Synthesis and properties control of fluorinated organic-inorganic hybrid films

Fluorinated organic-inorganic hybrid films were prepared by free-radical random copolymerization and sol-gel process through dodecafluoroheptyl methacrylate (DFMA), vinyltriethoxysilane (VTES), and tetramethoxysilane (TMOS). It was found that the prepared fluorinated organic-inorganic hybrid film was very hydrophobic and exhibits excellent water repellency. Hydrophobic fluorocarbon side chains were preferentially enriched to the outermost layer at the interface of coating film-air, and three layers probably exist in the coating films. The fluorinated hybrid films possessed fluorocarbon side chains orient toward the air originating from DFMA as the top layer, hydrocarbon backbone chain originating from vinyl polymerization as the middle layer, and silica network originating from the hydrolysis and condensation of siloxane as the bottom layer. It demonstrated that most of TMOS added might be arranged to the bottom layer of the fluorinated hybrid films, and had a slight impact on the enrichment of fluorocarbon side chains of the outermost layer. However, the useful properties of the fluorinated organic-inorganic hybrid films such as thickness and corrosion resistant can be significantly improved by the increase of TMOS content.     

Effect of sequence structure on wetting behaviors of fluorinated methacrylate polymers based on perfluorohexylethyl methacrylate and stearyl acrylate

Due to the non-crystalline properties of short chain perfluoroalkyl groups,using short chain perfluoroalkyl to stabilize low surface free energy polymers has been a challenging task.In this study,we prepare a series of random copolymers poly(perfluorohexylethyl methacrylate)-co-poly(stearyl acrylate) (P13FMA-co-PSA) and block copolymers poly(perfluorohexylethyl methacrylate)-b-poly(stearyl acrylate) (P13FMA-b-PSA),and systematically investigate the effects of the sequence structure and the content of 13FMA of the fluorinated copolymers on surface free energy and surface reorganization.Static/dynamic contact angle goniometry and water/oil repellency analyses demonstrate that the random polymer P13FMA-co-PSA could not achieve low surface free energy and low surface reorganization at the same time.In contrast,for the block copolymer P13FMA-b-PSA,both low surface free energy and low surface reorganization are acquired simultaneously.The results of X-ray photoelectron spectroscopy (XPS),dynamic contact angle goniometry and differential scanning calorimetry (DSC) reveal the above-mentioned properties.The consecutive 13FMA segments improve the surface fluorine density,while the consecutive SA chains enhance the crystallinity of the SA segments,and further hinder the surface reorganization of the perfluoroalkyl groups.Therefore,P13FMA-b-PSA exhibits a higher utilization efficiency of fluorine atoms and a better structural stability than P13FMA-co-PSA.     

Insecticidal,Repellent and Antifeedant Activity of Essential Oils from Blepharocalyx cruckshanksii (Hook. & Arn.) Nied. Leaves and Pilgerodendron uviferum (D. Don) Florin Heartwood against Horn Flies,Haematobia irritans (Diptera: Muscidae)

Haematobia irritans is a cosmopolitan obligate blood-feeding ectoparasite of cattle and is the major global pest of livestock production. Currently, H. irritans management is largely dependent on broad-spectrum pesticides, which has led to the development of insecticide resistance. Thus, alternative control methods are needed. Essential oils have been studied as an alternative due to their wide spectrum of biological activities against insects. Thus, the main aim of this study was to evaluate the insecticidal, repellent and antifeedant activity of the essential oils from Blepharocalyx cruckshanksii leaves and Pilgerodendron uviferum heartwood against horn flies in laboratory conditions. The composition of the essential oils was analyzed using gas chromatography coupled to mass spectrometry. Accordingly, α-pinene (36.50%) and limonene (20.50%) were the principal components of the B. cruckchanksii essential oil, and δ-cadinol (24.16%), cubenol (22.64%), 15-copaenol (15.46%) and δ-cadinene (10.81%) were the most abundant compounds in the P. uviferum essential oil. Mortality of flies and feeding behavior were evaluated by non-choice tests, and olfactory response was evaluated using a Y-tube olfactometer. Both essential oils were toxic to horn flies, with LC₅₀ values for B. cruckchanksii essential oil of 3.58 µL L⁻¹ air at 4 h, and for P. uviferum essential oil of 9.41 µL L⁻¹ air and 1.02 µL L⁻¹ air at 1 and 4 h, respectively. Moreover, the essential oils exhibited spatial repellency in the olfactometer using only 10 µg of each oil, and these significantly reduced the horn fly feeding at all doses evaluated. Although further laboratory and field studies related to the insectistatic and insecticide properties of these essential oils against H. irritans are necessary, B. cruckshanksii leaves and P. uviferum heartwood essential oils are promising candidates for horn fly management.     

含氢硅油表面接枝改性PET织物的拒水性能

通过接枝率、接触角、透水时间、拉伸应力应变、ＥＳＣＡ的测定以及不冲击实验研究了在ＤＣＰ和ＢＰ等存在下电晕放电引发含氢硅油接枝ＰＥＴ织物及其拒水性能,实验结果表明：电晕放电能有效引发含氢硅油在ＰＥＴ织物表面的接枝共聚反应,随电晕放电处理时间的延长,ＰＥＴ织物表面接枝率增大;接枝后ＰＥＴ织物拒水效果明显增强;电晕放电引发接枝改性后ＰＥＴ织物无损伤,力学性能基本保持不变。     

The Controllable Surface Morphology of Polyimide (PI) Electrospun Fibers

Electrospun materials have been proposed for application for gas filtration, drug carriers, and tissue engineering. The surface morphology of electrospun fibers is the key for consideration for the above applications, such as pore size on the fiber surface, surface area, and roughness. In this work, we investigated the influence of polymer/solvent properties on soluble polyimide (PI) fibers. The studied PIs included three fluorinated aromatic polyimides containing naphthalene pendant groups. By using various solvents we adjusted the size, shape, and structure of the fibers. As a result, PI electrospun fibers could be achieved with width around 10 μm. The rough and smooth surface morphologies were studied by scanning electron microscopy (SEM). Surface wettability of the electrospun fiber membranes were characterized by contact angle measurement. The contact angles on the electrospun PI fiber mats for water and glycerol were in the range of 137.6°–144.5° and 139.1°–143.6°, respectively. Moreover, the rough fiber surface could make the electrospun fiber membrane possess good adhesive force for liquids. The results suggest that we could widen the application of electrospun membranes through controlling the fiber morphology.     

