Effects of plasma treatments for improving extreme wettability behavior of cotton fabrics

A simple, environmentally benign and energy efficient process for fabricating single faced superhydrophilic/hydrophobic cotton fabrics by controlling surface texture and chemistry at the nano/microscale is reported here. Stable ultra-hydrophobic surfaces with advancing and receding water droplet contact angles in excess of 146° as well as extreme superhydrophilic surfaces are obtained. Hydrophobic water-repellent cotton fabrics were obtained following plasma treatment through diamond-like carbon (DLC) coating by plasma enhanced chemical vapour deposition. The influence of changing different precursor’s plasma pre-treatments such as H₂, Ar or O₂ on the properties of DLC coatings is also evaluated using atomic force microscopy, X-ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, and analysed in terms of contact angle measurements. Because of the DLC coating, the coated fabric showed to endure its superhydrophobic character even after 12 months.     

Effect of zinc oxide on flame retardant finishing of plasma pre-treated cotton fabric

An organic phosphorus compound (flame retardant agent, FR) in combination with a melamine resin (crosslinking agent, CL), phosphoric acid (catalyst, PA) and zinc oxide (co-catalyst, ZnO/nano-ZnO) imparted effective and durable flame retardant properties. Also, atmospheric pressure plasma jet was applied as pre-treatment to improve post-finishing (flame retardant finishing) on cotton fabrics. In the present paper, surface morphology, chemical structure analysis, combustibility and mechanical properties of plasma pre-treated cotton fabrics subjected to flame-retardant treatment were investigated. Surface morphology of treated cotton specimens showed roughened and wrinkled fabric surface with high deposition of the flame retardant finishing agent, which was caused by the plasma etching effect and attack of acidic FR. The FTIR-ATR spectra for the treated cotton specimens showed some new characteristic peaks in chemical structure, interpreted as carbonyl bands, OH stretching vibration, COO⁻ stretching vibration, CH₂ rocking band and CH₃ asymmetric and CH₂ symmetric stretching. Moreover, FR-CL-PA-treated specimens showed remarkable flame-retardant property, which was further improved by the plasma pre-treatment and ZnO/nano-ZnO co-catalyst. However, flame-retardant-treated cotton specimens had poor mechanical strength when compared with control sample, resulting from side effects of the crosslinking agent used, while plasma pre-treatment and ZnO/nano-ZnO co-catalyst may compensate for the reduction in tensile and tearing strength caused by flame-retardant agents.     

Functionalization of cotton fabrics with corona/air RF plasma and colloidal TiO2 nanoparticles

This study discusses the possibility of using a corona discharge at atmospheric pressure and air RF plasma at low pressure for the cotton fibre activation prior to deposition of colloidal TiO₂ nanoparticles in order to enhance antibacterial, UV protective and self-cleaning properties. X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of TiO₂ nanoparticles on the surface of cotton fibres. XPS elemental mapping indicated that TiO₂ nanoparticles were more evenly distributed across the surface of untreated and corona pre-treated cotton fabrics in comparison with RF plasma pre-treated fabric. Atomic absorption spectroscopy measurements revealed that the equivalent total content of TiO₂ in the cotton fabrics pre-treated by corona and RF plasma was 31% higher than in the fabric that did not undergo any treatment prior to loading of TiO₂ nanoparticles. In order to achieve maximum bacteria (Gram-negative bacteria Escherichia coli) reduction, untreated cotton fabric had to be loaded with colloidal TiO₂ nanoparticles twice, but only once following corona or RF plasma pre-treatment. Deposition of TiO₂ nanoparticles onto cotton fabrics provided maximum UV protective rating of 50+. Extraordinary photocatalytic activity of TiO₂ nanoparticles deposited onto cotton fabrics was proved by self-cleaning of blueberry juice stains and photodegradation of methylene blue in aqueous solution under UV illumination.     

The influence of Ti plasma etching pre-treatment on mechanical properties of DLC film on cemented carbide

The pre-treatment of substrate surface had been a key part of DLC film preparation to improve mechanical and tribological properties. Ti plasma etching pre-treatment was investigated in this paper as a new effective surface pre-treatment method to substitute transition layer. This pre-treatment used high-energy Ti plasma to impact substrate surface. Ti plasma etched the substrate to a depth of 407 nm and increased the roughness from 1.36 to 40.39 nm. A trace layer of substrate, together with cobalt, oxides, and other impurities, was removed. Ti plasma broke some top WC crystals and combined with the free carbon ions separating from the substrate. A DLC film was deposited on the etched surface. Compared with DLC films deposited on the untreated substrate and Ti transition layer, the DLC film on the Ti plasma etched substrate had best adhesion strength of 34.14 N. The three DLC films had the same sp³ bonding carbon content, but Ti plasma etching treatment could promote the formation of sp³ bonds on the interface of substrate and DLC film. This DLC film had low friction coefficient of 0.12 and low wear rate of 5.11 × 10⁻⁷ mm³/m·N. In summary, Ti plasma etching pre-treatment could significantly improve the adhesion of DLC film and keep its excellent tribological properties.     

