Hydrophobic Polymer Surfaces Research Articles

Studying the Feasibility of Creating Anisotropic Highly Hydrophobic Polymer Surfaces by Ion-Track Technology

Studying the Feasibility of Creating Anisotropic Highly Hydrophobic Polymer Surfaces by Ion-Track Technology

Growth of micro-flowers behind hydrophobic polymer surface and impact of silver and tungsten oxide on the wetting characteristics

In this work, a simple and one-step process was demonstrated to develop hydrophobic polymer surfaces. Commercially available polycarbonate (PC) was treated to turn the front surface hydrophobic with an average wetting contact angle (WCA) as high as 110.5°. The formation of micro-flowers with a coverage density of 9.29 × 106/cm2 on the top of fine base nanostructures was confirmed by a high-resolution field emission scanning electron microscope (FESEM). Impact of typical metal and metal oxide such as silver (Ag) and tungsten oxide (WO3) deposited on such hydrophobic surfaces was demonstrated. Petals of micro-flowers and fine base nanostructures were well decorated with functional metals such as Ag and thus the front surface remained hydrophobic with an average WCA as high as 106.6°. Abundant sharp spikes on the top of narrow hills and dips as revealed in the high-resolution FESEM investigation, were speculated to be the reason behind this hydrophobic characteristic. On the other hand, the hydrophobic surface (WCA of ∼ 110.5°) turned hydrophilic (WCA of ∼11.7°) when the surface was decorated with functional metal oxides, such as WO3. Sessile drop tests were carried out to record average WCA and to understand the wetting characteristics of the specimens. A plausible mechanism for such hydrophobic characteristics as well as the transition from a hydrophobic state to a hydrophilic state has been elucidated.

Lens epithelial cell response to polymer stiffness and polymer chemistry.

Posterior capsule opacification (PCO) is the most common complication of cataract surgery, and intraocular lens (IOL) implantation is the standard of care for cataract patients. Induction of post-operative epithelial-mesenchymal transition (EMT) in residual lens epithelial cells (LEC) is the main mechanism by which PCO forms. Previous studies have shown that IOLs made with different materials have varying incidence of PCO. The aim of this paper was to study the interactions between human (h)LEC and polymer substrates. Polymers and copolymers of 2-hydroxyethyl methacrylate (HEMA) and 3-methacryloxypropyl tris (trimethylsiloxy) silane (TRIS) were synthesized and evaluated due to the clinical use of these materials as ocular biomaterials and implants. The chemical properties of the polymer surfaces were evaluated by contact angle, and polymer stiffness and roughness were measured using atomic force microscopy. In vitro studies showed the effect of polymer mechanical properties on the behavior of hLECs. Stiffer polymers increased α-smooth muscle actin expression and induced cell elongation. Hydrophobic and rough polymer surfaces increased cell attachment. These results demonstrate that attachment of hLECs on different surfaces is affected by surface properties in vitro, and evaluating these properties may be useful for investigating prevention of PCO.

A novel marine bacterium Exiguobacterium marinum a-1 isolated from in situ plastisphere for degradation of additive-free polypropylene

As the ecological niche most closely associated with polymers, microorganisms in the ‘plastisphere’ have great potential for plastics degradation. Microorganisms isolated from the ‘plastisphere’ could colonize and degrade commercial plastics containing different additives, but the observed weight loss and surface changes were most likely caused by releasing the additives rather than actual degradation of the plastics itself. Unlike commercial plastics that contain additives, whether marine microorganisms in the ‘plastisphere’ have adapted to additive-free plastics as a surface to colonize and potentially degrade is not yet known. Herein, a novel marine bacterium, Exiguobacterium marinum a-1, was successfully isolated from mature ‘plastisphere’ that had been deployed in situ for up to 20 months. Strain a-1 could use additive-free polypropylene (PP) films as its primary energy and carbon source. After strain a-1 was incubated with additive-free PP films for 80 days, the weight of films decreased by 9.2%. The ability of strain a-1 to rapidly form biofilms and effectively colonize the surface of additive-free PP films was confirmed by Scanning Electron Microscopy (SEM), as reflected by the increase in roughness and visible craters on the surface of additive-free PP films. Additionally, the functional groups of –CO, -C-H, and –OH were identified on the treated additive-free PP films according to Fourier Transform Infrared (FTIR). Genomic data from strain a-1 revealed a suite of key genes involved in biosurfactant synthesis, flagellar assembly, and cellular chemotaxis, contributing to its rapid biofilm formation on hydrophobic polymer surfaces. In particular, key enzymes that may be responsible for the degradation of additive-free PP films, such as glutathione peroxidase, cytochrome p450 and esterase were also recognized. This study highlights the potential of microorganisms present in the ‘plastisphere’ to metabolize plastic polymers and points to the intrinsic importance of the new strain a-1 in the mitigation of plastic pollution.

