Fabrication of superhydrophobic surfaces with tunable water droplet adhesion force by a two-step method

In this paper, we present a convenient approach to prepare hierarchical structured superhydrophobic coatings with tunable adhesion force, composed of micro-size glass beads, nano-size SiO₂ particles and epoxy resin. Surfaces of two types with different roughness were fabricated, one type is only with single-scale roughness demonstrating lotus effect with low sliding angle, the other type is hierarchically micro-nano-structured roughness exhibiting petal effect with high adhesion force. The surface roughness is pivotal for controlling the wetting behavior and regulating the contact angle including the contact angle hysteresis. Varying the density of micro-size glass beads could adjust the roughness of the surface, which means the adhesion force of the prepared surface could be easily controlled based on the proposed method. Through variation of glass beads’ amount, the surface could be designed to pin the water droplet with different adhesion force when the surface turned upside down. The surface wettability, surface morphology, adhesion force of the prepared samples are investigated and mechanism of the Cassie-to-Wenzel state transition are discussed in detail. Furthermore, the convenient method provides a possibility for controlling surface morphology, composition and corresponding surface adhesion which could be applied to various substrates such as tile, wood, steel and fabric.     

Wettability investigations on the cellulosic surface of alfa fibers

A wettability study was performed on samples of alfa fibers with the Wilhelmy plate technique. The set of test liquids employed in the measurement of the contact angles was composed of water, heptane, diiodomethane, α‐bromonaphthalene, and formamide. During their first immersion in high‐surface‐energy test liquids, the alfa fibers showed anisotropic behavior: they had an advancing contact angle of 67 ± 6° in one orientation of immersion and an angle of 112 ± 9.5° in the opposite one. Optical microscopy revealed the existence of fibrils on the alfa‐fiber surface. They kept almost the same orientation and were responsible for the interesting hydrophobic/hydrophilic behavior of the fibers. Contact angle measurements and investigations of the hysteresis were also performed. The various results were examined according to the heterogeneities of the fibers. The surface energy of the alfa fibers was determined with three theoretical models: the geometric model, the Good–Van Oss–Chaudhury model, and the Chang model. A comparative study of these models was undertaken. The study of the wetting properties of alfa fibers will provide essential information for optimized composites and so will help us in choosing the right chemical treatment necessary to enhance adhesion in alfa‐fiber‐based composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The nature of adhesion in composites of modified cellulose fibers and polypropylene

Cellulose fibers were surface modified with polypropylene–maleic anhydride copolymer. The physical properties of such fibers were characterized by contact angle measurements, and the chemical structure was identified with ESCA and FTIR. ESCA showed that the modifying agent was localized at the surface of the fibers. The modified fibers were compounded with polypropylene, and composites with various amount of fibers were manufactured by injection molding. All mechanical properties were improved when treated fibers were used. SEM showed improved dispersion, wetting of fibers, and adhesion. The nature of adhesion was studied using FTIR. It was found that the surface modifying agent is covalently bonded to the fibers through esterification. The degree of esterification is enhanced by activating the modifying agent before fiber treatment. This study has shown the effects of treatment conditions on activation of reactive species and chemical reaction between fiber and modifying agent. Moreover, a better understanding has been achieved of the nature of adhesion for the system.     

Studies on surface energetics of glass fabrics in an unsaturated polyester matrix system: Effect of sizing treatment on glass fabrics

The surfaces of glass fibers were sized by polyvinyl alcohol (PVA), polyester, and epoxy resin types in order to improve the mechanical interfacial properties of fibers in the unsaturated polyester matrix. The surface energetics of the glass fibers sized were investigated in terms of contact angle measurements using the wicking method based on the Washburn equation, with deionized water and diiodomethane as the wetting liquids. In addition, the mechanical behaviors of the composites were studied in the context of the interlaminar shear strength (ILSS), critical stress intensity factor (K_IC), and flexural measurements. Different evolutions of the London dispersive and specific (or polar) components of the surface free energy of glass fibers were observed after different sizing treatments. The experimental result of the total surface free energies calculated from the sum of their two components showed the highest value in the epoxy‐sized glass fibers. From the measurements of mechanical properties of composites, it was observed that the sizing treatment on fibers could improve the fiber–matrix interfacial adhesion, resulting in improved final mechanical behaviors, a result of the effect of the enhanced total surface free energy of glass fibers in a composite system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1439–1445, 2001     

