charge recombination. Moreover, unexpectedly the addition of glass fiber did not increase the mechanical properties of modified gypsum plasters, which may be because gypsum does not strongly adhere to the surface of glass fibers. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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10 pages, 5091 KiB

Open AccessArticle

Electrophoresis Assembly of Novel Superhydrophobic Molybdenum Trioxide (MoO₃) Films with Great Stability

by Xiaogang Guo and Taotao Liang

Materials 2019, 12(3), 336; https://doi.org/10.3390/ma12030336 - 22 Jan 2019

Cited by 7 | Viewed by 3634

Abstract

This work presents a hydrothermal synthesis approach to produce novel schistose molybdenum trioxide (MoO₃) powders with wide application, and introduces a facile electrophoresis assembly technique to construct the superhydrophobic MoO₃ films (SMFs) with contact angle up to 169 ± 1° [...] Read more.

This work presents a hydrothermal synthesis approach to produce novel schistose molybdenum trioxide (MoO₃) powders with wide application, and introduces a facile electrophoresis assembly technique to construct the superhydrophobic MoO₃ films (SMFs) with contact angle up to 169 ± 1° at normal pressure and temperature. The microstructures and chemical compositions of product were analyzed by field emission scanning electron microcopy (FESEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD). The wettability and stability studies indicate that the SMFs all show great resistance in various environments with adjusting factors, including droplets with different surface tension, pH, relative humidity, etc., and the stability can be maintained at least for five months. Notably, this paper will provides a valuable reference for designing novel oxide powders and their high-efficient hydrophobic film formation with self-cleaning or water proof properties. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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10 pages, 2452 KiB

Open AccessArticle

Super-Efficient Synthesis of Mesh-like Superhydrophobic Nano-Aluminum/Iron (III) Oxide Energetic Films

by Xiaogang Guo and Taotao Liang

Materials 2019, 12(2), 234; https://doi.org/10.3390/ma12020234 - 11 Jan 2019

Cited by 5 | Viewed by 3026

Abstract

In this study, a novel superhydrophobic nano-aluminum/iron (III) oxide composite has been prepared by a facile one-step process of electrophoretic deposition, with wide potential applications. The optimal suspension included ethanol, acetyl-acetone, and the additives of fluorotriphenylsilane and perfluorodecyltriethoxysilane. The microstructure, wettability, and exothermic [...] Read more.

In this study, a novel superhydrophobic nano-aluminum/iron (III) oxide composite has been prepared by a facile one-step process of electrophoretic deposition, with wide potential applications. The optimal suspension included ethanol, acetyl-acetone, and the additives of fluorotriphenylsilane and perfluorodecyltriethoxysilane. The microstructure, wettability, and exothermic performance were analyzed by field emission scanning electron microcopy (FESEM), X-ray diffraction (XRD), water contact angle measurements, and the differential scanning calorimetry (DSC) technique. The water contact angle and the heat-release of the target composites could reach to ~170° and 2.67 kJ/g, and could still keep stable, after exposure for six months, showing a great stability. These results provided an exquisite synthesis of ideas, for designing other superhydrophobic energetic materials with self-cleaning properties, for real industrial application. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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13 pages, 4985 KiB

Open AccessFeature PaperArticle

Solid-Gas Phase Photo-Catalytic Behaviour of Rutile and TiO_n (1 < n < 2) Sub-Oxide Phases for Self-Cleaning Applications

by Manuel Nuño, Vaia Adamaki, David M. Tobaldi, Maria J. Hortigüela Gallo, Gonzalo Otero-Irurueta, Chris R. Bowen and Richard J. Ball

Materials 2019, 12(1), 170; https://doi.org/10.3390/ma12010170 - 7 Jan 2019

Cited by 6 | Viewed by 4176

Abstract

The solid-gas phase photo-catalytic activities of rutile TiO₂ and TiO_n (1 < n < 2) sub-oxide phases have been evaluated. Varying concentrations of Ti³⁺ defects were introduced into the rutile polymorph of titanium dioxide through carbo-thermal reduction at temperatures ranging [...] Read more.