Surface hydrophilicity-mediated migration of nano/microparticles under temperature gradient in a confined space

HypothesisParticle transport by a temperature gradient is prospective in many biomedical applications. However, the prevalence of boundary confinement in practical use introduces synergistic effects of thermophoresis and thermo-osmosis, causing controversial phenomena and great difficulty in understanding the mechanisms. ExperimentsWe developed a microfluidic chip with a uniform temperature gradient and switchable substrate hydrophilicity to measure the migrations of various particles (d = 200 nm − 2 μm), through which the effects of particle thermophoresis and thermo-osmotic flow from the substrate surface were decoupled. The contribution of substrate hydrophilicity on thermo-osmosis was examined. Thermophoresis was measured to clarify its dependence on particle size and hydrophilicity. FindingsThis paper reports the first experimental evidence of a large enthalpy-dependent thermo-osmotic mobility χ ∼ ΔH on a hydrophobic polymer surface, which is 1–2 orders of magnitude larger than that on hydrophilic surfaces. The normalized Soret coefficient for polystyrene particles, ST/d = 18.0 K-1µm−1, is confirmed to be constant, which helps clarify the controversy of the size dependence. Besides, the Soret coefficient of hydrophobic proteins is approximately-four times larger than that of hydrophilic extracellular vesicles. These findings suggest that the intrinsic slip on the hydrophobic surface could enhance both surface thermo-osmosis and particle thermophoresis.

Ion Concentration Influences the Charge Transfer Due to a Water-Air Contact Line Moving over a Hydrophobic Surface: Charge Measurements and Theoretical Models.

A metal electrode covered by an inert, hydrophobic polymer surface is dipped into water, and the charge transfer was measured as a function of ion concentration for different chlorides, sulfates, and nitrates. A generic behavior is observed wherein the charge transfer first increases and then decreases as the ion concentration increases. However, for acids, the charge transfer decreases monotonously with concentration and even reverses polarity. Two different models, both in which the charge transfer is attributed to removal of ions from the electrical double layer as the contact line passes by, are discussed and shown to provide possible explanations of the experimental data.

Surprising Hydrophobic Polymer Surface with a High Content of Hydrophilic Polar Groups.

The wetting property of a solid surface has been a hotspot for centuries, and many studies suggest that the hydrophobicity is highly related to the polar components. However, the underlying mechanism of polar moieties on the hydrophobicity remains unclear. Here, we tailor the surface polar moieties of epoxy resin (EP) by ozone modification and assess their wetting properties. Our results show that, for the modified EP with more (60.54%) polar moieties, the polar effect on hydrophobicity cannot be empirically observed. To reveal the underlying mechanism, the absorption parameters, including equilibrium distance, adsorption radius, and effective adsorption sites for water on EP before and after ozone treatment, are calculated on the basis of molecular simulations. After ozone modification, the equilibrium distance (from 1.95 to 1.70 Å), adsorption radius (from 3.80 to 4.50 Å), and effective adsorption sites (from 1 to 2) change slightly and the EP surface remains hydrophobic, although the polar groups significantly increase. Therefore, it is concluded that the wetting properties of solid surfaces are dominated by the equilibrium distance, adsorption radius, and effective adsorption sites for water on solids, and the nonlinear relationship between polar groups and hydrophilicity is clarified.