Facile Fabricating Strategy for Bioinspired Flexible Film with Cavitation: Liquid Super-Repellent Material with Stimulate-Response on Liquid Adhesion

Inspired by liquid super-repellent skin of springtail, air pockets with tiny openings are fabricated on the surface of polydimethylsiloxane (PDMS) to achieve a stable existence of gas between liquid and micro-nanostructure. After further low-energy grafting, the PDMS with air pocket microstructures shows a well hydrophobic and oleophobic property. When the liquid droplet fell on the fabricated surface, the positive pressure generated by the air pocket promotes the wetting state to be much fitting with the Cassie–Baxter model. Based on the super-repellent microstructures, the flexible material shows properties of anti-icing and anti-fog. Additionally, the positive pressure of the air pocket to liquid droplet changed to be negative when stretching stress is applied to the PDMS elastomer. Based on the changed pressure, wetting state of the liquid droplet reversed from super-low adhesion to high adhesion. The stimulus-responsive material with reversible wettability has great potential in the applications of microfluidic chip and controlled releasing liquid micro-droplets.     

Hierarchical Structured Electrospun Nanofibers for Improved Fog Harvesting Applications

Collection of clean water from humid air has attracted immense attention in recent years due to the lack of access to pure drinking water among large section of population in several parts of the world. Hence, there is a persistent demand for the fabrication of robust, scalable membranes for efficient harvesting of pure water, especially in fog‐laden areas. Herein, three different membranes based on neat nanofibers, nanofibers with microparticles, and nanofibers with hierarchical structures (nanopillars) are successfully fabricated using poly(vinylidene fluoride‐co‐hexafluoropropylene) and fluorinated polyhedral oligomeric silsesquioxane composite mixture. Neat nanofibers and nanofibers with microparticles are fabricated by employing direct electrospinning and electrospinning combined with electrospraying process, respectively. Hierarchical structured fibers are fabricated by growing nanopillars on the surface of the fibers using electrospinning combined with template‐wetting method. The wettability properties including water contact angle and hysteresis of these membranes are investigated. Due to the increased surface roughness and low surface energy, the hierarchical fibers exhibit higher contact angle (153°) and lower hysteresis (3°) compared to the neat nanofibers and nanofibers with microparticles. Furthermore, the results demonstrate that the presence of nanopillars on the surface of the nanofibers improves the membrane's water collection efficiency when exposed to humid air.

     

Study on surface- and mechanical fiber characteristics and their effect on epoxy composite properties tuned by continuous anodic carbon fiber oxidation

Continuous anodic oxidation was employed to alter the surface chemical properties of carbon fibers. As expected, the wetting behavior by water improved and that of non-polar liquid diiodomethane deteriorated. The calculated surface tensions mirror the changes in the physicochemical surface properties. The zeta (ζ)-potential measurements performed also reflect changes in the surface chemistry of the investigated carbon fibers. A correlation between the measured ζ-potentials and the wetting behavior of water on anodically oxidized carbon fibers was found. The influence of anodic carbon fiber oxidation on the epoxy composite properties was studied by a modified axial tensile test, which allows additionally the measurement of the so-called 'notching force' as a measure of the interfacial composite properties. Common model-composite samples were used to check the reliability of this test. The determined 'notching force' as a measure of adhesion correlates with the increased polar component of the fiber surface tension.     

Study on long fiber–reinforced thermoplastic composites prepared by in situ solid‐state polycondensation

Long glass fiber–reinforced thermoplastic composites were prepared by a new process, in situ solid‐state polycondensation (INSITU SSP). In this process reinforcing continuous fibers were impregnated by the oligomer of PET melt, and then the impregnated continuous fibers were cut to a desired length (designated prepreg); finally, the prepreg was in situ polymerized in the solid state to form the high molecular weight matrix. SEM, FTIR spectra, short‐beam shear stress test, flexural strength test, impact strength test, and the intrinsic viscosity measurement were used to investigate the wetting and interfacial adhesion, the mechanical properties of the composite, and the molecular weight of matrix resin in the composite. The results showed that the molecular weight of PET in the matrix resin and mechanical properties could be adjusted by controlling the SSP time and that the high level of interfacial adhesion between reinforcing fibers and matrix resin could be achieved by this novel INSITU SSP process, which are attributed to the good wetting of reinforcing fibers with low molecular weight oligomer melt as the impregnation fluid, the in situ formation of chemical grafting of oligomer chains onto the reinforcing fiber surface, and the in situ formation of the high molecular weight PET chains in the interphase regions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3959–3965, 2004     

