Switchable water absorption of paper via liquid flame spray nanoparticle coating

Surface wetting/anti-wetting and liquid absorption are relevant properties of many porous solids including paper and other cellulose-based materials. Here we demonstrate how surface wetting by water and water absorption of commercially available kraft paper can be altered by thin nanoparticle coatings fabricated by liquid flame spray in facile and continuous one-step process. Surface wettability and absorption properties of paper increased with silica and decreased with titania (TiO₂) nanoparticle coatings. Moreover, the water-repellent (superhydrophobic) TiO₂ nanoparticle coated paper could be switched to superhydrophilic and water absorbing by ultraviolet illumination. The experiments revealed that although surface wetting and liquid absorption of nanoparticle coated paper are strongly related to each other, they are two distinct phenomena which do not necessarily correlate. We propose wetting regimes on the nanoparticle coated paper samples on the basis of the experimental observations.     

High- and low-adhesive superhydrophobicity on the liquid flame spray-coated board and paper: structural effects on surface wetting and transition between the low- and high-adhesive states

Surface wetting is an important and relevant phenomenon in several different fields. Scientists have introduced a large number of applications where special surface wetting could be exploited. Here, we study wetting phenomena on high- and low-adhesive superhydrophobic liquid flame spray (LFS)-generated TiO₂ coatings on paper and pigment-coated board substrates using water–ethanol solution as a probe liquid. Submicrometer-scale air gaps, which exist on superhydrophobic surfaces below the liquid droplets, were more stable with the ethanol increment than the larger-scale micrometric air gaps. With the droplet ethanol concentration of 15 wt%, static contact angle as high as 155?±?2° was measured on the LFS–TiO₂-coated board. Transition from the low-adhesive wetting state to the high-adhesive state was demonstrated on the LFS–TiO₂-coated paper. The LFS method enables efficient roll-to-roll production of surfaces with special wetting properties on economically viable board and paper substrate materials.     

Photocatalytic Activity and Photo-Induced Wettability Conversion of TiO2 Thin Film Prepared by Sol-Gel Process on a Soda-Lime Glass

We have developed the transparent photoactive TiO₂ thin film coated on soda lime glass (SLG) by sol-gel process. Titanium dioxide thin films coated on SLG exhibit lower photocatalytic activity due to the thermal diffusion of Na ion from the SLG substrate. Thin SiO₂ film precoating is very effective to prevent the thermal diffusion of Na ion. We have evaluated the photocatalytic decomposition of gaseous acetaldehyde and the photo-induced surface wettability of TiO₂ films with and without SiO₂ precoating layer. As expected, the TiO₂ film on SiO₂/SLG is more photoactive to decompose acetaldehyde than that on SLG. However, as for wettability conversion, there was little difference in the conversion rate between TiO₂ film without SiO₂, and TiO₂ film with SiO₂. Different dependence of Na ion diffusion on two kinds of photo-induced reaction on TiO₂ is discussed based on the difference of the photo-induced reaction mechanism.     

Effect of Titanium Dioxide Film Thickness on Photocatalytic and Bactericidal Activities Against Listeria monocytogenes

Structural, microstructural and bactericidal surface properties of TiO₂‐coated glass substrates elaborated by reactive Radiofrequency sputtering are investigated. As pathogenic bacteria in biofilms are a major concern in food industries due to their growing resistance to cleaning and sanitizing procedures, the development of photoactive surfaces exhibiting bactericidal properties is acknowledged as an effective approach to tackle bacterial contaminations. Our principal aim concerns the study of the photoactive top‐layer thickness impact (from 80 nm to ~500 nm) on Listeria monocytogenes. Structural characterization of the TiO₂ layers demonstrates that anatase and rutile phases are both present, depending on the film thickness. Photocatalytic activity of the samples has been evaluated through the degradation of aqueous methylene blue (MB) solutions under UVA light illumination for various time periods. The results show an efficiency rating increase according to TiO₂ film thickness up to a threshold value close to 400 nm. Moreover, a significant decrease of the adherent bacteria number is observed after 20 min of UVA illumination. The quantitative study of the bactericidal activity associated with scanning electron microscopy observations of the postprocess bacteria damaged cells demonstrates the efficiency of the 240‐nm‐thick TiO₂ coating sample. The results are correlated with the production of hydroxyl radicals during the process of photocatalysis.     