High efficiency ultra-deep dyeing of cotton via mercerization and cationization

A potentially environmentally responsible dyeing procedure for ultra-deep shades on cotton was developed using a cationization method in combination with mercerization. The effects of both treatments on dyeing performance and colorfastness properties of cotton fabrics dyed with reactive dyes were analyzed individually and in combination. Both mercerization and cationization have been proved to be effective in increasing the depth of shade on cotton. The colorfastness properties, except colorfastness to wet crocking, of mercerized–cationized cotton fabrics dyed without salt were much better than untreated cotton dyed using a conventional dyeing procedure. Unlike untreated cotton fabrics, the concentration of Na₂CO₃ in the dyeing process of mercerized–cationized cotton fabrics was lowered from 20 to 5 g/L without compromising dye fixation and colorfastness properties. With low concentrations of dyes and Na₂CO₃ and no electrolyte in the dye bath effluent, the dyeing procedure of mercerized–cationized cotton fabrics for ultra-deep shades is potentially a more environmentally benign method than conventional dyeing with reactive dyes.     

Influence of Cotton Pre-Treatment on Dyeing with Onion and Pomegranate Peel Extracts

In this paper the possibility of applying natural dyes on cellulose fibres were researched with respect to the impact of cotton material pre-treatment (scouring, chemical bleaching, mercerization and mordanting), using renewable sources of natural dyes (waste as a source). As mordants, metal salts of copper, aluminium and ferrum were used, and the influence on colour change as well as on fastness properties were analysed. The natural dyes were extracted from onion peel (Allium cepa L.) and pomegranate peel (Punica granatum L.). In spectrophotometric analysis performed of the plant extracts, the onion extract has peaks at 400 and 500 nm, resulting in red-orange colourations and the pomegranate extract shows a maximum at 400 nm, i.e., in the yellow region, which is characteristic of punicalin. Results show significant influence of cotton pre-treatments on colour appearance and fastness properties, caused by pre-treatments affecting the properties and structure of the cotton itself. The positive effect of mercerization on dye absorption and bonding is confirmed. For wash and light fastness properties, more satisfactory results have been obtained for yarns dyed with pomegranate peel natural dye, and the key importance of mordants for fastness properties has been confirmed.     

Novel cotton cellulose by cationization during mercerization—part 2: the interface phenomena

Cationisation during the mercerisation process with an epihalohydrin results in novel cotton cellulose that gives a new dimension to cotton pre-treatment and finishing. The modified cotton retains all the beneficial properties of mercerised cotton with a change of the surface charge that ensures further quality improvement. The present paper deals with systematic investigations of the interface phenomena of cationised cotton fabric with an epihalohydrin; 2,3-epoxypropyl trimethyl ammonium chloride during and after mercerisation process. The water, ionic surfactant and dyestuff adsorption, as well as surface free energy, electrokinetic potential, isoelectric point and point of zero charge determined according to the streaming current/streaming potential method; and specific amount of surface charge of modified cotton fabrics are researched.     

Preparation and characterization of flame‐retardant lamellar Mg(OH)2 thin films on citric acid‐treated cotton fabrics

Preparation and characterization of lamellar magnesium hydroxide (Mg(OH)₂) thin films on cotton fabrics are reported in this paper. Mercerized cotton fabrics were treated with citric acid, so carboxyl groups were introduced to the surface of the fabrics. Mg(OH)₂ seeds were first adsorbed on the citric acid‐treated cotton fabrics and then Mg(OH)₂ thin films grew on the fabric through secondary growth method. Kinetics and isotherm studies found that the adsorption of Mg(OH)₂ seeds on citric acid‐treated cotton fabrics followed pseudo second‐order kinetic model and Langmuir isotherm. This indicated that Mg(OH)₂ seeds adsorption was monolayer chemical adsorption driven by electric attraction between positively charged Mg(OH)₂ seeds and ? COO^? ions on the cotton fiber surface. The X‐ray diffraction (XRD) and SEM characterizations of the Mg(OH)₂ thin films covered cotton fabrics found that standing flaky Mg(OH)₂ crystals formed a shell of porous but continuous network on cotton fabric surface. Owing to the Mg(OH)₂ thin film covering, the fabric had fireproof property, lower thermal conductivity and higher optical absorbance in the UV, Vis and IR regions. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural,chemical and nanomechanical investigations of SiC/polymeric a-C:H films deposited by reactive RF unbalanced magnetron sputtering