Superhydrophobic polymer‐particle composite films produced using various particle sizes

Hydrophilic alumina (Al₂O₃) nanoparticles (25, 35, and 150 nm) are dispersed in different concentrations in solutions of a commercial hydrophobic poly(alkyl siloxane) (Silres BS‐290), and the suspensions are sprayed on glass surfaces. Static contact angles (θ_S), measured on surfaces of siloxane‐nanoparticle composite films that were prepared from dilute dispersions, increase rapidly with particle concentration. Composite films prepared from concentrated dispersions exhibit a maximum, constant θ_S (at saturation θ_S is 160°), which is not affected by the size of the particles. These films exhibit also very small contact angle hysteresis (5°), which is also independent of the particle size. Consequently, the same superhydrophobic character can be induced in siloxane films using nanoparticles, which can range from a few up to several tenths of nanometers. However, the particle size and more precisely the particle specific surface area affects dramatically the minimum critical particle concentration, which must be used in the dispersions to induce superhydrophobicity on the surface of the composite films, that is, to achieve θ_S = 150°. It is shown that critical particle concentration decreases exponentially with specific surface area. This result can be important for manufacturers of superhydrophobic surfaces who are interested in having a good control on the wettability of the composite films. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of dichlorodimethylsilane on plasma-treated cotton fabric

Cotton fabric was treated with dichlorodimethylsilane (DCDMS) solution by two methods. In the first method, the fabrics were directly dipped into DCDMS solution for different time intervals and in the second method, the fabric was first subjected to radiofrequency (RF) plasma treatment for different durations and optimized exposure power condition and then immersed in DCDMS solution. The physical properties of cotton fabrics, treated with DCDMS in the presence/absence of air plasma have been compared with those of the control fabrics. Changes in the surface morphology structure and composition were observed through scanning electron microscopy and attenuated total reflectance-IR. The change in colour parameters of the fabric due to the treatment was assessed by Dataflash 100 colour measurement spectrophotometer with colourtools QC 1.3 colour quality software. The water repellent property of untreated and modified fabrics was studied using AATCC test method 39 (1971). The effectiveness of the water repellent property was checked by washing the treated fabrics up to ten cycles. Article presented at the International Conference on the Frontiers of Plasma Physics and Technology, 9–14 December 2002, Bangalore, India.     

Room temperature synthesis of water repellent silica coatings by the dip coat technique

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings onto stainless steel substrates using 1,1,1,3,3,3-hexamethyldisilazane as a surface modifying agent. The hydrophobic property of the silica coating was enhanced by increasing its surface roughness, which was achieved by a proper control over the MeOH/TMOS molar ratio (S) during the synthesis. The contact angle of a water droplet (10 μl) increased from 72° to 145° with an increase in the S value from 9.1 to 36.4. The silica coating showed a minimum sliding angle of 15° for a water droplet of 10 μl. The water repellent silica coatings are thermally stable up to a temperature of 340 °C. The results have been discussed by taking into consideration the contact angle measurements, surface morphology and sol-gel parameters.     

Fabrication and superhydrophobicity of fluorinated titanium dioxide nanocoatings

This study demonstrates the fabrication of a stable superhydrophobic surface with low contact angle hysteresis (CAH) using an arrangement of nanoscale TiO₂ spheres. The control of precursor quantity is selected as the key factor in determining surface roughness that significantly intensifies water contact angle (CA) of TiO₂ films. After surface fluorination treatment, the anatase-type crystalline surfaces exhibit good water repellency (CA 166.1°), low CAH (6°), and superhydrophobic stability (>60 min). Enhanced water repellency is attributed to the fact that the higher density of TiO₂ spheres results in more tortuous three-phase contact line, leading to the self-cleaning effect. Such a unique textured surface imparts many promising potentials for engineering and the development of optics devices with robust superhydrophobic materials.     

Water and oil repellency of flexible silica-coated polymeric substrates

A facile coating technique was used for the one-step creation of silica-sphere layers onto flexible polypropylene (PP) substrates, which showed the enhanced repellency toward liquid droplets with different surface tensions, ranging from 25.6 to 72.3 mN/m. One-step solution preparation comprised the homogenous mixing of colloidal silica nanospheres and perfluoroalkyl methacrylic copolymer, and the resulting F-silica slurry was subsequently deposited over the PP films, which showed good adhesion. The flexible silica-coated polymeric film displayed a remarkable repellency toward water and oil drops, when compared with the F-coated PP flat film. The silica-stacking layers on the PP substrate generated a roughened surface, owing to the creation of bionic surface hierarchically combined with multiple-scale architecture. To clarify this, the wetted fraction was determined from Cassie-Baxter equation, and the work of adhesion, based on Young-Duprè equation, was used to examine the sliding ability of the resulting polymeric films. The cross-cut test incorporated with film bending proved the excellent adherence between silica layer and PP substrate. A satisfactory durability in water and oil immersions for 10 days showed that the resulting PP film possesses strong adhesion and better repellency for a long period, confirming a promising commercial feasibility.