Influence of transition metal-doped titanium(IV) dioxide on the photodegradation of polystyrene

The effects of adding dispersed powders of various forms of titanium(IV) dioxide on the photodegradation of polystyrene have been examined using FT-IR spectroscopy from the following points of view: effect of crystal form, concentration of pigment, transition metal ion, dopant concentration, calcination temperature of pigment, and pigment coating.The rate of photodegradation of polystyrene is reduced by adding certain grades of TiO₂ such as coated TiO₂ particles or TiO₂ doped with small percentages of Cr or Mn ions. The rate is increased on adding TiO₂ doped with V and especially Mo or W ions. The anatase form of TiO₂ is more photoactive than the rutile form, as is the effect of increasing the calcination temperature of the pigment. The concentration dependences of the degradation rates are complex, but can be directly related to the percentage of anatase achieved after calcination. Even the most aggressive of the metal-doped pigments are less photoactive than a Degussa P25 material, containing rutile and anatase.     

Influence of transition metal-doped titanium(IV) dioxide on the photodegradation of polyethylene

The effects of adding dispersed powders of various forms of titanium(IV) dioxide on the photodegradation of polyethylene have been examined from the following points of view: effect of crystal form, concentration of pigment, transition metal ion, dopant concentration, calcination temperature of pigment, and pigment coating.The rate of photodegradation of polyethylene is reduced by adding certain grades of TiO₂ such as coated TiO₂ particles or TiO₂ doped with small percentages of Cr or Mn ions. The rate is increased on adding TiO₂ doped with V and especially Mo or W ions. The anatase form of TiO₂ is more photoactive than the rutile form, and the effect of increasing the calcination temperature of the pigment is to reduce photoactivity by boosting the rutile fraction. The concentration dependences of the degradation rates are complex, but can be directly related to the percentage of anatase achieved after calcination. Even the most aggressive of the metal-doped pigments are less photoactive than the Degussa P25 material, containing both rutile and anatase.     

Superhydrophobic Polypropylene Surfaces Prepared with TiO2 Nanoparticles Functionalized by Dendritic Polymers

Hybrid inorganic–organic nanomaterials have received increasing interest due to the possibility of implementing different functions and characteristics within a single material. Their functionalities are a consequence of the synergy of the properties of distinct building blocks and are related to their varied natures and spatial locations. In this work, we present the development of superhydrophobic properties on polypropylene (PP) surfaces using hybrid nanomateriales from TiO₂ nanoparticles (NPs) and dendronized polymers. The dendron acryl Behera's amine was successfully grafted on the TiO₂ NP surfaces by Surface‐Initiated Atom Transfer Radical Polymerization (SI‐ATRP) and a core‐brush material was obtained. Finally, PP substrates were coated with NP hybrids to produce superhydrophobic surfaces with water contact angles of over 158 degrees. Controlling the organic silane concentration on the TiO₂ NPs allowed the dendronized process to be driven and thereby permitted the selection of specific wettability properties on PP substrate surfaces with high water adhesion or self‐cleaning conditions. This dendronized effect with consequent steric congestion of the polymeric brushes on the NPs changed their behaviors from Wenzel to the Cassie Baxter state. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2019–2029     

Fabrication of durable superhydrophobic nanofibrous filters for oil‐water separation using three novel modified nanoparticles (ZnO‐NSPO,AlOO‐NSPO,and TiO2‐NSPO)

Three reusable and durable superhydrophobic nanofibrous filters were prepared by dip coating the nanofibrous fabric in the three different dispersed solutions of the newly modified nanoparticles (ZnO‐NSPO, AlOO‐NSPO, and titanium dioxide [TiO₂]‐NSPO). The contact angle results proved that the TiO₂‐NSPO coated nanofibrous polyacrylonitrile (PAN) filter was hydrophobic with the water contact angle (WCA) of 141° while the ZnO‐NSPO and AlOO‐NSPO coated nanofibrous PAN filters were superhydrophobic with the WCA of 168° and 152°, respectively. The as‐prepared filters can be utilized as an effective martial for oil‐water separation with separation efficiency of over 98%.     

