Hexadecane Contact Angles Research Articles

Superhydrophobic terpolymer nanofibers containing perfluoroethyl alkyl methacrylate by electrospinning

A new statistical terpolymer containing perfluoroethyl alkyl methacrylate (Zonyl-TM), methyl methacrylate and butyl acrylate, poly(Zonyl-TM–ran-MMA–ran-BA) was synthesized in supercritical carbon dioxide at 200bar and 80°C using AIBN as an initiator by heterogeneous free radical copolymerization. Nanofibers of this terpolymer were produced by electrospinning from its DMF solution. The structural and thermal properties of terpolymers and electrospun poly(Zonyl-TM–MMA–BA) nanofibers were analyzed using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and differential scanning calorimetry. Nanofiber morphology was investigated by scanning electron microscopy. Electrospun nanofiber layer was found to be superhydrophobic with a water contact angle of 172±1° and highly oleophobic with hexadecane, glycerol and ethylene glycol contact angles of 70±1°, 167±1° and 163±1° respectively. The change of the contact angle results on the electrospun fiber layer and flat terpolymer surfaces by varying feed monomer composition were compared and discussed in the text.

Thermal imprint techniques for preparation of superhydrophobic polymer coatings

The self-cleaning property of superhydrophobic surfaces has raised considerable interest among scientists. Many preparation methods require complex and expensive fabrication techniques that cannot be used to directly modify substrates. We designed an imprint process using a micro/nano-structured mold to emboss several polymer coatings in order to introduce superhydrophobicity and still maintain their transparent/translucent properties. Polydimethylsiloxane (PDMS) elastic molds with various micro and nano features were fabricated using different grades of sandpaper as master molds, increasing the water contact angles (WCAs) on the PDMS surfaces from 120° (plain) to more than 170°. The PDMS molds were then applied to replicate some commercial polymer coatings at an elevated temperature of about 140°C to transfer the mold pattern to the coatings. The hydrophobic property of those polymer coatings was then enhanced to a WCA of greater than 150°. After fluoroalkylsilane deposition on the surfaces, the surfaces displayed an improved lipophobic property (hexadecane contact angle (HCA) went from 90° to 110°). The arbitrarily-rough surfaces displayed ‘sticky superhydrophobicity’ due to the water drops being adsorbed and not rolling off from the surfaces. Atomic force microscopy (AFM) was employed to measure the morphologies of imprinted coatings and also estimate the roughness, occupying polymer ratios, and critical CA to evaluate the wetting of sample surfaces. From the evaluation of surface properties, all the samples using sandpaper as templates exhibited stable Cassie or metastable wetting. The rougher surfaces provided some large protrusions to contact with and be immersed into water droplets, leading to high water penetration depth and thus stickiness. Additionally, the rougher the mold was, the greater the WCA was, but the transparency of the coating was reduced. However, the imprinted polymer surfaces could still maintain sufficient transparency for use in applications requiring preservation of the appearance of the underlying surface.

Can We Predict the Spreading of a Two-Liquid System from the Spreading of the Corresponding Liquid–Air Systems?

We present new data obtained from the spreading of a series of oil droplets, on top of a hydrophobic grafted silicon substrate, in air and immersed in water. We follow the contact angle and radius dynamics of hexane, dodecane, hexadecane, dibutyl phthalate, and squalane from the first milliseconds to approximately 1 s. Analysis of the images allows us to make several hundred contact angle and droplet radius measurements with great accuracy. The G-Dyna (Seveno et al. Langmuir 2010, 25, 13034) software is then used to fit the data with one of the wetting theories, the molecular-kinetic theory (MKT) (Blake et al. J. Colloid Interface Sci.1969, 30, 421), which takes into account the dissipation at the three-phase zone at the contact line. This theory allows us to extract the coefficient of friction of the contact line, which expresses the relationship between the driving force, that is, the unbalanced Young force, and the contact-line velocity V. It is first shown that the MKT is appropriate to describe the experimental data and then that the contact-line friction is a linear function of the viscosity as theoretically predicted. This is checked for oil-air and oil-water systems. A linear relation between the contact-line friction measured in oil-water systems and the contact-line frictions of the parent single liquid system seems plausible. To the best of our knowledge, this is the first trial to establish a link between the dynamics of wetting in liquid-liquid and in liquid-air systems.