Amorphous carbon (or diamond-like carbon, DLC) films have shown a number of important properties usable for a wide range of applications for very thin coatings with low friction and good wear resistance. DLC films alloyed with (semi-)metals show some improved properties and can be deposited by various methods. Among those, the widely used magnetron sputtering of carbon targets is known to increase the number of defects in the films. Therefore, in this paper an alternative approach of depositing silicon-carbide-containing polymeric hydrogenated DLC films using unbalanced magnetron sputtering was investigated. The influence of the C₂H₂ precursor concentration in the deposition chamber on the chemical and structural properties of the deposited films was investigated by Raman spectroscopy, X-ray photoelectron spectroscopy and elastic recoil detection analysis. Roughness, mechanical properties and scratch response of the films were evaluated with the help of atomic force microscopy and nanoindentation. The Raman spectra revealed a strong correlation of the film structure with the C₂H₂ concentration during deposition. A higher C₂H₂ flow rate results in an increase in SiC content and decrease in hydrogen content in the film. This in turn increases hardness and elastic modulus and decreases the ratio H/E and H³/E². The highest scratch resistance is exhibited by the film with the highest hardness, and the film having the highest overall sp³ bond content shows the highest elastic recovery during scratching.     

Surface and bulk cotton fibre modifications: plasma and cationization. Influence on dyeing with reactive dye

The surface of cotton fabrics was functionalized through corona plasma treatments and/or by cationising the whole of the fibre with an epihalohydrin. The effects of both treatments, individually and in combination are analyzed through wettability studies, by X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), and also by dyeing studies with an hetero bis functional reactive dye. Plasma improved wetting properties, exhaustion of the dyebaths and K/S_corr of the fabrics through surface functionalisation. Cationising of the cotton highly increased the exhaustion of the dyebaths and produced a dramatic improvement in K/S_corr. Plasma treatment previous to cationising increased the impregnation of the fabrics, but the effects of both treatments on dyeing parameters are additive only in column water rise and generally the effects obtained by cationising with the epihalohydrin prevail. The differences between both treatments are discussed in terms of surface functionalisation of the cotton fibres.     

Using graphene/TiO2 nanocomposite as a new route for preparation of electroconductive,self-cleaning,antibacterial and antifungal cotton fabric without toxicity

A novel and efficient process is reported for fabrication of electroconductive, self-cleaning, antibacterial and antifungal cellulose textiles using a graphene/titanium dioxide nanocomposite. Cotton fabric was loaded with graphene oxide using a simple dipping coating method. The graphene oxide-coated cotton fabrics were then immersed in TiCl₃ aqueous solution as both a reducing agent and a precursor to yield a fabric coated with graphene/titanium dioxide nanocomposite. The crystal phase, morphology, microstructure and other physicochemical properties of the as-prepared samples were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and UV-Vis reflectance spectroscopy. Electrical resistance, self-cleaning performance, antimicrobial activity and cytotoxicity of treated fabrics were also assessed. The electrical conductivity of the graphene/titanium dioxide nanocomposite-coated fabrics was improved significantly by the presence of graphene on the surface of cotton fabrics. The self-cleaning efficiency of the treated fabrics was tested by degradation of methylene blue in aqueous solution under UV and sunlight irradiations. The results indicated that the decomposition rates of methylene blue were improved by the addition of graphene to the TiO₂ treatment on fabrics. Moreover, the graphene/titanium dioxide nanocomposite-coated cotton samples had negligible toxicity and possessed excellent antimicrobial activity.     