Conversion of plastic/cellulose waste into composites. I. Model of the interphase

This article proposes a mechanism for a significant improvement in the mechanical performance of a simulated waste fraction, composed of an immiscible low-density polyethylene (LDPE) and high-impact polystyrene (HIPS) blend (70:30 proportion), when chemithermomechanical pulp (CTMP) fibers and maleic acid anhydride grafted styrene–ethylene/butylene–styrene block copolymer (MAH-SEBS) were added. SEM micrographs of composites showed an increased contact between the continuous LDPE phase and CTMP fibers when the functionalized compatibilizer (MAH-SEBS) was used. By employing a model study using LDPE and regenerated cellulose, we investigated the interphase properties between the plastic phase and the cellulosic component. The model study utilized ESCA, FTIR, and contact angle analysis to follow the reaction between the cellulose surface and the functionalized compatibilizer. All three methods showed that MAH-SEBS was bonded to the surface of the cellulose. The single-fiber fragmentation test showed that the adhesion between cellulose fibers and the plastic matrix was significantly improved for MAH-SEBS–modified samples. The effect of enhanced adhesion on increased mechanical properties of cellulose composites is also discussed, and a prediction of composite strength given, based on interfacial adhesion promotion and fiber properties. © 1995 John Wiley & Sons, Inc.     

An investigation of sound absorption coefficient on sisal fiber poly lactic acid bio‐composites

In this research, the mechanical, acoustical, thermal, morphological, and infrared spectral properties of untreated, heat and alkaline‐treated sisal fiber‐reinforced poly‐lactic‐acid bio‐composites were analyzed. The bio‐composite samples were fabricated using a hot press molding machine. The properties mentioned above were evaluated and compared with heat‐treated and alkaline‐treated sisal fibers. Composites with heat‐treated sisal fibers were found to exhibit the best mechanical properties. Thermo‐gravimetric analysis (TGA) was conducted to study the thermal degradation of the bio‐composite samples. It was discovered that the PLA‐sisal composites with optimal heat‐treated at 160°C and alkaline‐treated fibers possess good thermal stability as compared with untreated fiber. The results indicated that the composites prepared with 30wt % of sisal had the highest sound absorption as compared with other composites. Evidence of the successful reaction of sodium hydroxide and heat treatment of the sisal fibers was provided by the infrared spectrum and implied by decreased bands at certain wavenumbers. Observations based on scanning electron microscopy of the fracture surface of the composites showed the effect of alkaline and heat treatment on the fiber surface and improved fiber‐matrix adhesion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42470.     

Effect of spin finish on fiber/binder adhesion in chemically bonded nonwovens

The purpose of this study is to better understand the mechanisms governing the phenomena of fiber/matrix adhesion by controlling the fiber surface properties. This adhesion is evaluated by studying the micromechanical and thermodynamical behavior of the fiber/matrix interface. The complexity of the interactions at the interface requires a global approach that takes into account the chemistry, morphology, and mechanics. The thermodynamical affinity between the binder and fibers is evaluated by the wetting behavior, whereas the mechanical resistance of the fiber/matrix interface is characterized with the pull‐out test. Three distinct approaches are used to classify the different systems according to the nature of the binder and the fiber surface. It is found that there is better adhesion when the spin finish is removed from the fibers, revealing the surface roughness on which the latex can mechanically anchor. © 2006 Wiley Periodicals Inc. J Appl Polym Sci 102: 4092–4100, 2006     

表面、界面的作用与粘接机理(一)

表面、界面的作用，对粘接过程有很大的贡献。本文介绍了材料表面、界面的湿润与吸附作用对粘接的影响，内容包括表面张力与界面张力，接触角，固体材料表面能的测算，湿润与湿润速度，粘附功与粘附界面的稳定性，粘附与吸附作用的对照等。     

Charaterization of UHMWPE fiber/matrix adhesion by dynamic mechanical spectrometry