Superhydrophilic–superhydrophobic micropattern on TiO2 nanotube films by photocatalytic lithography

The present paper describes an unconventional approach to fabricate the superhydrophilic–superhydrophobic micropatterns on the TiO₂ nanotube structured film by photocatalytic lithography with a two-step process. At the first step, the superhydrophobic TiO₂ nanotube film is fabricated through electrochemical and self-assembled techniques. And at the second step, the superhydrophobic film is selectively exposed to UV light through a photomask to locally photocatalyse the organic monolayer assembled on the TiO₂ nanotube surface. The superhydrophilic–superhydrophobic micropatterns have thus been developed, as a novel template to fabricate a define micropatterned coating of nano octacalcium phosphate by electrochemical deposition. It is indicated that these combined processes reveal a very promising approach for constructing well-defined micropatterns of various functional materials.     

Photocatalytic TiO2 coatings on limestone

The application of photocatalytic coatings on stone has been investigated for providing surface protection and self-cleaning properties. Sol–Gel and hydrothermal processes were used to synthesise TiO₂ colloidal suspensions and coatings with enhanced photocatalytic activity without any thermal curing of the coated stone. The stone was a porous limestone (apulian sedimentary carbonatic, calcite stone). Films and powders prepared from TiO₂ sols were studied using X-ray diffraction to evaluate the microstructure and identify rutile and anatase phases. A morphological and physical characterisation was carried out on coated and uncoated stone to establish the changes of appearance, colour, water absorption by capillarity and water vapour permeability. The photocatalytic activity of the coated surface was evaluated under UV irradiation through NO _x and organics degradation tests. The performances of the synthesised TiO₂ sols were compared with commercial TiO₂ suspension. Since the coating doesn’t need temperature treatments for activating the photocatalytic properties, the nano-crystalline hydrothermal TiO₂ sols seem good candidate for coating applications on stone that cannot be annealed after the coating application.     

Functionalization of cotton fabrics with rutile TiO<Subscript>2</Subscript> nanoparticles: Applications for superhydrophobic,UV-shielding and self-cleaning properties

The superhydrophobic cotton fabrics were prepared by combining the coating of titanium dioxide (TiO₂) with the subsequent dodecafluoroheptyl-propyl-trimethoxysilane (DFTMS) modification. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements revealed that the nanosized TiO₂ sphere consisted of granular rutile. The TiO₂ layer coated on the cotton altered both the surface roughness for enhancing the hydrophobicity and UV-shielding property. The cotton fabric samples showed excellent water repellency with a water contact angle as high as 162°. The UV-shielding was characterized by UV-vis spectrophotometry, and the results indicated that the fabrics could dramatically reduce the UV radiation. The photocatalytic progress showed that organic stains were successfully degraded by exposure of the stained fabric to UV radiation. Such multifunctional cotton fabrics may have potentials for commercial applications.     