A Method for the Immobilization of Chitosan onto Urinary Catheters

A method for the immobilization of an antibacterial chitosan coating to polymeric urinary medical catheters is presented. The method comprises a two-step plasma-treatment procedure, followed by the deposition of chitosan from the water solution. In the first plasma step, the urinary catheter is treated with vacuum-ultraviolet radiation to break bonds in the polymer surface film and create dangling bonds, which are occupied by hydrogen atoms. In the second plasma step, polymeric catheters are treated with atomic oxygen to form oxygen-containing surface functional groups acting as binding sites for chitosan. The presence of oxygen functional groups also causes a transformation of the hydrophobic polymer surface to hydrophilic, thus enabling uniform wetting and improved adsorption of the chitosan coating. The wettability was measured by the sessile-drop method, while the surface composition and structure were measured by X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy. Non-treated samples did not exhibit successful chitosan immobilization. The effect of plasma treatment on immobilization was explained by noncovalent interactions such as electrostatic interactions and hydrogen bonds.

Field evaluation of two types of EDS-integrated PV modules with different configurations and surface properties

In this study, two prototypes of PV modules with integrated electrodynamic dust shield (EDS) were characterized in the lab and tested in the field to determine their effectiveness in soiling mitigation. The surface properties of the prototype modules’ front cover were measured to evaluate their effects on the EDS dust removal performance. The soiling of each EDS-PV module was assessed based on its PV power output, from which the EDS cleaning efficiency was quantified in field conditions during winter and summer periods. The dust removal efficiency of glass-surface EDS-PV modules was approximately 30%, about three times higher than that of polymer-surface modules. The EDS technology cleaned more effectively in dry and windy weather conditions. The EDS modules’ front surfaces varied significantly with respect to thickness, hydrophobicity, and the electrostatic potential pattern, contributing to the variation of the EDS efficiency of modules. The EDS-PV module with a hydrophobic polymer surface had a higher soiling rate and lower cleaning efficiency than a thinner, hydrophilic glass surface. The results of this study may help improve design and manufacturing methods for more efficient and robust EDS devices integrated into PV modules.

Effect of Moisture and Feedstock Variability on the Rheological Behavior of Corn Stover Particles

Continuous feeding, processing, and handling of biomass powders is pivotal to the economic viability of integrated biorefineries. However, current challenges associated with the operational reliability of bulk solids handling and transport greatly impact the process economics and ultimately the widespread commercialization of integrated biorefineries. In this work, we examine the effect of moisture and feedstock variability on the flow behavior of corn stover biomass particles. The total flow energy, compressibility, shear properties, and wall friction angles were measured for corn stover samples A and B containing 0%, 15%, 25%, 50%, and 75% (mass fraction) moisture contents using a FT4 powder rheometer. In general, the flowability of both A and B was reduced when moisture was present as indicated by the stability and variable flow rate, compressibility, and shear tests. The 15% moisture sample had the highest flow energy, revealing the interplay between the increased surface tension and looser packing both of which were caused by liquid bridging. The 75% moisture sample had the highest compressibility and the lowest flowability factor (ffc). The trend in wall friction angle was found to be dependent upon the surface hydrophobicity of the wall material. The wall friction angle on the hydrophilic, stainless-steel surface increased with moisture and therefore poses additional handling challenges. On the other hand, the wall friction angle on the hydrophobic polymer surfaces were the lowest for samples with intermediate moisture contents. Sample B had greater bulk density, smaller compressibility, and greater flowability than the sample A, as suggested by the compressibility and shear tests. The wall friction angle of sample B was higher than or equal to that of sample A depending on both the type and the surface roughness of the wall material.

Plasma Electroless Reduction: A Green Process for Designing Metallic Nanostructure Interfaces onto Polymeric Surfaces and 3D Scaffolds.

