Anti-icing performance of superhydrophobic surfaces

This article studies the anti-ice performance of several micro/nano-rough hydrophobic coatings with different surface chemistry and topography. The coatings were prepared by spin-coating or dip coating and used organosilane, fluoropolymer or silicone rubber as a top layer. Artificially created glaze ice, similar to the naturally accreted one, was deposited on the nanostructured surfaces by spraying supercooled water microdroplets (average size ∼80 μm) in a wind tunnel at subzero temperature (−10 °C). The ice adhesion strength was evaluated by spinning the samples in a centrifuge at constantly increasing speed until ice delamination occurred. The results show that the anti-icing properties of the tested materials deteriorate, as their surface asperities seem to be gradually broken during icing/de-icing cycles. Therefore, the durability of anti-icing properties appears to be an important point for further research. It is also shown that the anti-icing efficiency of the tested superhydrophobic surfaces is significantly lower in a humid atmosphere, as water condensation both on top and between surface asperities takes place, leading to high values of ice adhesion strength. This implies that superhydrophobic surfaces may not always be ice-phobic in the presence of humidity, which can limit their wide use as anti-icing materials.     

Surface texturing of polytetrafluoroethylene by hot embossing

In this study, hot embossing by reusable Ni mold with features in the form of rectangular diffraction gratings of 4 μm period was successfully employed for surface texturing of polytetrafluoroethylene (PTFE) film above the glass transition temperature of PTFE amorphous phase with the aim to enhance surface hydrophobicity. Imprint pressure was set to 0.5 MPa and it was at least tenfold lower than reported by other authors using cold stamping. Embossed gratings were clearly seen on the surface of all imprinted samples even after the annealing at 140 °C and aging for 1 month at room temperature. The best results were achieved when imprint temperature was 150 °C. Measurements of the water contact angle on imprinted PTFE surfaces have showed that increase of the average contact angle for the current test setup was 8°. Using imprint stamp with the more favorable features may lead to somewhat higher hydrophobicity.     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and short chain alcohol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and methanol and ethanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA). Using measured contact angle values the relationships between cos θ, adhesion tension and surface tension of the solutions were determined, and on their basis the critical surface tension of PTFE and PMMA wetting was calculated. The obtained average value of the critical surface tension of PTFE wetting is lying in the range of the PTFE surface tension values which can be found in the literature, while for PMMA it is even lower than the Lifshitz-van der Waals component of its surface tension. From the relationship between the adhesion and surface tension and Lucassen-Reynders equation it results that in the case of PTFE the adsorption at the PTFE-solution and solution-air interfaces is the same, which was confirmed by a linear relationship between the cos θ and 1/γ_LV and intercept on cos θ axis equal to −1. However, for PMMA the adsorption of the surface active agents at solution-air interface is higher than at PMMA-solution. Using the values of the contact angle the values of the adhesion work of solution to the PTFE and PMMA surface were also determined, which are constant for PTFE, but for PMMA decrease with alcohol concentration increase. Next, using the contact angle values in the Young equation, the PTFE(PMMA)-solution interface tension was also calculated. The obtained values of PTFE-solution interface tension were compared with those evaluated from the Szyszkowski, Connors and Fainerman and Miller equations, and good agreement between these values was observed for all series of TX-100 and alcohol mixtures at a low alcohol concentration.     

The effect of ultrasonic waves on the nucleation of pure water and degassed water

In order to clarify the mechanism of nucleation of ice induced by ultrasound, ultrasonic waves have been applied to supercooled pure water and degassed water, respectively. For each experiment, water sample is cooled at a constant cooling rate of 0.15 °C/min and the ultrasonic waves are applied from the water temperature of 0 °C until the water in a sample vessel nucleates. This nucleation temperature is measured. The use of ultrasound increased the nucleation temperature of both degassed water and pure water. However, the undercooling temperature for pure water to nucleate is less than that of degassed water. It is concluded that cavitation and fluctuations of density, energy and temperature induced by ultrasound are factors that affect the nucleation of water. Cavitation is a major factor for sonocrystallisation of ice.     