The solid-gas phase photo-catalytic activities of rutile TiO₂ and TiO_n (1 < n < 2) sub-oxide phases have been evaluated. Varying concentrations of Ti³⁺ defects were introduced into the rutile polymorph of titanium dioxide through carbo-thermal reduction at temperatures ranging from 350 °C to 1300 °C. The resulting sub-oxides formed were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, impedance spectroscopy and UV-visible diffuse reflectance spectroscopy. The presence of Ti³⁺ in rutile exposed to high reduction temperatures was confirmed by X-ray diffraction. In addition, a Ti³⁺-Ti⁴⁺ system was demonstrated to enhance the photo-catalytic properties of rutile for the degradation of the air pollutants NO₂ and CO₂ under UV irradiation of wavelengths (λ) 376–387 nm and 381–392 nm. The optimum reduction temperature for photo-catalytic activity was within the range 350–400 °C and attributed to improved charge-separation. The materials that were subject to carbo-thermal reduction at temperatures of 350 °C and 400 °C exhibited electrical conductivities over one hundred times higher compared to the non-reduced rutile. The results highlight that sub-oxide phases form an important alternative approach to doping with other elements to improve the photo-catalytic performance of TiO₂. Such materials are important for applications such as self-cleaning where particles can be incorporated into surface coatings. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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16 pages, 4286 KiB

Open AccessArticle

Hydrophobicity and Photocatalytic Activity of a Wood Surface Coated with a Fe³⁺-Doped SiO₂/TiO₂ Film

by Luning Xuan, Yunlin Fu, Zhigao Liu, Penglian Wei and Lihong Wu

Materials 2018, 11(12), 2594; https://doi.org/10.3390/ma11122594 - 19 Dec 2018

Cited by 15 | Viewed by 3988

Abstract

A Fe³⁺-doped SiO₂/TiO₂ composite film (Fe³⁺-doped STCF) was prepared on a wood surface via a sol–gel method to improve its photocatalytic activity and hydrophobicity. The structure of the composite film was analyzed by Fourier Transform infrared [...] Read more.

A Fe³⁺-doped SiO₂/TiO₂ composite film (Fe³⁺-doped STCF) was prepared on a wood surface via a sol–gel method to improve its photocatalytic activity and hydrophobicity. The structure of the composite film was analyzed by Fourier Transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity toward degradation of methyl orange and its hydrophobic nature were investigated. The results showed that the composite film was anatase TiO₂ crystal form, and the addition of Fe³⁺ ions and SiO₂ enhanced the diffraction peaks for the anatase crystal form. The photocatalytic activity of the wood coated with the composite film was enhanced. The highest degradation percentage was at 1 wt % Fe³⁺ (40.37%), and the degradation ability of the wood towards methyl orange solution was further improved under acidic conditions. In addition, the composite film was hydrophobic, and the hydrophobic property was enhanced as the immersion time in the sol increased. The wood surface coated with Fe³⁺-doped STCF exhibited strong hydrophobicity and photocatalytic activity, which could effectively prevent moisture from adhering to the surface and degrade organic pollutants; thus, the modified wood surface had good self-cleaning function. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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11 pages, 7023 KiB

Open AccessArticle

Preparation of Assembled Carbon Soot Films and Hydrophobic Properties

by Lei Zhao, Kang Zhao, Wei-Guo Yan and Zhifeng Liu

Materials 2018, 11(11), 2318; https://doi.org/10.3390/ma11112318 - 19 Nov 2018

Cited by 10 | Viewed by 4378

Abstract

In this paper, a simple, inexpensive, and rapid method for the fabrication of controlled layer candle soot film has been reported by interface self-assembly and transferred method. The mechanism of candle soot self-assembly is explained and their morphology, elemental composition, optical, and wetting [...] Read more.