The tensile and dynamic mechanical properties of polystyrene and a poly(styrene-co-buty1 acrylate-co-cyclohexy1 methacrylate) statistical terpolymer (terpolymer) reinforced by randomly oriented, discontinuous ultra-high molecular weight polyethylene (UHMWPE) fibers are presented in terms of the fiber/matrix interfacial properties. Using a thermomechanical block model based on the parallel rule of mixtures, the adhesion characteristics of poly(butyl acrylate) (PBA) and poly(cyclohexyl methacrylate) (PCHM) grafted, plasma treated, and untreated fibers were determined. The model successfully predicts the tan δ response of the composites including peak height variations and the development of additional loss dispersions associated with the interphase. Moreover, the model yields a fiber reinforcement efficiency factor, K, which gives a quantitative measure of adhesion. The contact angle of PBA and PCHM grafted high density polyethylene (HDPE) films are also included and are compared to the contact angle of plasma treated fibers. The results indicate that PBA and PCHM grafts enhance adhesion through polymer graft/matrix interactions, not simply by improved wetting.     

Investigations on the adhesion and interfacial properties of polyurethane foam/thermoplastic materials

The adhesion and interfacial properties of polyurethane (PU) foams with thermoplastic (TP) materials were investigated using different techniques. The adhesion performance of PU foam with TP materials was evaluated using the peel test method, and the adhesion durability was checked after different climate treatments. X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements were used to study the surface and interface morphology of PU foam and TP material system. Three types of PU foam samples which differ in their composition and also five commercially available TP blends systems, based on poly(carbonate), poly(styrene‐co‐maleic anhydride), poly(acrylonitrile‐butadiene‐styrene), and silicone acrylate rubber have been used. The slow reacting foam shows the best adhesion properties with all the TP materials. The climate treatments strongly effected the PU foam adhesion durability with poly(carbonate) containing TP materials (70–80% loss in adhesion), but nearly no effect with poly(styrene‐co‐maleic anhydride). The samples with lowered adhesion could be separated by peeling without visible foam residues on the TP surface. AFM, XPS, and surface tension studies have shown that the surface properties of the TP material are still governed by the PU foam. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 479–488, 2007     

Exploring the spinning and operations of multibore hollow fiber membranes for vacuum membrane distillation

Hollow fiber membranes with a multibore configuration have demonstrated their advantages with high mechanical strength, easy module fabrication, and excellent stability for membrane distillation (MD). In this work, the microstructure of multibore fibers was optimized for vacuum MD (VMD). A microstructure consisting of a tight liquid contact surface and a fully porous cross‐section is proposed and fabricated to maximize the wetting resistance and VMD desalination performance. The new membrane exhibited a high VMD flux of 71.8 L m^?2 h^?1 with a 78°C model seawater feed. Investigations were also carried to examine various effects of VMD operational conditions on desalination performance. The 7‐bore membrane showed higher flux and superior thermal efficiency under the VMD configuration than the direct contact MD configuration. Different from the traditional single‐bore hollow fiber, the VMD flux of multibore membrane at the lumen‐side feed configuration was higher than that of the shell‐side feed due to the additional evaporation surface of multibore geometry. © 2013 American Institute of Chemical Engineers AIChE J, 60: 1078–1090, 2014     

Surface modification of drawn gel-cast ultra-high molecular weight polyethylene films

Gel-spun ultra-high molecular weight polyethylene (UHMWPE) fibers have superior properties but their use in composite material applications is limited by their poor adhesion to polymer matrices. Previous studies have shown that etching improves the adhesion of epoxy to the fibers, but leads to a reduction in mechanical properties. The purpose of this research was to use uniaxially drawn gel-cast UHMWPE films as a model system since both films and fibers have a highly oriented fibrillar structural hierarchy. Etching has detrimental effects on the mechanical properties and crystallinity of these very thin films. The small amount of carbonyl and carboxyl groups added to the surface through etching raises the film's surface tension and enhances wetting by epoxy. Even though the unmodified film cannot be bonded with epoxy, the interlaminar shear strength between epoxy and the etched films approaches the cohesive strength of the epoxy. A combination of interfacial and UHMWPE cohesive failures is observed. The increase in adhesion is attributed to the slight increase in surface oxygen.     