Effect of surface roughness and release layer on anti-adhesion performance of the imprint template

UV imprint lithography has been initiated as an enabling, cost-effective technique to achieve 100 nm resolution patterning in recent years. However, the adhesion between resist and imprint template is one of the critical problems for the industrial application of imprint lithography. In this paper, two kinds of measures, including increase of surface roughness of template and application of a fluorinated release agent as self-assembled monolayers (SAMs) to the template surface, were taken to overcome the adhesion between resist and template. The test results of contact angle showed that the appropriate increase of surface roughness could improve hydrophilicity of template surface greatly, and improved the hydrophobicity of template surface when it was combined with self-assembled monolayers. The XPS, DRIR spectra indicated that the fluorinated release layers were successfully prepared on the surface of template using the process in the paper. The surface free energy of the template was 16.6 mN/m, and less than that of PTFE (18 mN/m). The imprint experiment results also showed that the anti-adhesion performance of treated template was improved greatly during detaching procedure, and the demolding force decreased by 56.64% in comparison with that of untreated template.     

Pulsed electron beam deposition of highly oriented thin films of polytetrafluoroethylene

Thin films of polytetrafluoroethylene (PTFE) were deposited by pulsed electron deposition (PED) technique. The transmission electron microscopy (TEM) image of the RT fabricated (20 Å thick) film on carbon coated copper grid shows crystalline nature. Infrared spectra show one to one correspondence between PED ablated film and the PTFE bulk target. The asymmetrical and symmetrical -CF₂- stretching modes were observed at 1220 and 1156 cm⁻¹, respectively. The -CF₂- wagging and bending modes occur at 644 and 512 cm⁻¹, respectively. X-ray diffraction patterns of the film deposited at room temperature (RT) show oriented film along (1 0 0) plane of hexagonal structure and the crystalline nature is retained up to 300 °C on vacuum annealing. The room temperature fabricated film shows smooth and pin hole free surface whereas post-annealing brings discontinuity, roughness and pin holes.     

The relationship between the adhesion work, the wettability and composition of the surface layer in the systems polymer/aqueous solution of anionic surfactants and alcohol mixtures

Measurements of advancing contact angle (θ) were carried out on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA) for aqueous solution of sodium dodecyl sulfate (SDDS) mixtures with methanol, ethanol and propanol in the range of SDDS concentration from 10⁻⁵ to 10⁻² M, and for sodium hexadecyl sulfonate (SHS) with the same alcohols at the SHS concentration ranging from 10⁻⁵ to 8 × 10⁻⁴ M at 293 K. The concentration of methanol, ethanol and propanol used for measurements varied from 0 to 21.1, 11.97 and 6.67 M, respectively. On the basis of the contact angles the critical surface tension of PTFE and PMMA wetting was determined by using for this purpose the relationship between the adhesion and the surface tension and cos θ and surface tension both at constant alcohol and surfactant concentration, respectively. The obtained contact angles were also used in the Young Dupre’ equation for calculations of the adhesion work of aqueous solution of mixtures of anionic surfactants and short chain alcohols to PTFE and PMMA surface. The adhesion work calculated in this way was compared to that of the particular components of aqueous solution to these surfaces determined on the basis of the surface tension components and parameters of the surface tension of the surface active agents, water, PTFE and PMMA from van Oss et al. equation. The calculated adhesion work was discussed in the light of the concentration of surface active agents at polymer-water and water-air interface determined from Lucassen-Reynders, Gibbs and Guggenheim-Adam equations.     

Effect of annealing temperature for Si0.8Ge0.2 epitaxial thin films

This study investigates the effect of annealing temperature on the Si_0.8Ge_0.2 epitaxial layers. The Si_0.8Ge_0.2 epitaxial layers were deposited by using ultrahigh vacuum chemical vapor deposition (UHVCVD) with different annealing temperatures (400-1000 °C). Various measurement technologies, including high-resolution X-ray diffraction (HRXRD), atomic force microscopy (AFM) and interfacial adhesion tester, were used to characterize the materials properties of the SiGe epilayers. The experimental results showed that the SiGe epilayers gradually reduced lattice-mismatch to the underlying substrate as annealing temperature increased (from 400 to 800 °C), which resulted from a high temperature enhancing interdiffusion between the epilayers and the underlying substrate. In addition, the average grain size of the SiGe films increased from 53.3 to 58 nm with increasing annealing temperature. The surface roughness in thin film annealed at 800 °C was 0.46 nm. Moreover, the interfacial adhesion strength increased from 476 ± 9 to 578 ± 12 kg/cm² with increasing the annealing temperature.     