Isoelectric points of plasma‐modified and aged silicon oxynitride surfaces measured using contact angle titrations

Acid‐base properties of metal oxides and polymers can control adhesion properties between materials, electrical properties, the physical structure of the material and gas adsorption behavior. To determine the relationships between surface isoelectric point, chemical composition and aging effects, plasma‐surface treatment of amorphous silicon oxynitride (SiO_xN_y) substrates was explored using Ar, H₂O vapor, and NH₃ inductively coupled rf plasmas. Overall, the Ar plasma treatment resulted in nonpermanent changes to the surface properties, whereas the H₂O and NH₃ plasmas introduced permanent chemical changes to the SiO_xN_y surfaces. In particular, the H₂O plasma treatments resulted in formation of a more ordered SiO₂ surface, whereas the NH₃ plasma created a nitrogen‐rich surface. The trends in isoelectric point and chemical changes upon aging for one month suggest that contact angle and composition are closely related, whereas the relationship between IEP and composition is not as directly correlated. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface modification of cotton fabrics by transesterification with ion-paired subtilisin Carlsberg in solvents

The transesterification-active enzyme subtilisin Carlsberg was successfully solubilized into organic solvents such as isooctane by enzyme–bis(2-ethylhexyl) sulfosuccinate (AOT) ion-pairing while retaining its natural secondary structure and catalytic activity. The optimal CaCl₂ concentration and pH for enzyme extraction were 2 mM and 5.0, respectively, while the optimal pH for transesterification capability of enzyme was around 7.5. Within the critical micellar concentration (CMC) of AOT in isooctane, increasing the initial AOT concentration enhanced the extraction efficiency. As the hydrophobicity of the solvent decreased, so did the catalytic efficiency of the enzyme, while transesterification of cotton fabrics (medical gauze and knitted cotton cloth) occurred only in less hydrophobic solvents such as toluene. Transesterification was verified by infrared spectral analysis. The final degree of substitution (DS, the number of propionate groups per cellulose monosaccharide unit) of the medical gauze and knitted cotton cloth was 0.00282 and 0.00228, respectively. The surface properties of the modified cotton fabrics were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetry, water contact angle, etc.     

Structural,optical and secondary electron emission properties of diamond like carbon thin films deposited by pulsed-DC plasma CVD technique

Plasma enhanced chemical vapor deposition (PECVD) technique using pulsed-DC power supply was used to fabricate diamond like carbon (DLC) films at deposition rates as high as 110 nm/min. The DLC films deposited by pulsed-DC and DC based power supplies under different gas flow ratios were studied for their suitability as dielectric layer coatings in plasma display panels (PDPs). The effect of deposition parameters on the properties of the DLC films were studied using Fourier transform infra-red spectroscopy (FTIR) and spectroscopic ellipsometry (SE). FTIR reveals that higher hydrogen dilution in gas mixture leads to higher sp³ content. SE studies in wide spectral range were analyzed using Tauc-Lorentz model dielectric function. A rise in the extracted refractive index was seen on increasing the H₂ content in the feed gas, thus resulting in optically denser films. Secondary electron emission coefficient (γ) was measured in the films deposited by the DC and pulsed-DC based PECVD. Firing voltage in the DLC samples was found to have very low variation in the operating pressure range used in commercial PDPs, suggesting possibility of enhanced long term reliability of DLC coatings in future PDP applications.     

Enhanced Self‐Cleaning Properties on Polyester Fabric Under Visible Light Through Single‐Step Synthesis of Cuprous Oxide Doped Nano‐TiO2

Nowadays, introducing self‐cleaning properties on various fabrics under daylight irradiation for automotive and upholstery application is in a central point of research. This can be achieved by application of metal‐doped TiO₂ nano particles on the textile fabrics. Here, alkali hydrolysis of polyester fabric has been carried out along with synthesis of Cu₂O/TiO₂ nanoparticles in a single‐step process by using sonochemical technique. CuSO₄.5H₂O was used as a source of copper in the presence of glucose as reducing and stabilizing agent. Moreover, central composite design based on response surface methodology (RSM) was used to determine the role of variables (CuSO₄.5H₂O, glucose and pH) and their effects on the self‐cleaning properties and weight of the fabric. The self‐cleaning property was investigated by degradation of Methylene blue on the surface of the treated fabrics under daylight. Further, the tensile properties, colorimetric measurement, and washing fastness of the treated fabric produced in the optimum conditions were investigated. The morphology of Cu₂O/TiO₂ nanoparticles was examined using X‐ray diffraction and field emission scanning electron microscopy (FESEM). The new polyester fabric obtained through in situ synthesis of Cu₂O/TiO₂ nanoparticles can be used as a desirable stable fabric with high tensile strength and visible‐light self‐cleaning properties.     

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.     