Enzyme‐mediated surface modification of jute and its influence on the properties of jute/epoxy composites

Surface modification of jute fibers is necessary to improve the adhesion and interfacial compatibility between fibers and resin matrix before using fibers in polymer composites. In this study, dodecyl gallate (DG) was enzymatically grafted onto the jute fiber by laccase to endow the fiber with hydrophobicity. A hand lay‐up technique was then adopted to prepare jute/epoxy composites. Contact angle and wetting time measurements showed that the surface hydrophobicity of the jute fabric was increased after the enzymatic graft modification. The water absorption and thickness swelling of the DG‐grafted jute fabric/epoxy composite were lower than those of the other composites. The tensile and dynamic mechanical properties of the jute/epoxy composites were enhanced by the surface modification. Scanning electron microscopy images revealed stronger fiber–matrix adhesion in composites with modified fibers. Therefore, the enzymatic graft modification increased the fiber–matrix interface area. The fiber–matrix adhesion was enhanced, and the mechanical properties of the composites were improved. POLYM. COMPOS., 38:1327–1334, 2017. © 2015 Society of Plastics Engineers     

Surface modification of polyimide fibers by novel alkaline–solvent hydrolysis to form high‐performance fiber‐reinforced composites

We modified polyimide (PI) fibers by a novel hydrolysis approach and fabricated PI‐fiber‐reinforced novolac resin (NR) composites with enhanced mechanical properties. We first used an alkaline–solvent mixture containing potassium hydroxide liquor and dimethylacetamide (DMAc) for the surface modification of the PI fibers. The results indicate that the surface roughness and structure of the PI fibers were controlled by the hydrolysis time and the content of DMAc. With the optimized hydrolysis conditions, the tensile modulus of modified PI fibers improved 15% without compromises in the fracture stress, fracture strain, or thermal stability. The interfacial shear strength between the modified PI fibers and NR increased 57%; this indicated a highly enhanced interfacial adhesion. Finally, the tensile and flexural strengths of the composites increased 72 and 53%, respectively. This research provides an effective method for the surface modification of PI fibers and expands their applications for high‐performance composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46595.     

Wetting and adhesion behavior of armos fibers after dielectric barrier discharge plasma treatment

To investigate the influence of atmospheric plasma treatment on aramid fiber wetting and adhesion behavior, an air dielectric barrier discharge (DBD) was applied to the Armos aramid fiber surface at different discharge power densities. Dynamic contact angle analysis indicated that the total surface free energy was increased from 49.6 to 68.3 mJ/m 2 , an increment of 37.7%, whereas the single-fiber tensile strength testing showed that the mechanical properties of the Armos fibers were almost unaffected. With the enhancement of fiber surface wettability, the interlaminar shear strength, which was used to determine the interfacial adhesion in Armos-fiber-reinforced thermoplastic poly(phthalazinone ether sulfone ketone) composites, increased by 17.2% to 71.4 MPa. Scanning electron microscopy photos showed that the predominant failure mode of the composites changed from interface failure to matrix and/or fiber failure after the plasma treatment. Taken together, these results suggest that the air DBD plasma was an effective technique for improving the surface and interfacial performance of the Armos fibers without damaging their bulk properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photoaging and stabilization of rigid PVC/wood‐fiber composites

Ultraviolet (UV) weathering performance of unpigmented and rutile titanium dioxide pigmented rigid polyvinyl chloride (PVC)/wood‐fiber composites has been studied. The composite samples were manufactured by dry‐blending PVC, wood fibers, and other processing additives in a high‐intensity mixer. The dry‐blended compounds were extruded and compression molded into panel samples. The manufactured samples were artificially weathered using laboratory accelerated UV tests. Composite samples were exposed to 340‐nm fluorescent UV lamps and assessed every 200 h, for a total of 1200 h of accelerated weathering. Each assessment consisted of a visual examination of surface roughness or erosion, a contact angle measurement, a FTIR collection, and a color measurement. The experimental results indicated that wood fibers are effective sensitizers and that their incorporation into a rigid PVC matrix has a deleterious effect on the ability of the matrix to resist degradation caused ultraviolet irradiation. The light stability of these composites could be improved quite efficiently with the addition of rutile titanium dioxide photoactive pigment during formulation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1943–1950, 2001