Recoverable and thermally stable superhydrophobic silica coating

A facile route to methyltrimethoxysilane (MTMS) based recoverable superhydrophobic silica coatings with dual-scale roughness obtained through the single step base catalyst sol–gel process. Superhydrophobic silica coatings have shown static water contact angle near about 170 ± 1° and dynamic water contact angle up to 2 ± 1°. Superhydrophobic-superhydrophilic switching feature also achieved by alternating heat treatment and bath surface modification with Trimethylchlorosilane (TMCS) at room temperature (26 °C). Furthermore, the superhydrophobic state could be transformed into superhydrophilic state by slow rate heat treatment. These studies present a very simple strategy for the fabrication of recoverable superhydrophobic surfaces.     

Surface modification by self-assembled polycation/azo dye multilayers

The formation and stability of some polycation/azo dye multilayers by the alternate adsorption of one polycation of integral type having 95 mol% of N,N-dimethyl-2-hydroxypropyleneammonium chloride repeat units (PCA₅) and four multicharged azo dyes: Crocein Scralet MOO (CSMOO), Ponceau SS (PSS), Direct Blue 1 (DB 1) and Direct Red 80 (DR 80) are discussed in this paper. The dyes were different either by the number of sulfonic groups (PSS, DB 1 and DR 80) or by their position (CSMOO and PSS). The multilayer growth, when PCA₅ was adsorbed from 0.2 M Na₂SO₄ aqueous solution, was followed by UV-Vis spectroscopy and by electrokinetic measurements. Solid state polycation/azo dye complexes were also prepared to get qualitative information on the charge compensation in the multilayers.     

Asymmetrically superhydrophobic cotton fabrics fabricated by mist polymerization of lauryl methacrylate

A graft-polymerization process with atomized lauryl methacrylate as monomer is used to fabricate fluorine-less and asymmetrically superhydrophobic cotton fabrics. The polymers synthesized in the process can form nanoscale hierarchical structures on the cotton surface, and the surface morphology can be controlled by choosing a suitable solvent or by varying the feeding quantity of the monomer mist stream. After applying the surface modification to cotton fabrics, an asymmetrically superhydrophobic surface is achieved without any additional nanosized particles, and the solvent damages on the cotton fabrics are controllable at a very low level. Surface characterization reveals that the modified side of the cotton fabric has laundering-durable and mechanically stable superhydrophobicity with a water contact angle of more than 150°, whereas the opposite inherits the hydrophilic property of pristine cotton fabric. The modified cotton fabrics are found to have medium-level water-absorbing ability between pristine cotton and PET fabrics, as well as good vapor transmissibility similar to pristine cotton fabric. These properties are of great significance in textile and medical applications.     

Polyelectrolyte/magnetite nanoparticle multilayers: preparation and structure characterization

Polyelectrolyte composite planar films containing a different number of iron oxide (Fe3O4) nanoparticle layers have been prepared using the layer-by-layer adsorption technique. The nanocomposite assemblies were characterized by ellipsometry, UV-vis spectroscopy, and AFM. Linear growth of the multilayer thickness with the increase of the layer number, N, up to 12 reflects an extensive character of this parameter in this range. A more complicated behavior of the refractive index is caused by changes in the multilayer structure, especially for the thicker nanocomposites. A quantitative analysis of the nanocomposite structure is provided comparing a classical and a modified effective medium approach taking into account the influence of light absorption by the Fe3O4 nanoparticles on the complex refractive index of the nanocomposite and contributions of all components to film thickness. Dominant influence of co-adsorbed water on their properties was found to be another interesting peculiarity of the nanocomposite film. This effect, as well as possible film property modulation by light, is discussed.     

Simple method for preparing superhydrophobic paper: spray-deposited hydrophobic silica nanoparticle coatings exhibit high water-repellency and transparency

Superhydrophobic and transparent coatings are deposited onto paper by spraying alcohol suspensions of SiO(2) nanoparticles. Superhydrophobicity depends on the aggregation states of nanoparticles, which are determined by the type of alcohol used in the suspensions. The superhydrophobicity of the paper is maintained after touching the paper with a bare finger.     