Wetting Behavior of Oleophobic Polymer Coatings Synthesized from Fluorosurfactant-Macromers

Architecturally similar monomers were copolymerized with a water-oil discriminate fluorosurfactant to create hydrophilic-oleophobic coatings. Acrylic acid, hydroxyethyl methacrylate, and methyl methacrylate were used as comonomers with the fluorosurfactant macromer. The homopolymers of the selected comonomers are water-soluble, water-swellable, and water-insoluble, respectively, thus coupling the surfactant monomer in varying concentration within polymers of varying hydrophilicity. Wetting behavior of water and hexadecane were examined as a function of copolymer composition, thus revealing critical structure-property relationships for the surfactant-based system. Acrylic acid copolymers and hydroxyethyl methacrylate copolymers both exhibited a hexadecane contact angle which exceeded the water contact angle. This condition predicted an ability to "self-clean" oil-based foulants. The most oleophobic of the self-cleaning copolymers had an advancing hexadecane contact angle of 73° and an advancing water contact angle of 40°. It was determined that the advancing and receding water and hexadecane contact angle response varies montonically for each copolymer type as the surface concentration of the surfactant is varied. Comparing between copolymer types revealed large differences in wetting response. Methyl methacrylate copolymers with 2.8 mol % surfactant had advancing water contact angle 82° and advancing hexadecane contact angle 26°, which is neither oleophobic nor self-cleaning. In contrast, acrylic acid copolymers with 3.1 mol % surfactant had advancing water contact angle of 44° and advancing hexadecane contact angle of 52°, creating a self-cleaning coating. Thus, the nature of the comonomer exerts a greater influence than the surfactant content on the wetting behavior and self-cleaning ability of the final coating.

Design, microfabrication and evaluation of robust high-performance superlyophobic surfaces

High-performance superlyophobic surfaces (SLSs) showing extremely low wettability for various liquids including water and oil are microfabricated following universal design criteria and formulated rules, and their wetting and hydrodynamic performances are systematically evaluated. Four design criteria are proposed to achieve reliable air-entrapped Cassie–Baxter (C–B) state for various liquids, especially low-surface-tension oils by considering the pressure balance and curvature requirement, as well as the pinning and suspending condition. By formulating the geometric design rules, a T-shaped configuration with a slight undercut is preferred as robust 3D structure for microfabricated high-performance of SLS. The static and dynamic contact angles (CAs) of water and hexadecane on SLS can be well tuned by varying the solid fraction. On the high-robustness and low-adhesion SLS, CAs up to 167° for hexadecane and 170° for water, and low contact angle hysteresis (CAH) ∼ 8° have been achieved. However, CAs on SLS cannot be well explained by three existing wetting models, which requires more efforts to exactly depict the droplet behavior on SLS.

Fabrication, Surface Properties, and Origin of Superoleophobicity for a Model Textured Surface

Inspired by the superhydrophobic effect displayed in nature, we set out to mimic the interplay between the chemistry and physics in the lotus leaf to see if the same design principle can be applied to control wetting and adhesion between toners and inks on various printing surfaces. Since toners and inks are organic materials, superoleophobicity has become our design target. In this work, we report the design and fabrication of a model superoleophobic surface on silicon wafer. The model surface was created by photolithography, consisting of texture made of arrays of ∼3 μm diameter pillars, ∼7 μm in height with a center-to-center spacing of 6 μm. The surface was then made oleophobic with a fluorosilane coating, FOTS, synthesized by the molecular vapor deposition technique with tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane. Contact angle measurement shows that the surface exhibits super repellency toward water and oil (hexadecane) with a water and hexadecane contact angles at 156° and 158°, respectively. Since the sliding angles for both liquids are also very small (∼10°), we conclude that the model surface is both superhydrophobic and superoleophobic. By comparing with the contact angle data of the bare silicon surfaces (both smooth and textured), we also conclude that the superoleophobicity is a result of both surface texturing and fluorination. Results from investigations of the effects of surface modification and pillar geometry indicate that both surface oleophobicity and pillar geometry are contributors to the superoleophobicity. More specifically, we found that superoleophobicity can only be attained on our model textured surface when the flat surface coating has a relatively high oleophobicity (i.e., with a hexadecane contact angle of >73°). SEM examination of the pillars with higher magnification reveals that the side wall in each pillar is not smooth; rather it consists of a ∼300 nm wavy structure (due to the Bosch etching process) from top to bottom. Comparable textured surfaces with (a) smooth straight side wall pillars and (b) straight side wall pillars with a 500 nm re-entrant structure made of SiO(2) were fabricated and the surfaces were made oleophobic with FOTS analogously. Contact angle data indicate that only the textured surfaces with the re-entrant pillar structure are both superoleophobic and superhydrophobic. The result suggests that the wavy structure at the top of each pillar is the main geometrical contributor to the superoleophobic property observed in the model surface.