Surface treatment of 25‐μm Kapton film by ammonia for improvement of TiO2/SiO2 coating's adhesion

Due to a smooth hydrophobic surface of Kapton film, it is very difficult to coat an inorganic oxide coating on its surface. In this study, the surface of Kapton was treated by NH₃·H₂O and silicon coupling agent to improve the polymer surface wettability. Changes in surface hydrophilicity were studied by contact angle measurement. The samples were irradiated by atomic oxygen (AO) in a ground‐based simulation system. TiO₂/SiO₂ multi‐layer coatings were prepared on the surface of Kapton by sol–gel method to resist AO erosion. The optical transmittance and surface morphology of samples were investigated by UV–vis spectroscopy and scanning electronic microscope. The results indicated that the TiO₂/SiO₂ sol could easily form a uniform thin coating on the surface of pretreated Kapton. After AO exposure, the coatings became more compact, without peeling off. The AO erosion yield value of coated Kapton was sharply down, and the samples had good optical transparency. Copyright © 2017 John Wiley & Sons, Ltd.     

Evaluation of in vitro bioactivity and MG63 Oesteoblast cell response for TiO2 coated magnesium alloys

The present investigation reports TiO₂ coating on magnesium alloy AZ31 by sol–gel method via dip coating technique. TiO₂ coated surface was characterized by thin film X-ray diffraction (TF-XRD), Fourier transform infrared red (FT-IR) spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) spectroscopy, atomic force microscopy (AFM) and transmission electron microscopy (TEM) techniques. From TF-XRD results, the peaks at 2θ values of 25.14, 32.12, 68.73 and 70.11 confirm the presence of TiO₂. The TiO₂ is crystalline in nature and the crystallite size is about 32.4 nm. SEM-EDX, TEM and AFM show that the coated surface is uniform and nanoporous. FT-IR analysis shows that the peak in the range of 692 cm^?1 is assigned to Ti–O–Ti stretching vibration. Contact angle measurements show that the coating is hydrophilic in nature. Bioactivity of the coating in simulated body fluid (SBF) was also examined, the hydroxyl functionalized surface greatly enhances the hydroxyapatite growth. The potentiodynamic polarization studies prove that the corrosion resistance of the TiO₂ coated surface after immersion in SBF for 7 days is improved dramatically. Cell adhesion studies confirm the increased cell attachment on TiO₂ coated surface when compared to uncoated alloy, due to less amount of Mg ion release from the substrate in the culture medium.     

Very Facile Polarity Umpolung and Noncovalent Functionalization of Inorganic Nanoparticles: A Tool Kit for Supramolecular Materials Chemistry

The facile assembly of shell‐by‐shell (SbS)‐coated nanoparticles [TiO₂?PAC₁₆]@shell 1 – 7 (PAC₁₆=hexadecylphosphonic acid), which are soluble in water and can be isolated as stable solids, is reported. In these functional architectures, an umpolung of dispersibility (organic apolar versus water) was accomplished by the noncovalent binding of ligands 1 – 7 to titania nanoparticles [TiO₂?PAC₁₆] containing a first covalent coating with PAC₁₆. Ligands 1 – 7 are amphiphilic and form the outer second shell of [TiO₂?PAC₁₆]@shell 1 – 7 . The tailor‐designed dendritic building blocks 3 – 5 contain negative and positive charges in the same molecule, and ligands 6 and 7 contain a perylenetetracarboxylic acid dimide (PDI) core ( 6 / 7 ) as a photoactive reporter component. In the redox and photoactive system [TiO₂?PAC₁₆]@shell 7 , electronic communication between the inorganic core to the PDI ligands was observed.     

Investigations on SnO2–TiO2 composite photoelectrodes for corrosion protection

Different compositions of SnO₂–TiO₂ composite electrode coatings were prepared on conducting ITO glass substrates and photoelectrochemical measurements were carried out on the coated substrates under illumination with ultraviolet light. Photopotential as well as polarization measurements were made on the samples to evaluate their performance with regard to application for cathodic protection of metals against corrosion. A composite electrode bearing SnO₂ and TiO₂ in a 1:1 molar ratio was found to exhibit the maximum photocurrent and a maximum lowering of potential under illumination when compared to the other compositions. A possibility of using a pure SnO₂ coating for cathodic protection of metals against corrosion under dark conditions was also explored.     