Synergistic effect of polycation and polyanion on silica polymerization

Colloidal silica (SiO(2)) is perhaps the most undesirable inorganic deposit formed in industrial water treatment systems. SiO(2) can either be found in bulk or on surfaces, such as heat exchangers, pipelines, or membrane. Conventional mineral scale inhibitors cannot inhibit its formation. Chemical cleaning is difficult and not free from hazards. This paper reports the excellent inhibition efficiency of adipic acid/amine-terminated polyethers D230/diethylenetriamine copolymer (AA/AT/DE). However, a small amount of silica-AA/AT/DE white insoluble floc appears in the solution. To overcome this problem, polyepoxysuccinic acid (PESA) is introduced. PESA by itself cannot inhibit silica polymerization. However, the combination of PESA and AA/AT/DE cannot only prevent the white floc, but also improve the inhibition performance of AA/AT/DE. The underlying mechanism is investigated based on zeta potentials and atomic force microscopy topography.     

Imparting durable antimicrobial properties to cotton fabrics using quaternary ammonium salts through 4-aminobenzenesulfonic acid-chloro-triazine adduct

A 4-aminobenzenesulfonic acid-chloro-triazine adduct was successfully synthesized in a laboratory scale and treated with cotton fabrics in order to increase the anionic sites and thereby % exhaustion of cationic compounds. Two Quaternary Ammonium Salts (QAS) was investigated namely, Cetylpyridinum chloride (CPC) and Benzyldimethylhexadecyl ammonium chloride (BDHAC) which are widely accepted as strong antimicrobial agents. The reaction mechanism involved in the synthesis of the reactive adduct as well its application to cotton fabric were demonstrated in detail. The effects of application parameters, namely pH, temperature and liquor ratio were examined. The reaction efficiency was determined through monitored % exhaustion of the adduct by cotton fabric. Antimicrobial activity of the treated cotton sample was studied against Staphylococcus aureus according to AATCC test method 100-1999. Results obtained show that the treated fabric shows higher antimicrobial activity compared with the untreated fabric. The results depict also that % exhaustion decreases as the pH, temperature and liquor ratio increase. Moreover, the appropriate predictable empirical models were developed using Excel solver function incorporating interaction effects of all variables to predict the % exhaustion and the satisfactory results (R² > 0.98) were obtained.     

Electrochemical characterization of polyelectrolyte/gold nanoparticle multilayers self-assembled on gold electrodes

Polyelectrolyte/gold nanoparticle multilayers composed of poly(l-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+). This paper reports a large sensitivity to the charge of the outermost layer for the permeability of these assemblies to the probe ions. With the former redox pair, dramatic changes in the impedance response were obtained for thin multilayers each time a new layer was deposited. In the latter case, the multilayer behaves as a conductor exhibiting a strikingly lower impedance response, the electric current being enhanced as more layers are added for Au NP terminated multilayers. These results are interpreted quite satisfactorily by means of a capillary membrane model that encompasses the wide variety of behaviors observed. It is concluded that nonlinear slow diffusion through defects (pinholes) in the multilayer is the governing mechanism for the [Fe(CN)(6)](3-/4-) species, whereas electron transfer through the Au NPs is the dominant mechanism in the case of the [Ru(NH(3))(6)](3+/2+) pair.     

Hydrophobicity modification of woven cotton fabric by hydrophobic fumed silica coating

Water repellency of woven cotton fabric was achieved by coating with the aqueous dispersion containing organosilane agent (HDTMS) and fumed silica. The coating agents were applied using padding method and then followed by batching the coated fabric at the ambient temperature for 24 h to allow the condensation reaction between HDTMS silanol group and fumed silica silanol group, rendering silica particles hydrophobic. An ultrasonicator was employed to prepare the homogenous coating dispersion. The water repellency evaluated by water contact angle determination which showed the contact angle over 110° was obtained with low amount of applied HDTMS of 1 wt%. The effect of fumed silica addition on an increase in fiber surface roughness geometry showed the influential result in improving the water contact angle. From durability to washing test, the hydrophobic coatings evidenced from SEM and ATR/FTIR remained adhering to fiber surface, indicating the durability. After washing, the coating on the fabric with fumed silica addition appeared to be scatter particles which made a contribution to the higher contact angle value when compared to sheet-like layer coating in case of HDTMS coating alone.     

Transparent superhydrophobic films based on silica nanoparticles

We demonstrate a layer-by-layer processing scheme that can be utilized to create transparent superhydrophobic films from SiO2 nanoparticles of various sizes. By controlling the placement and level of aggregation of differently sized nanoparticles within the resultant multilayer thin film, it is possible to optimize the level of surface roughness to achieve superhydrophobic behavior with limited light scattering. Transparent superhydrophobic films were created by the sequential adsorption of silica nanoparticles and poly(allylamine hydrochloride). The final assembly was rendered superhydrophobic with silane treatment. Optical transmission levels above 90% throughout most of the visible region of the spectrum were realized in optimized coatings. Advancing water droplet contact angles as high as 160 degrees with low contact angle hysteresis (<10 degrees ) were obtained for the optimized multilayer thin films. Because of the low refractive index of the resultant porous multilayer films, they also exhibited antireflection properties.     