Studies on surface graft polymerization of acrylic acid onto PTFE film by remote argon plasma initiation

The graft polymerization of acrylic acid (AAc) was carried out onto poly(tetrafluoroethylene) (PTFE) films that had been pretreated with remote argon plasma and subsequently exposed to oxygen to create peroxides. Peroxides are known to be the species responsible for initiating the graft polymerization when PTFE reacts with AAc. We chose different parameters of remote plasma treatment to get the optimum condition for introducing maximum peroxides (2.87 × 10⁻¹¹ mol/cm²) on the surface. The influence of grafted reaction conditions on the grafting degree was investigated. The maximum grafting degree was 25.2 μg/cm². The surface microstructures and compositions of the AAc grafted PTFE film were characterized with the water contact angle meter, Fourier-transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Contact angle measurements revealed that the water contact angle decreased from 108° to 41° and the surface free energy increased from 22.1 × 10⁻⁵ to 62.1 × 10⁻⁵ N cm⁻¹ by the grafting of the AAc chains. The hydrophilicity of the PTFE film surface was greatly enhanced. The time-dependent activity of the grafted surface was better than that of the plasma treated film.     

Surface modification of porous poly(tetrafluoraethylene) film by a simple chemical oxidation treatment

A simple, inexpensive and environmental chemical treatment process, i.e., treating porous poly(tetrafluoroethylene) (PTFE) films by a mixture of potassium permanganate solution and nitric acid, was proposed to improve the hydrophilicity of PTFE. To evaluate the effectiveness of this strong oxidation treatment, contact angle measurement was performed. The effects of treatment time and temperature on the contact angle of PTFE were studied as well. The results showed that the chemical modification decreased contact angle of as-received PTFE film from 133 ± 3° to 30 ± 4° treated at 100 °C for 3 h, effectively converting the hydrophobic PTFE to a hydrophilic PTFE matrix. The changes in chemical structure, surface compositions and crystal structure of PTFE were examined by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), respectively. It was found that the F/C atomic ratio decreased from untreated 1.65-0.10 treated by the mixture at 100 °C for 3 h. Hydrophilic groups such as carbonyl (CO) and hydroxyl (OH) were introduced on the surface of PTFE after treatment. Furthermore, hydrophilic compounds K_0.27MnO₂·0.54H₂O was absorbed on the surface of porous PTFE film. Both the introduction of hydrophilic groups and absorption of hydrophilic compounds contribute to the significantly decreased contact angle of PTFE.     

Investigation of the effect of power ultrasound on the nucleation of water during freezing of agar gel samples in tubing vials

Nucleation, as an important stage of freezing process, can be induced by the irradiation of power ultrasound. In this study, the effect of irradiation temperature (−2 °C, −3 °C, −4 °C and −5 °C), irradiation duration (0 s, 1 s, 3 s, 5 s, 10 s or 15 s) and ultrasound intensity (0.07 W cm⁻², 0.14 W cm⁻², 0.25 W cm⁻², 0.35 W cm⁻² and 0.42 W cm⁻²) on the dynamic nucleation of ice in agar gel samples was studied. The samples were frozen in an ethylene glycol-water mixture (−20 °C) in an ultrasonic bath system after putting them into tubing vials. Results indicated that ultrasound irradiation is able to initiate nucleation at different supercooled temperatures (from −5 °C to −2 °C) in agar gel if optimum intensity and duration of ultrasound were chosen. Evaluation of the effect of 0.25 W cm⁻² ultrasound intensity and different durations of ultrasound application on agar gels showed that 1 s was not long enough to induce nucleation, 3 s induced the nucleation repeatedly but longer irradiation durations resulted in the generation of heat and therefore nucleation was postponed. Investigation of the effect of ultrasound intensity revealed that higher intensities of ultrasound were effective when a shorter period of irradiation was used, while lower intensities only resulted in nucleation when a longer irradiation time was applied. In addition to this, higher intensities were not effective at longer irradiation times due to the heat generated in the samples by the heating effect of ultrasound. In conclusion, the use of ultrasound as a means to control the crystallization process offers promising application in freezing of solid foods, however, optimum conditions should be selected.     