One-step vapour-phase formation of patternable, electrically conductive, superamphiphobic coatings on fibrous materials

Patternable, electrically conductive coatings having a superhydrophobic and superoleophobic surface have been prepared by one-step vapour-phase polymerisation of polypyrrole in the presence of a fluorinated alkyl silane directly on fibrous substrates. The coated fabrics showed a surface resistance of 0.5–0.8 kΩ □−1 with water and hexadecane contact angles of 165° and 154°, respectively.

Superamphiphobic Web of PTFEMA Fibers via Simple Electrospinning Without Functionalization

AbstractThis paper reports on a web of superamphiphobic fluoro‐compound fibers that forms as a result of a typical electrospinning method without any additional treatment. An electrospun web of poly(2,2,2‐trifluoroethyl methacrylate) fibers exhibits superamphiphobicity when the water and hexadecane contact angles both exceed 150°. The morphology of a web is modulated by changing the polymer solution concentration from 24 to 30 wt.‐% with other fixed processing conditions. The fiber diameter length depends mainly on the polymer concentration. A web formed from a 26 wt.‐% solution has the smallest and most uniform fiber diameter; it also has the highest robustness parameter on wetting, thus the highest water and hexadecane contact angles. This result offers the possibility of simple industrial production of an amphiphobic surface. magnified image

Preparation and characterization of super-hydrophobic and oleophobic surface

A novel method for preparing and characterizing super-hydrophobic and oleophobic surface is presented. Aluminum (Al) substrate was roughened by sandblasting and electrolytic etching to obtain micro- and nano-sized complex morphologies. Then, its substrate was covered by a chemically adsorbed monolayer (CAM) containing a fluorocarbon group. The surface of Al substrate roughened and covered with CAM was observed by scanning electron microscope and atomic force microscope. The roughnesses of the surface were ca. 100 μm and ca. 30–60 nm, respectively. The surface of the wettability was characterized by contact angle measurements and its surface indicated super-hydrophobicity and oleophobicity: the water contact angle (WCA) and oil contact angle (OCA) of hexadecane was 158.9° and 139.6°, respectively. The wettability was also characterized by solid surface energy. The solid surface energy of each solvent was obtained from the equation by Neumann et al. These values were extremely low, ranging from 0.31 to 1.29 mN/m. The total solid surface energy was obtained from the equation by Kaelble et al. The value was 0.3 mN/m. Their values indicated that the hydrophobicity and oleophobicity of our sample reached the highest level possible. In addition, our research demonstrates that it is easy to compare many different surfaces with super-hydrophobicity and oleophobicity using the solid surface energy.

Superoleophobic and Superhydrophobic Surfaces from Microtextured ZnO-Based Surfaces on Si Substrate

Theoretical calculations suggest that creating superoleophobic surfaces would require a surface energy lower than that of any known materials. In the present work, we demonstrate micronanostructured ZnO-based surfaces displaying apparent contact angles (CA) greater than 150, even with hexadecane (surface tension l = 27.5 mN/m). The specific ZnO microtextures were fabricated by a chemical solution method, and fluoroalkylsilane (FAS) was then used to tune the surface wettability. The combination of ZnO microtextures and FAS modification resulted in a superoleophobicity with CA for hexadecane was 154.6 (161.9 for diethylene glycol (l = 45.2 mN/m). This apparent superoleophobic behavior was induced on intrinsically oleophilic materials mainly by topography (i.e. the specific ZnO microtextures), which form a composite surface of air and solid with oil drop sitting partially on air. Such special wetting state is a metastable Cassie state. The results are expected to promote the study on self-cleaning applications, especially in the condition with oil contaminations.

Aerogels from nanofibrillated cellulose with tunable oleophobicity

The formation of structured porous aerogels of nanofibrillated cellulose (NFC) by freeze-drying has been demonstrated. The aerogels have a high porosity, as shown by FE-SEM and nitrogen adsorption/desorption measurements, and a very low density (<0.03 g cm−3). The density and surface texture of the aerogels can be tuned by selecting the concentration of the NFC dispersions before freeze-drying. Chemical vapor deposition (CVD) of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFOTS) was used to uniformly coat the aerogel to tune their wetting properties towards non-polar liquids. An XPS analysis of the chemical composition of the PFOTS-modified aerogels demonstrated the reproducibility of the PFOTS-coating and the high atomic fluorine concentration (ca. 51%) in the surfaces. The modified aerogels formed a robust composite interface with high apparent contact angles (θ* ≫ 90°) for castor oil (γlv = 35.8 mN m−1) and hexadecane (γlv = 27.5 mN m−1).