The design of metal nanoparticle-modified polymer surfaces in a green and scalable way is both desirable and highly challenging. Herein, a new green low-temperature plasma-based in situ surface reduction strategy termed plasma electroless reduction (PER) is reported for achieving in situ metallic nanostructuring on polymer surfaces. Proof of concept for this new method was first demonstrated on hydrophilic cellulose papers. Cellulose papers were dip-coated with different metal ion (Ag+ and Au3+) solutions and then subjected to hydrogen plasma treatment for this PER process. Transmission electron microscopy (TEM) analysis has revealed that this PER process caused anisotropic growth of either gold or silver nanoparticles, resulting in the time-dependent formation of both distinct spherical nanoparticles (∼20 nm) and anisotropic 2D nanosheets. Furthermore, we have demonstrated the adaptability of this process by applying it to hydrophobic fibrous and 3D printed polymeric materials such as surgical face masks and 3D printed polylactic acid scaffolds. The PER process on these hydrophobic polymer surfaces was accomplished via a sequential combination of air plasma and hydrogen plasma treatment. The metallic nanostructuring caused by the PER process on these hydrophobic surfaces was systematically studied using different surface imaging techniques including 3D confocal laser surface scanning microscopy and scanning electron microscopy. We have also systematically optimized the PER process on the surface of 3D scaffolds via varying the concentration of the silver ion precursor and by different postprocessing methods such as sonication and medium soaking. These optimization processes were found to be very important in generating uniform metallic nanoparticle-modified 3D printed scaffolds while simultaneously improving cytocompatibility. Through joint disk diffusion and inhibitory concentration testing, the antibacterial efficacy of silver coatings on face masks and 3D scaffolds was established. Altogether, these results clearly suggest the excellent futuristic potential of this new PER method for designing metallic nanostructured interfaces for different biomedical applications.

Probing Hydrophobic Interactions between Polymer Surfaces and Air Bubbles or Oil Droplets: Effects of Molecular Weight and Surfactants.

Hydrophobic interaction plays an important role in numerous interfacial phenomena and biophysical and industrial processes. In this work, polystyrene (PS) was used as a model hydrophobic polymer for investigating its hydrophobic interaction with highly deformable objects (i.e., air bubbles and oil droplets) in aqueous solutions. The effects of polymer molecular weight, solvent (i.e., addition of ethanol to water), the presence of surface-active species, and hydrodynamic conditions were investigated, via direct surface force measurements using the bubble/drop probe atomic force microscopy (AFM) technique and theoretical calculations based on the Reynolds lubrication theory and augmented Young-Laplace equation by including the effect of disjoining pressure. It was found that the PS of low molecular weight (i.e., PS590 and PS810) showed slightly weaker hydrophobic interactions with air bubbles or oil droplets, as compared to glassy PS of higher molecular weight (i.e., PS1110, PS2330, PS46300, and PS1M). The hydrophobic interaction between PS and air bubbles in a 1 M NaCl aqueous solution with 10 vol % ethanol was weaker than that in the bare aqueous solution. Such effects on the hydrophobic interactions are possibly achieved by influencing the structuring/ordering of water molecules close to the hydrophobic polymer surfaces by tuning the surface chain mobility and surface roughness of polymers. It was found that the addition of three surface-active species, i.e., cetyltrimethylammonium chloride (CTAC), Pluronic F-127, and sodium dodecyl sulfate (SDS), to the aqueous media could suppress the attachment of the hydrophobic polymer and air bubbles or oil droplets, most likely caused by the additional steric repulsion due to the adsorbed surface-active species at the bubble/polymer/oil interfaces. Our results have improved the fundamental understanding of the interaction mechanisms between hydrophobic polymers and gas bubbles or oil droplets, with useful implications on developing effective methods for modulating the related interfacial interactions in many engineering applications.

Plasma-Induced Hemi-Wicking on Sanded Polymer Surfaces

In this paper, a plasma-induced hemi-wicking phenomenon observed on hydrophobic sanded polymer surfaces, polypropylene (PP), polyethylene terephthalate (PET) and polyethylene (PE) is reported. An atmospheric-pressure argon plasma jet was used to treat a limited area of the carefully sanded polymer surfaces to induce the hemi-wicking phenomenon. Such hemi-wicking triggered by the plasma activation is different from the traditional type, which is achieved purely by the surface topography. Surface analyses by X-ray photoelectron spectroscopy (XPS) and water contact analysis (WCA) show that the combination of sanding and plasma treatment increased the oxygen-to-carbon ratio, which is highly beneficial for surface hydrophilicity. The shear stress tests show that the combination of sanding and plasma treatment can enhance the shear stress by 125%, 95%, and 296% on PP, PET, and PE, respectively. The study shows that the newly developed technique by combining the sanding and plasma processing for polymers could be a potentially useful method in future industry applications.