A One‐Step Process for the Antimicrobial Finishing of Textiles with Crystalline TiO2 Nanoparticles

Titanium oxide (TiO₂) nanoparticles (NPs) in their two forms, anatase and rutile, were synthesized and deposited onto the surface of cotton fabrics by using ultrasonic irradiation. The structure and morphology of the nanoparticles were analyzed by using characterization methods such as XRD, TEM, STEM, and EDS. The antimicrobial activities of the TiO₂–cotton composites were tested against Escherichia coli (Gram‐negative) and Staphylococcus aureus (Gram‐positive) strains, as well as against Candida albicans. Significant antimicrobial effect was observed, mainly against Staphylococcus aureus. In addition, the combination of visible light and TiO₂ NPs showed enhanced antimicrobial activity.     

Characterization of cerium-based conversion coatings for corrosion protection of AISI-1010 commercial carbon steel

The role of hydrogen peroxide in the formation of cerium conversion coatings by immersing AISI 1010 commercial carbon steel substrates into solutions containing various concentrations of CeCl₃ (0.1, 1, and 10 g L⁻¹) has been investigated as an alternative method for their protection against corrosion. The deposits prepared from the solutions with H₂O₂ consist of yellow thin and non-uniform coatings with agglomerates of small CeO₂ and Ce₂O₃ crystallites whose sizes increased over the metallic surface as the cerium concentration was increased. Cerium pre-treatments in the presence of H₂O₂ displayed layers that were rougher than those synthesized without H₂O₂. A comparison with the chromate conversion pre-treatment is also simultaneously carried out with the discussion of the possible reactions involved in the different stages of process. The coating obtained from the solution containing 0.1 g in 1,000 mL produced better corrosion resistance on the substrate than that observed for its counterparts due to the fact that the surface was more uniformly covered by the conversion coating. The addition of H₂O₂ to the cerate baths improves visible roughness, corrosion resistance of the conversion coatings and bond strength because hydrogen peroxide acts as an oxygen source during the formation of the coatings.     

Textile grade long natural cellulose fibers from bark of cotton stalks using steam explosion as a pretreatment

Textile grade long natural cellulose fibers with fineness of 27 dtex have been extracted from bark of cotton stalks by a combination of steam explosion, potassium hydroxide and peroxide treatments (explosion–KOH–H₂O₂). It was reported that natural cellulose fibers from bark of cotton stalks had significantly better mechanical properties than those from other lignocellulosic agricultural byproducts such as rice and wheat straws. Fibers from bark of cotton stalks were used to reinforce thermoplastic composites but could not be spun into yarns for textile applications due to their high fineness value (around 50 dtex) and/or low aspect ratio (around 660). In this research, barks of cotton stalks were treated using three methods, including steam explosion, a combination of steam explosion and potassium hydroxide treatments (explosion–KOH) and explosion–KOH–H₂O₂. The morphology, composition, carding yield, crystalline structures and tensile properties of three different cotton stalk fibers were analyzed. Results showed that cotton stalk fibers extracted by explosion–KOH–H₂O₂ had the lowest fineness value of 27 dtex and moderate aspect ratio of 1,150 in three kinds of fibers. The fibers also had most clean and smooth surfaces, highest carding yield of 68.6 %, and highest cellulose content of 82.1 wt% due to effective removal of non-cellulose impurities. Moreover, the fibers had tensile properties close to cotton fibers. Overall, the cotton stalk fibers presented a better potential to be used as textile fibers than those reported by previous researches. explosion–KOH–H₂O₂ could be an efficient method for exploring textile applications of bark of cotton stalks.     

In situ growth of MnO2 on pDA-templated cotton fabric for degradation of formaldehyde

Degradation of formaldehyde (HCHO) in interior decoration has been an urgent issue due to its toxicity nature and potential threats to human health. In this work, manganese dioxide nanoparticles (MnO₂ NPs) were in situ grown on the polydopamine (pDA)-templated cotton fabrics for environmentally friendly HCHO degradation applications. The morphology, elemental composition, and crystal structure of the cotton/pDA/MnO₂ were characterized by scanning electron microscopy–energy dispersive X-ray spectrum, Fourier transform infrared, X-ray diffractometer and X-ray photoelectron spectroscopy, respectively. The degradation of HCHO by the as-developed cotton/pDA/MnO₂ was measured in a self-made quartz reactor, and the stability of adsorption was evaluated by cyclic experiments. The results showed that the HCHO removal efficiency reached to 100% within 20 min after three cycles, suggesting that the as-prepared fabrics exhibited good stability for the degradation of HCHO. The development of MnO₂ NPs coated fabrics provides new strategies in degradation HCHO in interior decoration.