Structural, morphological, wettability and thermal resistance properties of hydro-oleophobic thin films prepared by a wet chemical process

The structural properties of fluorine containing polymer compounds make them highly attractive materials for hydro-oleophobic applications. However, most of these exhibit low surface energy and poor adhesion on the substrates. In the present investigation, crack free, smooth and uniform thin films of poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole]-co-tetrafluoroethylene (TFD-co-TFE) with good adhesion have been deposited by wet chemical spin-coating technique on polished AISI 440C steel substrates. The as-deposited films (xerogel films) have been subjected to annealing for 1 h at different temperatures ranging from 100 to 500 °C in an argon atmosphere. The size growth of the nano-hemispheres increased from 8 nm for xerogel film to 28 nm for film annealed at 400 °C. It was found that as the annealing temperature increased from 100 to 400 °C, nano-hemisphere-like structures were formed, which in turn have shown increase in the water contact angle from 122° to 147° and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80 °C as well as exposed to steam for 8 days for 8 h/day indicating thermal stability of the film.     

Organic modification of TEOS based silica aerogels using hexadecyltrimethoxysilane as a hydrophobic reagent

The experimental results on the synthesis and characterization of tetraethoxysilane (TEOS) based hydrophobic silica aerogels using hexadecyltrimethoxysilane (HDTMS) as a hydrophobic reagent by two step sol-gel process, are described. The molar ratio of tetraethoxysilane (TEOS), methanol (MeOH), acidic water (0.001 M, oxalic acid) and basic water (10 M, NH₄OH) was kept constant at 1:55:3.25:1.25 and the molar ratio of HDTMS/TEOS (M) was varied from 0 to 28.5 × 10⁻². The organic modification was confirmed by infrared spectroscopic studies, and the hydrophobicity of the aerogels was tested by the contact angle measurements. The maximum contact angle of 152° was obtained for M = 22.8 × 10⁻². The aerogels retained the hydrophobicity up to a temperature of 240 °C and above this temperature the aerogels became hydrophilic. The aerogels were characterized by the thermal conductivity, density, contact angle measurements, optical transmission and scanning electron micrographs.     

Aberration athermal design for infrared search and trace optical system

To satisfy environment requirement of infrared search and trace optical system, an infrared diffractive/refractive hybrid optical system in 3.7–4.8 μm with 11.42° of field of view for passive athermalization is presented. The system is consisted of three lenses, including two aspheric surfaces and a diffraction surface, which has only two materials Ge and Si. The optical system has compact structure, small volume and light weight. The image quality of the system approaches the diffraction limit in the temperature range −80 °C to 160 °C. It is compatible with staring focal plane array which has a format of 320 × 240 and the pixel pitch of 30 μm. The system need not move the compensated lens repeatedly to obtain the best images from −80 °C to 160 °C and enhances the performance of target tracking and recognition.     

Wet oxidation behaviors of Hi-Nicalon fibers

Wet oxidation behaviors of Hi-Nicalon fibers were investigated in environment of PH₂O:O₂:Ar=14:8:78 kPa with a slow gas flow rate of 3.5 cm s⁻¹ above 1300 °C for 1 h. Experimental results indicated that oxidized Hi-Nicalon fibers were covered by silica. The weight gains and surface micromorphologies were strongly affected by temperature. Below 1500 °C, the surface of the oxidized fibers were rough-hewn and cracked, and there were no changes detected in fiber diameter. After oxidation at 1600 °C, the silica locally spalled and the fiber swelled in diameter. The Young-Laplace equation was applied to interpret surface micromorphologies change during wet oxidation of the specimens. The cracks in silica produced by oxidation and the microcrystal growth of the fibers at high temperature were considered for the strength degradation of the fibers.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