Fabrication of asymmetrically superhydrophobic cotton fabrics via mist copolymerization of 2,2,2‐trifluoroethyl methacrylate

We report here a simple strategy for fabricating asymmetrically superhydrophobic cotton fabric via a mist copolymerization of three monomers, 2,2,2‐trifluoroethyl methacrylate (TFMA), 2‐isocyanatoethyl methacrylate (IEM), and divinylbenzene (DVB). The copolymer layer on the cotton surface was confirmed by X‐ray photoelectron spectroscopy (XPS) analysis and attenuated total reflection (ATR) accessory, and the nanoscale hierarchical structures in the polymeric layer were demonstrated by observation of field emission scanning electron microscope (FE‐SEM). Surface characterization reveals that the modified surface is superhydrophobic, but the opposite side of the modified cotton fabric has the hydrophilic nature of cotton. More experimental data suggest that the good water adsorptivity and vapor transmissibility of the original cotton fabric were inherited after the surface modification. These properties are of great significance in textile and medical applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1862–1871     

Surface cationization of cellulose to enhance durable antibacterial finish in phytosynthesized silver nanoparticle treated cotton fabric

Cellulose - Elimination of disease-causing bacteria from cotton fabrics is critically important to control several bacteria-mediated infections in humans. Antibacterial nanoparticles, particularly...     

Thermal and fire stability of cotton fabrics coated with hybrid phosphorus-doped silica films

Hybrid phosphorus-doped silica films have been prepared through sol?Cgel processes to enhance the thermal and fire stability of cotton. To this aim, 3-aminopropyltriethoxysilane and N,N,N??,N??,N??,N??-hexakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine have been reacted with diethylphosphatoethyltriethoxysilane. FT-IR spectroscopy was exploited for assessing the formation of the silica skeleton on the cotton surface and for evaluating the interactions between the cellulosic fibres and the doped film. The effect of the concurrent presence of Si, P and N on cotton has been investigated by thermogravimetric analyses and the flammability behaviour has been assessed by vertical flammability tests, as well. The sol?Cgel treatments in the presence of phosphorus and nitrogen turned out to play a protective role on the degradation of the cotton fibres, hindering the formation of volatile species that fuel the further degradation and favouring the formation of a carbonaceous structure.     

Relationship between the growth regime of polyelectrolyte multilayers and the polyanion/polycation complexation enthalpy

The alternate deposition of polyanions and polycations leads to the formation of films called polyelectrolyte multilayer films (PEMs). Two types of growth processes are reported in the literature, leading to films that grow either linearly or exponentially with the number of deposition steps. In this article we try to establish a correlation between the nature of the growth process and the heat of complexation between the polyanions and the polycations constituting the PEM film. Isothermal titration microcalorimetry experiments performed on several polyanion/polycation systems seem to indicate that an endothermic complexation process is characteristic of an exponential film growth, whereas a strongly exothermic process corresponds to a linear growth regime. Finally, weakly exothermic processes seem to be associated with weakly exponentially growing films. These results thus show that exponentially growing processes are mainly driven by entropy. This explains why the exponential growth processes are more sensitive to temperature than the linear growing processes. This temperature sensitivity is shown on the poly-L-glutamic acid/poly(allylamine) system which grows either linearly or exponentially depending on the ionic strength of the polyelectrolyte solutions.     