In this paper, a simple, inexpensive, and rapid method for the fabrication of controlled layer candle soot film has been reported by interface self-assembly and transferred method. The mechanism of candle soot self-assembly is explained and their morphology, elemental composition, optical, and wetting properties are characterized. The uniformity and thickness of prepared films especially depend on the concentration of candle soot mixed solution (alcohol and deionized water). The results show that the optimal concentration of candle soot solution is approximately ~0.2% wt/mL. In addition, the absorption spectra of the controlled-layer candle soot films are determined by the number of layers and the surface morphology. The hydrophobic properties of candle soot films are closely related to their layer number. When these films reach to the fourth layer, the water contact angle and roll-off angle are measured as 142° ± 2° and 6°, respectively. The controlled assembly CS films have the potential application in photo/electrocatalysis, solar cells, lithium-ion batteries, and water splitting. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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14 pages, 5768 KiB

Open AccessArticle

Preparation and Surface Properties Study of Novel Fluorine-Containing Methacrylate Polymers for Coating

by Ding Zhang, Ping Xing, Renming Pan, Xiangyang Lin, Min Sha and Biao Jiang

Materials 2018, 11(11), 2258; https://doi.org/10.3390/ma11112258 - 13 Nov 2018

Cited by 12 | Viewed by 3881

Abstract

A new structural fluorine-containing methacrylate monomer CH₂=C(CH₃)COOC–(CF₃)₂CF₂CF₂CF₃ (5) was synthesized derived from perfluoro-2-methyl-2-pentene (D₂). A homopolymer of 5 and copolymers of 5 and methacrylate with different [...] Read more.

A new structural fluorine-containing methacrylate monomer CH₂=C(CH₃)COOC–(CF₃)₂CF₂CF₂CF₃ (5) was synthesized derived from perfluoro-2-methyl-2-pentene (D₂). A homopolymer of 5 and copolymers of 5 and methacrylate with different alkyl chain length (chain length n = 1, 2, 4, 6, 8, 12, 18) were obtained. These new fluorinated acrylate polymers showed excellent water and oil repellency. The contact angle of the films of the homopolymer and part of the copolymers were similar with the corresponding polymers prepared from CH₂=CHC(O)OCH(C₃F₇)(CF(CF₃)₂), but greater than that of the C₆F₁₃(CF₃)CHOC(O)CH=CH₂ homopolymer. The structure-property relationship research indicated that the copolymers’ hydrophobicity decreased first and then increased with the increase of alkyl chain length. T_d of all the polymers were greater than 220 °C and T_g fluctuated within the range of −51~103.8 °C. Contact angle and T_g could be adjusted by controlling the feed ratio of monomer to meet the requirements of technical indicators in the practical applications. The outstanding liquid repellency and thermal stability make monomer 5 a promising alternative to perfluorinated long-chain fluorosurfactants. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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16 pages, 4555 KiB

Open AccessArticle

Transparent Photocatalytic Thin Films on Flexible Polymer Substrates

by Nives Vodišek, Andraž Šuligoj, Dorota Korte and Urška Lavrenčič Štangar

Materials 2018, 11(10), 1945; https://doi.org/10.3390/ma11101945 - 11 Oct 2018

Cited by 25 | Viewed by 4084

Abstract

Self-cleaning and/or photocatalytic films on polymer substrates have found numerous applications during the past decades. However, the common demand for high-temperature post synthesis treatment limits the application to temperature resistant substrates only. Herein, we prepared self-cleaning photocatalytic films on four thermosensitive polymeric substrates: [...] Read more.

Self-cleaning and/or photocatalytic films on polymer substrates have found numerous applications during the past decades. However, the common demand for high-temperature post synthesis treatment limits the application to temperature resistant substrates only. Herein, we prepared self-cleaning photocatalytic films on four thermosensitive polymeric substrates: polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), and acryl coated polyester (PES) fabric (D2) with poly(vinylidene fluoride) (PVDF) containing lacquer (D1). TiO₂ was prepared via a low-temperature sol-gel process using titanium(IV) isopropoxide and zirconium(IV) butoxide as precursors with various loading levels of Zr; 0, 5, 10, and 20 mol.%, and deposited on the substrates by using a SiO₂ binder in form of thin films (ca. 200 nm thick) via dip-coating. The films were characterized by SEM, hardness test, UV-Vis, photothermal beam deflection spectroscopy, and IR spectroscopy, while photocatalytic activity was measured by the fluorescence-based method of the terephthalic acid probe and wetting by contact angle measurements. Films containing 10 mol.% of Zr showed the best compromise regarding photocatalytic activity and mechanical stability while from substrates point of view PVC performed the best, followed by PMMA, D1, and D2. The beneficial role of SiO₂ binder was not only guaranteeing excellent mechanical stability, but also to prevent the D1 polymer from deterioration; the latter was found to be labile to long-term solar-light exposure due to degradation of the top PVDF layer. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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15 pages, 4514 KiB