The preparation of superhydrophilic surface of TiO2 coating without ultraviolet irradiation through annealing treatment

The superhydrophilic surface without ultraviolet light irradiation is obtained only through the modulation of annealing process on surface morphology of TiO₂ coating. Meantime, the influence of annealing temperature on the structural, optical and wetting properties of the TiO₂ coating is investigated. As the increase of annealing temperature, the root mean square roughness of the TiO₂ coating surface increases from 8.6 to 30.7 nm and the nanoparticle surface is formed. Meanwhile, the refractive index increases linearly from 2.02 to 2.22, the thickness decreases from 120 to 82 nm, the transmittance varies from 90 to 62 %, and it is more important the WCA is reduced from 68° to 0°. Furthermore, through analyzing the thickness variation, it is illustrated that the structure variation of TiO₂ coating includes the removal process of solvent and the crystallization process with the increase of annealing temperature, and the 400 °C is a critical temperature. When the annealing temperature is above 400 °C, the TiO₂ coating starts to be crystallized and exhibits excellent antifogging property.     

Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

RuO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript> mixed oxide composite coating for improvement of Al-alloy sacrificial anodes

It has been recently proved that RuO₂ can act as an effective surface activator of aluminum alloy sacrificial anodes. TiO₂ has the property of stabilizing RuO₂ coating and resisting biofouling on metal surfaces. Hence, a mixed oxide catalytic coating of TiO₂ and RuO₂ can enhance the galvanic performance of aluminum alloy sacrificial anodes and resists biofouling on the anode surface. In the present work RuO₂–TiO₂ mixed oxide was coated on aluminum alloy sacrificial anodes. The large and uniform porous nature of the coating was found to facilitate efficient ion diffusion. The coating was found to persist on the anode even after 3 months of galvanic exposure. The anode having an optimum combination of the mixed oxide had 70% TiO₂ as the major component in the coating. The catalytic coating significantly improved the performance of the anodes to a large extent.     

Removal Mechanism Investigation of Ultraviolet Induced Nanoparticle Colloid Jet Machining

Ultraviolet induced nanoparticle colloid jet machining is a new ultra-precision machining technology utilizing the reaction between nanoparticles and the surface of the workpiece to achieve sub-nanometer ultra-smooth surface manufacturing without damage. First-principles calculations based on the density functional theory (DFT) were carried out to study the atomic material removal mechanism of nanoparticle colloid jet machining and a series of impacting and polishing experiments were conducted to verify the mechanism. New chemical bonds of Ti-O-Si were generated through the chemical adsorption between the surface adsorbed hydroxyl groups of the TiO₂ cluster and the Si surface with the adsorption energy of at least −4.360 eV. The two Si-Si back bonds were broken preferentially and the Si atom was removed in the separation process of TiO₂ cluster from the Si surface realizing the atomic material removal. A layer of adsorbed TiO₂ nanoparticles was detected on the Si surface after 3 min of fixed-point injection of an ultraviolet induced nanoparticle colloid jet. X-ray photoelectron spectroscopy results indicated that Ti-O-Si bonds were formed between TiO₂ nanoparticles and Si surface corresponding to the calculation result. An ultra-smooth Si workpiece with a roughness of Rq 0.791 nm was obtained by ultraviolet induced nanoparticle colloid jet machining.     

Basic Indole Ring Enantiomer Separation on Cellulose Tris(3,5‐dimethylphenylcarbamate) Coated TiO2/SiO2 Chiral Stationary Phase

Abstract

Cellulose tris(3,5‐dimethylphenylcarbamate) (CDMPC) coated TiO₂/SiO₂ has been prepared by coating CDMPC on TiO₂/SiO₂ which consists of micrometer‐sized silica spheres as core and nanometer‐sized titania particles as surface coating. Eight basic indole ring derivative enantiomers were separated on this CDMPC coated CSP and symmetrical peaks were obtained using hexane as the mobile phase and various alcohols as modifiers. The influence of the mobile phase composition and structural variation of the solutes on the enantioseparation was investigated and discussed.