Enhancing PET hydrolytic enzyme activity by fusion of the cellulose–binding domain of cellobiohydrolase I from Trichoderma reesei

The large amounts of polyethylene terephthalate (PET) that enter and accumulate in the environment have posed a serious threat to global ecosystems and human health. A PET hydrolase from PET-assimilating bacterium Ideonella sakaiensis (IsPETase) that exhibits superior PET hydrolytic activity at mild conditions is attracting enormous attention in development of plastic biodegrading strategies. In order to enhance the PET hydrolysis capacity of IsPETase, we selected several polymer-binding domains that can adhere to a hydrophobic polymer surface and fused these to a previously engineered IsPETaseS121E/D186H/R280A (IsPETaseEHA) variant. We found that fusing a cellulose–binding domain (CBM) of cellobiohydrolase I from Trichoderma reesei onto the C-terminus of IsPETaseEHA showed a stimulatory effect on enzymatic hydrolysis of PET. Compared to the parental enzyme, IsPETaseEHA_CBM exhibited 71.5 % and 44.5 % higher hydrolytic activity at 30 ℃ and 40 ℃, respectively. The catalytic activity of IsPETaseEHA_CBM was increased by 86 % when the protein concentration was increased from 2.5 μg/mL to 20 μg/mL. These findings suggest that the fusion of polymer-binding module to IsPETase is a promising strategy to stimulate the enzymatic hydrolysis of PET.

Interaction of Bulk Nanobubbles (Ultrafine Bubbles) with a Solid Surface.

The experimental results [Kanematsu, W. Chem. Eng. Sci. 2020, 219, 115594] on the temporal variations of number concentrations of bulk nanobubbles (ultrafine bubbles) in contact with polymer materials are theoretically analyzed based on the dynamic equilibrium model of bulk nanobubbles partly covered with hydrophobic materials (impurities). It is suggested that bulk nanobubbles are adsorbed on a polymer surface by attractive hydrophobic interaction between a polymer surface and a hydrophobic material partly covering the bubble surface, overcoming the repulsive double-layer interaction. There are two mysteries. One is that the maximum surface number concentration of bulk nanobubbles of about 70 nm in diameter adsorbed on a hydrophobic polymer surface is more than an order of magnitude lower than the typical value for colloid particles of a similar or larger size. The other is that the experimental adsorption rate of bulk nanobubbles on hydrophobic polymer surface is several orders of magnitude lower than the theoretically estimated one. The mysteries are resolved if many of the bulk nanobubbles adsorbed on a hydrophobic polymer surface change to surface nanobubbles with a footprint diameter of about 1 μm.

Influence of synthetic wastewater on entrapped air on the isotactic and atactic polypropylene microplastic surfaces.

The municipal wastewater collection system is recognized as an initial point of interaction between microplastics (MPs) and the urban wastewater matrix. The raw wastewater contains a wide variety of organic and inorganic substances including chemicals and heavy metals. However, the fate of MPs in urban sewer systems is not yet well understood. In this work two types of virgin polypropylene (PP) samples, isotactic (iPP) and atactic (aPP), were exposed to two synthetic wastewater solutions in order to study their effects on the physical properties of the hydrophobic polymer surfaces. Particular attention was paid to the pollution adhesion at the air-liquid-solid interfaces of the surface air pockets entrapped on the polymer surfaces. The first wastewater solution consists of mixed fat, oil and grease (FOG) - surfactant and another which is an exclusively contained wastewater surfactant. The interaction experiment over a period of 10min between the polymer's air pocket and solutions indicated that the size of the bubble in the mixed FOG-surfactant solution increased more pronouncedly for iPP (%152) in contrast to aPP (%31) and was also compared with the greater surface roughness of the polymers. The size variation of the spherical cap on the immersed polymer surfaces were measured between 17µm and 85µm using image processing techniques while the data was analyzed by the Young-Laplace equation. The corresponding technical surface roughness of the polymers, the surface tension of the liquids and their air/water contact angle on the flat polymer surfaces were also measured. The results of this study indicated that surface air pockets influence the adsorption capacity of MPs and thus their buoyancy and contamination potential.