Open AccessArticle

Preparation of Parabolic Superhydrophobic Material for Oil-Water Separation

by Xiaoying Qiao, Chunyan Yang, Qian Zhang, Shengke Yang, Yangyang Chen, Dan Zhang, Xiaoyu Yuan, Wenke Wang and Yaqian Zhao

Materials 2018, 11(10), 1914; https://doi.org/10.3390/ma11101914 - 9 Oct 2018

Cited by 12 | Viewed by 3024

Abstract

In order to prepare parabolic superhydrophobic materials, copper meshes were used as the substrate and ultrasonic etching and oxidative corrosion were carried out with FeCl₃ solution and H₂O₂ solution, respectively, and then the surface was modified with stearic acid [...] Read more.

In order to prepare parabolic superhydrophobic materials, copper meshes were used as the substrate and ultrasonic etching and oxidative corrosion were carried out with FeCl₃ solution and H₂O₂ solution, respectively, and then the surface was modified with stearic acid (SA). The topological structure and surface wettability of the prepared mesh were characterized by fluorescence microscope, scanning electron microscopy and contact angle measurement. Finally, the as-prepared copper meshes were applied to oil-water separation. The results showed that the micro-nano-mastoid structure on the surface of the copper mesh was flaky bulges, forming a rough structure similar to a paraboloid. When the oxidative corrosion time of H₂O₂ was 1 min, it is more beneficial to increase the hydrophobicity of the surface of the copper mesh and increase the contact angle of water droplets on the surface of the membrane. Additionally, based on superhydrophobic materials of the parabolic copper mesh, the static contact angles of the water droplets, engine oil and carbon tetrachloride with the surface were approximately 153.6°, 5° and 0.1°, respectively and the sliding angle of the water droplets with the surface were approximately 4.9°. The parabolic membrane was applied to discuss the separation efficiency of different oils with deionized water and the separation efficiency was obtained as benzene > carbon tetrachloride > oil > machine oil. Therefore, based on the research, the parabolic superhydrophobic material has good efficiency of oil-water separation. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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12 pages, 2575 KiB

Open AccessArticle

Biomimetic Superhydrophobic Hollowed-Out Pyramid Surface Based on Self-Assembly

by Weipeng Luo, Bin Yu, Dingbang Xiao, Meng Zhang, Xuezhong Wu and Guoxi Li

Materials 2018, 11(5), 813; https://doi.org/10.3390/ma11050813 - 16 May 2018

Cited by 9 | Viewed by 3906

Abstract

In this paper, we present a periodic hollowed-out pyramid microstructure with excellent superhydrophobicity. In our approach, T-topping pillars and capillary-induced self-assembly methods were combined with the photolithography process to fabricate a hollowed-out pyramid structure. First, a wideband ultraviolet source without a filter was [...] Read more.

In this paper, we present a periodic hollowed-out pyramid microstructure with excellent superhydrophobicity. In our approach, T-topping pillars and capillary-induced self-assembly methods were combined with the photolithography process to fabricate a hollowed-out pyramid structure. First, a wideband ultraviolet source without a filter was used to fabricate the T-topping pillars during the exposure process; then, the evaporation-induced assembly collapsed the pillars and formed the hollowed-out pyramid structure. Scanning electron microscopy images showed the microstructures of the prepared surface. The contact angle of the surface was 154°. The surface showed excellent high temperature and ultraviolet irradiation tolerance, and the contact angle of the surface barely changed when the temperature dropped. This excellent environmental durability of our superhydrophobic surface has potential applications for self-cleaning and friction drag reduction under water. Full article

(This article belongs to the Special Issue Self-Cleaning Surfaces)

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