Simple nanofabrication of a superhydrophobic and transparent biomimetic surface

This paper describes a simple fabrication method for creating superhydrophobic and transparent glass surfaces that mimic natural surfaces such as lotus leaves, moth eyes or cicada wings. Nanostructured glass surfaces were created by a combination of colloidal lithography and plasma etching. A colloidal mask was formed simply by the spin coating of the polystyrene beads and with modification of the interparticle distance between the beads. The etching of the glasses was conducted by CF4 plasma. Tower-shaped nanostructures at an aspect ratio of 1:4 were treated using fluoroalkylsilane self-assembled monolayers (SAMs) to obtain the hydrophobic surfaces. The treated glass surfaces showed superhydrophobicity with a water contact angle of around 150° and a hexadecane contact angle of around 110°. Furthermore, the nanostructured glass was transparent to visible light.

Micropatterning of perfluoroalkyl self-assembled monolayers for arraying proteins and cells on chips

Organosilane self-assembled monolayers (SAMs) with perfluoroalkyl groups ( R f) on glass surfaces were used for arraying proteins and cells on chips. Quartz crystal microbalance measurements confirmed the inhibition of protein adsorption on R f-SAM-modified surfaces and showed efficient adsorption on hydroxyl-, carboxyl-, and amino group-modified surfaces. The characteristics of R f-modified surfaces were evaluated using solvent contact angle measurement and Fourier transform infrared (FTIR) spectroscopy. The R f surface was highly water- and oil-resistant, as inferred from the contact angles of water, oleic acid, and hexadecane. Specific peaks of IR spectra were detected in the region from 1160 to 1360 cm −1. Etching with dry plasma completely exfoliated the R f-SAM, exposing the underlying intact glass surface. Modification conditions were optimized using contact angle and FTIR measurements. After dry plasma processing, the contact angles of all solvents became undetectable, and the IR peaks disappeared. Micrometer scale protein and cell patterns can be fabricated using the proposed method. Protein adsorption on micropatterned R f-SAM-modified chips was evaluated using fluorescence analysis; protein adsorption was easily controlled by patterning R f-SAM. PC12 and HeLa cells grew well on micropatterned R f-SAM-modified chips. Micropatterning of R f-SAM by dry plasma treatment with photolithography is useful for the spatial arrangement of proteins and cells.

Hydrophobic and oleophobic surface modification using fluorinated bis-urea and bis-amide gelators

A series of fluorinated bis-urea and bis-amide derivatives were synthesized from fluorinated amines and explored as surface modifiers for nonwoven substrates. A majority of these derivatives showed excellent gelation properties both in organic solvents as well as in supercritical carbon dioxide (scCO 2) at concentrations ranging from 0.3 to 3 wt%. Gelation in the presence of a nonwoven substrate led to a gel-impregnated surface, which upon drying produced a composite with porous microstructure morphology on the surface. The composites thus produced showed high water and hexadecane contact angles, indicative of excellent hydrophobic and lyophobic properties. The superior hydrophobic and oleophobic behaviors observed in these composites are attributed to a combination of increased surface roughness and the presence of fluoroalkyl functionalities in the gelator backbone.

Superoleophobic Cotton Textiles

Common cotton textiles are hydrophilic and oleophilic in nature. Superhydrophobic cotton textiles have the potential to be used as self-cleaning fabrics, but they typically are not super oil-repellent. Poor oil repellency may easily compromise the self-cleaning property of these fabrics. Here, we report on the preparation of superoleophobic cotton textiles based on a multilength-scale structure, as demonstrated by a high hexadecane contact angle (153 degrees for 5 microL droplets) and low roll-off angle (9 degrees for 20 microL droplets). The multilength-scale roughness was based on the woven structure, with additional two layers of silica particles (microparticles and nanoparticles, respectively) covalently bonded to the fiber. Superoleophobicity was successfully obtained by incorporating perfluoroalkyl groups onto the surface of the modified cotton. It proved to be essential to add the nanoparticle layer in achieving superoleophobicity, especially in terms of low roll-off angles for hexadecane.

Amphiphile grafted membranes for the separation of oil-in-water dispersions

Perfluorinated end-capped polyethylene glycol surfactants were covalently attached to fritted glass membranes as a means to improve the separation of oil-in-water emulsions. Hexadecane was used as representative oil for the oil-in-water emulsions; membrane pore size was varied between 10 and 174 μm. Membranes were characterized with respect to contact angle, permeability of bulk fluids, and separation efficiency. Performance was compared to similar metrics applied to unmodified membranes. Modified membranes demonstrated static hexadecane contact angles which were higher than static water contact angles converse to their unmodified counterparts. The relative hydrophilicity and corresponding oleophobicity of the modified membranes resulted in greater water permeability as compared to hexadecane permeability. The presence of the perfluorinated constituent of the amphiphile retarded the flow of hexadecane. For modified membranes, suspended hexadecane coalesced at the membrane surface, was undercut by water, and floated to the surface such that only trace amounts of oil were present in the permeate. Therefore, modified membranes resisted fouling from oil due to the self-cleaning properties of the attached amphiphile.