Simple Fabrication of Water Harvesting Surfaces Using Three-Dimensional Printing Technology

A biomimetic surface for water collection was successfully engineered using three-dimensional (3D) printing technology. The fused deposition modeling-type 3D printing was used to create a reusable mold. This was used to cast waveform microstructures on a hydrophobic polymer surface, which was induced by using stacked filaments. The etching was performed on the printed mold by using a chemical solvent to generate nano/micro pores, which enhanced the rolling-off motion of water droplets. To create a hydrophilic region on the hydrophobic surface, the metal deposition was achieved using a 3D-printed mask and the self-masking effect of the tilted tips of waveform microstructures. The metal array served as seeding points for the growth of water droplets in foggy conditions. As a result, the fabricated biomimetic surface exhibited the highest water-collecting performance (average 0.77 g for 10 min) compared with the other four different surfaces. This study demonstrates the use of 3D printing technology to rapidly and simply fabricate engineered (hybrid) surfaces for various applications involving facile control of wettability.

Surface Characterization of Oleic Acid Coated Marble Dust

Calcite, being the most abundant mineral on earth crust, have wide application areas especially in polymer industry as a micronized functional filler material. It is hydrophilic in natural form, and made hydrophobic after surface modification to meet the requirements of polymer industry: the incompatibility between high energetic hydrophilic surface of calcite and the low-energy surface of hydrophobic polymers is a major problem. Treatment of micronized calcite with fatty acids is one of the most common method to obtain modified mineral surface. In present study, oleic acid (OA), fatty acid type surface modifying agent was used for the surface characterization of OA coated marble dust. Fine tailings of slab cutting unit of a marble processing plant was supplied. The sample was subjected to wet classification process to obtain micronized calcite fraction for experimental works. Surface modification of finely sized fraction was performed in a laboratory type flotation unit. Thermogravimetric analysis (TGA) and Transmission Electron Microscopy (TEM) were used as characterization techniques.

Effects of mould wear on hydrophobic polymer surfaces replicated using plasma-treated and laser-textured stainless steel inserts

ABSTRACT The mass production of polymeric parts with functional surfaces requires economically viable manufacturing routes. Injection moulding is a very attractive option, however, wear and surface damage can be detrimental to the lifespan of replication masters. In this research, austenitic stainless steel inserts were hardened by low temperature plasma carburising and then different micro and nano scale surface textures, inspired by Lotus leaves and Springtail skins, were laser fabricated. A commonly available talc-loaded polypropylene was used to produce 5000 replicas and thus to investigate the evolution of surface textures both on inserts and replicas together with their functional response. The progressive wear or surface damage on the inserts during the injection moulding process had a clear impact on surface roughness and peak-to-peak topographies of the replicas. In general, polymer replicas produced with the carburised inserts retained wetting properties for longer periods compared with those produced with the untreated replication masters.

Assembling Sn3O4 nanostructures on a hydrophobic PVDF film through metal-F coordination to construct a piezotronic effect-enhanced Sn3O4/PVDF hybrid photocatalyst

Abstract Piezotronic effect has been thought as a general approach for building high performance hybrid photocatalysts by integrating semiconductor nanostructures on piezoelectric materials. Although polyvinylidene fluoride (PVDF) has been widely applied as a flexible piezoelectric material, it is thought that assembling inorganic semiconductor nanostructures on PVDF surface is promising owing to the high hydrophobic property of PVDF. In this study, we proposed that the coordination effect between a metal ion and an exposed fluorine atom on the surface of PVDF can be used to assemble a layer of photocatalytic metal oxide nanostructures on the PVDF film surface. Using Sn3O4 as a model oxide, a Sn3O4/PVDF hybrid nanostructured photocatalyst was successfully synthesized. The X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy results confirmed the existence of coordinated bonds between F ions and metal ions, which could explain the stable growth of inorganic nanostructures on the hydrophobic surface of PVDF. At the interface between Sn3O4 and PVDF in the hybrid nanostructured photocatalyst, a built-in electric field was constructed on the basis of the ferroelectric field of the PVDF film, which induced an enhanced photocatalytic property. Most importantly, the swing driven by flowing water can considerably enhance photocatalytic properties owing to the piezotronic effect-driven alternating reconstruction of built-in electric field induced by the deformation of PVDF film. This study provides an approach for the synthesis of metal oxide semiconductor nanostructures on hydrophobic PVDF polymer surface. The developed material will have many applications in the photodegradation of organic pollutants in waste water.