A study on superhydrophobic coating in anti-icing of glass/porcelain insulator

This paper focuses on the preparation of a superhydrophobic coating on glass/porcelain insulators which possess anti-icing property below freezing temperature. Inspired by lotus-effect, the fabrication of a superhydrophobic coating has two steps: the first step is to construct a hierarchical SiO₂ coating on the substrate surface, and the second step is the chemical modification of the SiO₂ coating with 1H,1H,2H,2H-Perfluorodecyltriethoxysilane (PDTS). The precursor for the hierarchical SiO₂ coating is a suspension of SiO₂ sol particles and dispersible SiO₂ powder particles. According to the TEM testing, SiO₂ sol particles prepared by sol–gel method has an average particle size about 2–5 nm, while the size of the dispersible SiO₂ particles is ca. 20 nm. The precursor was sprayed on glass/porcelain insulators, and then dried at ambient condition, finally heat-treated at 773 K for 2 h. The morphology of the superhydrophobic coating was characterized by TEM and AFM, and experimental results indicated that the coating featured [hierarchical structure consisting of both large bumps with micron-sized height (0.8 μm) and tiny papillae with the size about 30 nm] micron-sized roughness (0.8 μm) combined with nano-sized roughness (about 2 nm). Moreover, the scratch test showed that the coating tightly adhered to the surface of the glass/porcelain insulators. The superhydrophobic property of the coating was examined by a contact angle measurement, and the results demonstrated that the static water contact angle is high up to 163.6°, and the sliding angle is 1.4°. The superhydrophobic property of the coating was also confirmed by the outdoor tests in winter, and it was found that the superhydrophobic coating had the function in anti-icing, based on which the anti-icing mechanism underlying was discussed in terms of the interaction between impacting droplets and superhydrophobic surface.     

Effect of precursor-layer surface charge on the layer-by-layer assembly of polyelectrolyte/nanoparticle multilayers

In this Article, we investigate the effect of a precursor layer, which is composed of four bilayers of polyethyleneimine (PEI) and poly(sodium styrene sulfonate) (PSS), on the subsequent LBL assembly of hybrid films composed of indium tin oxide (ITO) nanoparticles and PSS. A precursor polyelectrolyte layer is usually deposited to minimize interference by the substrate. It is shown here that the "effective" surface charge of the precursor layer can significantly affect the subsequent assembly behavior of [ITO/PSS](9.5) hybrid thin films. Depending on the surface charge of the precursor layer, the subsequent LbL assembly of [ITO/PSS](9.5) hybrid films can exhibit either one or two regimes. When two growth regimes are present, the first one consists of a "recovery regime", and the second is the expected "linear growth regime." The length of the "recovery regime" is dependent on how much positive charge the precursor layer possesses and how fast this surface charge can be compensated. This work reveals for the first time that changes in the surface charge of the precursor layer can have a significant effect on the subsequent LBL assembly process. The surface charge of the precursor layer was investigated using ζ-potential measurements on model silica microspheres. These experiments showed that the surface charge of the precursor layer, [PEI/PSS](4), is dependent on the pH of the solution in which it is immersed, and that it can reverse from a negatively charged surface to a positively charged one, at sufficiently low pH due to the protonation of PEI, despite having the negatively charged PSS layer as the outermost layer.     

Influence of antimicrobial finishes on the biodeterioration of cotton and cotton/polyester fabrics: Leaching versus bio-barrier formation

The influence of antimicrobial activity of two contemporary finishes, specifically a dispersion of colloidal silver (Ag) and 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride (Si-QAC), on the degree of biodeterioration of 100% cotton (CO) fabric and fabric composed of a mixture of cotton and polyester (CO/PET) was studied. Ag was chosen for the leaching agent, while Si-QAC was used as the bio-barrier-forming agent. The biodeterioration of samples finished with different concentrations of Ag and Si-QAC was analysed from a standard soil burial test after 3, 6 and 12 days of exposure to soil microflora. SEM micrographs revealed intensive biodeterioration of the unfinished cellulose fibres, while the highly biologically resistant polyester fibres remained undamaged. A controlled release of Ag successfully inhibited biodeterioration of the cellulose fibres in the CO and CO/PET fabrics when its concentration reached a lethal, biocidal concentration. Contrary to the effects of Ag, the bio-barrier formation of Si-QAC on CO and CO/PET fabrics was insufficient to protect the cellulose fibres during longer periods of soil burial, irrespective of its concentration. Intensive chemical changes to the cellulose were clearly seen from the FT-IR spectra of all of the samples. The resistance of the polyester component to biodeterioration did not provide any significant protection for the cotton component in CO/PET fabric.     

Sonochemical coating of cotton and polyester fabrics with "antibacterial" BSA and casein spheres

A novel antibacterial coating for cotton and polyester fabrics has been developed by using drug-loaded proteinaceous microspheres made of bovine serum albumin and casein proteins. The microbubbles were created and anchored onto the fabrics (see figure) in a one-step reaction that lasts 3 min. The sonochemically produced "antibacterial fabrics" have been characterized. The efficiency of the sonochemical process in converting the native proteins into microspheres, encapsulating the drug, and coating the fabric has also been studied.