Well‐defined polycaprolactone precursors for low surface‐energy polyurethane films

AbstractFor the purpose of developing model coating systems, it is important to use well‐defined coating precursors. In this work, polyester oligomers were synthesized by controlled ring‐opening polymerization of ε‐caprolactone and 4‐tert‐butyl‐ε‐caprolactone via an activated monomer mechanism. These well‐defined oligomers, including 3‐armed hydroxyl‐functionalized polyesters and perfluoroalkyl‐end‐capped linear polyesters, have been obtained with controlled functionality and low‐molecular weight polydispersity and without the formation of cyclic structures, as demonstrated by MALDI‐ToF MS analyses. The polymer architecture and functionality can be tuned by using different initiating alcohols. These oligomers have been used as precursors to prepare model low surface‐energy polyurethane coatings. Upon the addition of about 1 wt % of fluorine in the polyurethane films, the advancing contact angles for water and hexadecane have been increased to 105° and 78°, respectively; the surface enrichment of fluorinated species has been confirmed by X‐ray photoelectron spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 218–227, 2008

Characterization of Self-assembled Monolayers from Lithium Dialkyldithiocarbamate Salts

We report the formation of self-assembled monolayers (SAMs) onto gold substrates by exposure to lithium dialkyldithiocarbamate salts [(Li+(R2DTC-), where R = n-propyl, n-butyl, n-octyl, n-decyl, n-dodecyl, or n-octadecyl] in ethanol or methylene chloride. The crystallinity and composition of the monolayers were assessed by polarized modulation infrared reflection absorption spectroscopy (PM-IRRAS), wettability was characterized by contact angles of water and hexadecane, thickness was measured by spectroscopic ellipsometry, and barrier properties determined by electrochemical impedance spectroscopy. While the shorter R2DTC-s formed monolayers with liquid-like packing, monolayers prepared from the longest R2DTC- (where R = n-octadecyl) exhibit similar thickness, crystallinity, wettability, and capacitance as monolayers prepared from n-octadecanethiol. The hydrocarbon chains within the monolayers prepared from (C18)2DTC- are less canted on average than those prepared from n-octadecanethiol. Nonetheless, the (C18)2DTC- SAM exhibits an order of magnitude lower resistance against the penetration of redox probes, which is attributed to a higher density of pinhole defect sites.

Effect of Ionic Strength on Oil Removal from Stainless Steel in the Presence of Ionic Surfactant

Contact angles of oil droplets on solid surfaces provide useful insight into surfactant cleaning behavior. Contact angles of hexadecane and MAR‐TEMP® 355, an industrial quench oil, on stainless steel were measured for ionic surfactant solutions as a function of ionic strength. The ionic strength of sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) solutions was modified by the addition of sodium chloride. Increases in the contact angle with additions of 1.0 mM and 2.5 mM NaCl were observed for the two oils in SDS and for hexadecane in CTAB. For the industrial quench oil, detachment occurred in CTAB concentrations above the critical micelle concentration; as a result, the equilibrium contact angle measurements were not measured. The critical concentration of CTAB decreased with increasing NaCl concentration. Oil‐removal studies indicate that increasing ionic strength by as little as 2.5 mM can result in improved cleaning. A theoretical insight previously used to explain contact‐angle behavior for a hexadecane‐gold system is used to describe the results obtained with the current system. Managed by UT-Battelle, LLC, for the U.S. Department of Energy under contract DE-AC05-00OR22725.

Influence of Aqueous/Solid Interactions on Organic Droplet Shape in Liquid/Liquid/Solid Systems

We report the results of a theoretical study of the complex phenomena relating to contact angle changes for hexadecane droplets on a gold surface in aqueous ionic surfactant solutions. This approach integrates changes in the nature of the solid absorbed surfactant phase through use of the quasi‐chemical approximation. This improvement is accomplished with minimal additional model complexity and provides evidence for changes in adsorbate structure as aqueous surfactant concentration is increased. The theoretical predictions are tested using previously published data regarding the contact angle of hexadecane on gold in sodium dodecyl sulfate and cetyl‐trimethylammonium bromide solutions.