Temperature effect on tyre-road noise

Tyre-road noise emission decreases when the outdoor temperature increases, with a variation that can exceed −0.1 dB(A)/°C. This effect depends on tyre-road combination, but semi-generic corrections can improve the accuracy of tyre-road noise measurements. In this paper, the variation of pass-by noise level of a passenger car at 90 km/h with temperature is investigated, on seven types of road surfaces, under different temperature conditions. A good correlation between air, road surface and tyre temperature is outlined. A linear relationship between noise level and air temperature variations is observed for bituminous pavements, of about −0.1 dB(A)/°C, but reduced to −0.06 dB(A)/°C for pavements having porosity. No temperature effect is observed on cement concrete pavements. A spectral analysis shows that the temperature effect is highest in low and high frequency range, what can be explained by generating mechanisms rather than propagation.     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and propanol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and propanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethyhmethacrylate (PMMA). Using obtained results the changes of cosθ and adhesional tension against surface tension of all series of aqueous solutions of TX-100 and propanol mixtures (γ_LV) for PTFE and PMMA surfaces were shown. On the basis of these changes it was deduced that adsorption of TX-100 and propanol mixtures at PTFE-solution and solution-air interfaces is the same but the adsorption of TX-100 and propanol mixtures at solution-air interface is considerably higher than at PMMA-solution one. In the case of PTFE this conclusion was confirmed by relationship between cosθ and the reciprocal of the surface tension of solution. Extrapolation of the relationships between cosθ and/or adhesional tension and the surface tension of solutions to the points corresponding to the cosθ = 1 and adhsional tension equal to the surface tension of solution, the critical surface tension of PTFE and PMMA wetting was determined. The average values of critical surface tension of wetting determined from these relationships for PTFE are lying in the range of its surface tension values determined from contact angles of different kinds of liquids, which can be find in the literature, but for PMMA are considerably lower than the surface tension. The double value of the critical surface tension of PTFE wetting is equal to adhesion work of the solution to its surface and for PMMA there is not any correlation between these magnitudes.Using the measured values of the contact angles and Young equation the PTFE(PMMA)-aqueous solution interfacial tension was determined. The interfacial tension values of PTFE-aqueous solution were also calculated from the Fainerman and Miller equation in which the correcting parameter of nonideality of the surface monolayer was introduced and compared to those obtained from Young equation. From this comparison it results that the changes of PTFE-solution interface tension as a function of propanol concentration can be described by the Fainerman and Miller equation.     

Electrical properties vs. microstructure of nanocrystallized V2O5-P2O5 glasses — An extended temperature range study

An electronically conducting nanomaterial was synthesized by nanocrystallization of a 90V₂O₅·10P₂O₅ glass and its electrical properties were studied in an extended temperature range from − 170 to + 400 °C. The conductivity of the prepared nanomaterial reaches 2 ? 10^− 1 S cm^− 1 at 400 °C and 2 ? 10^− 3 S cm^− 1 at room temperature. It is higher than that of the original glass by a factor of 25 at room temperature and more than 100 below − 80 °C. A key role in the conductivity enhancement was ascribed to the material's microstructure, and in particular to the presence of the large number of small (ca. 20 nm) grains of crystalline V₂O₅. The observed conductivity dependencies are discussed in terms of the Mott's theory of the electronic hopping transport in disordered systems. Since V₂O₅ is known for its ability to intercalate lithium, the presented results might be helpful in the development of cathode materials for Li-ion batteries.     

Preparation of activated carbons from cherry stones by activation with potassium hydroxide

Using cherry stones, the preparation of activated carbon has been undertaken in the present study by chemical activation with potassium hydroxide. A series of KOH-activated products was prepared by varying the carbonisation temperature in the 400-900 °C range. Such products were characterised texturally by gas adsorption (N₂, −196 °C), mercury porosimetry, and helium and mercury density measurements. FT-IR spectroscopy was also applied. The carbons prepared as a rule are microporous and macroporous solids. The degree of development of surface area and porosity increases with increasing carbonisation temperature. For the carbon heated at 900 °C the specific surface area (BET) is 1624 m² g⁻¹, the micropore volume is 0.67 cm³ g⁻¹, the mesopore volume is 0.28 cm³ g⁻¹, and the macropore volume is 1.84 cm³ g⁻¹.