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.     

Planar step-index waveguides obtained via sol–gel synthesis from organometallic precursors

Inorganic and hybrid sols obtained from Si, Ti, Zr and Ce organometallic precursors were used to prepare single and multilayer coatings with different thicknesses. Planar step-index waveguides with different refractive indices were thus prepared by dip-coating the above sols onto commercial soda-lime glass substrates, followed by appropriate thermal annealing. The resultant coatings were characterized by transmission electron microscopy and energy dispersive X-ray spectrometry to elucidate the interface and bonding between the sol–gel derived coatings and the glass substrates. Diffusion of alkali and alkaline earth elements from the glass into the coating layer was confirmed and proposed to play a role in the coating-substrate bonding, inducing excellent optical quality planar interfaces. Optical waveguide characterization performed on a 4.15 μm thick hybrid SiO₂:CeO₂ (95:5) step-index waveguide yielded losses of 1.50 dB/cm.     

Asymmetric effects in catalytic membranes

A catalytic membrane hybrid system based on a cermet membrane with a channel size 〈d〉 of ～0.12 μm has been produced using sol-gel processing. A layer of a superfine methanol conversion catalyst with the composition Cr₂O₃ · Al₂O₃ · ZnO has been formed on the inner surface of the channels, and a thin oxide coating of composition P_0.03Ti_0.97O_{2 ± δ} with a homogeneous porous structure and 〈d〉 ～ 2 nm has been formed on the geometric membrane surface. The methanol conversion rate and the gas permeability of the membrane depend considerably on the methanol vapor and gas (H₂, He, CO₂, Ar, CH₄) flow directions. When methanol vapor diffuses toward the mesoporous layer, the catalytic activity is one order of magnitude higher and the gas permeability coefficients are 3–8 times lower than in the case of the reverse flow of the gaseous molecules. The temperature dependence of the gas permeability taking into account the possible types of mass transfer in porous solids suggests that, when the gases move toward the mesoporous coating consisting of phosphorus-modified titanium oxide, surface flow and activated diffusion dominate, whereas the reverse gas motion is dominated by free molecular flow.     

玻璃微-纳流控芯片的制备及在蛋白质电动富集中的应用

发展了一种以"二次刻蚀"技术制备玻璃微-纳流控芯片的新方法. 首先, 采用紫外光刻和化学湿法刻蚀技术在玻璃基片上加工微米深度的微通道; 去除剩余的光胶后, 在刻有微通道的基片上旋涂一层新的光胶; 再通过二次紫外光刻和湿法刻蚀在该基片上加工深度小于100 nm的纳通道; 最后, 采用室温键合技术, 将带有微纳结构的基片与盖片封合制成玻璃微-纳流控复合芯片. 利用本方法可以在普通化学实验室以简易的设备制得具有微-纳米复合结构的玻璃芯片. 将此玻璃微-纳流控复合芯片成功地应用于以电动离子捕集技术富集荧光素钠异硫氰酸酯(FITC)标记的人血清蛋白(HSA). 结果表明, 对于0.5 mg/mL的FITC-HSA, 30 s内富集倍率可达到200倍以上.     

Synthesis and coating of silica supported Nickel Oxide particles over ceramic pre-forms through sol–gel derived layered double hydroxides

Silica supported Nickel Oxide fine particles have been synthesized through sol–gel derived Ni–Al Layered Double Hydroxide (LDH) and coated over honeycomb ceramic pre-forms through dip-coating technique. The powder products of supported materials have low crystallinity, negative zeta potential, exhibit high dispersibility and suitable for further processing by coating techniques. The powder X-ray diffraction (XRD) patterns have shown that there is an increase of basal spacing by 3.02 Å in acetylacetonate intercalated LDH. The particles of <2 μm size increase with the rise of LDH component in the composite. The particles of NiO structure formed on decomposition of composites have crystallite size <20 nm. Due to the interlayer reduction of NiO crystallites, the unsupported LDH on calcination gives Ni⁰ particles of size around 4.18 nm. The Scanning Electron Microscopy (SEM) patterns of coated supported suspensions over ceramic substrates show formation of thin, crack free coats with uniform distribution of particles.     

Sol-enhanced triple-layered Ni–P–TiO2 composite coatings

A novel coating process, TiO₂ sol enhanced Ni–P electroless composite coatings on carbon steel, is presented in this paper. Transparent TiO₂ sol was added into the electroless plating Ni–P solution at a controlled rate, leading to in situ synthesis of a triple-layered Ni–P–TiO₂ composite coating, i.e. the inner, transition and outer layers. The inner layer has a thickness of ~3 μm, mainly composed of Ni and P elements. The transition layer of the coating has a relatively high content of TiO₂ with a thickness of ~500 nm and a columnar-structure. The thickness of the outer layer was ~7 μm, with almost evenly distributed Ni, P and TiO₂. The hardness and Young’s modulus of the composite coating were greatly improved to ~10 and ~200 GPa, respectively, compared to ~6 and ~110 GPa of the traditional Ni–P coating.     

Fabrication of arrays of sub-20-nm silica walls via photolithography and solution-based molecular coating

We report herein fabrication of arrays of sub-20-nm silica walls via photolithography and the surface sol-gel process. A photolithographically fabricated line template on a silicon wafer was coated with a silica nanolayer using the surface sol-gel process, and then the topmost portion of the silica layer and the template were successively removed using CHF(3) and oxygen plasma, respectively, leaving the sidewalls of the silica layers remaining on the substrate. These walls were fully self-supporting, and the thicknesses of silica wall were 6, 8, and 12 nm at 20, 30, and 60 cycles, respectively. The height/width ratio of the wall was 38 at the 30-cycle coating. This ratio is surprisingly high when compared to that of the conventional photolithography processes. Successive formation of the silica, polymer, and silica layers yielded a trilayer sidewall, and the spacer polymer layer could be selectively removed to form a doubled sidewall. Size reduction and proliferation of sub-20-nm silica wall was thus achieved. The reported method is simple and cost-efficient and opens a gateway to further miniaturization of nanostructures.     

Automated and parallel microfluidic DNA extraction with integrated pneumatic microvalves/pumps and reusable open-channel columns

A novel microfluidic DNA extraction protocol based on integrated diaphragm microvalves/pumps and silica-deposited open-channel columns was developed specifically for automated and parallel DNA solid-phase extraction (SPE). The method uses microfluidic chips with a sandwiched structure containing three layers, which are the upper fluidic layer with surface-deposited silica on glass open channels as the extraction phase, the lower actuation layer with valve actuation channels on a glass wafer, and the middle poly(dimethylsiloxane) (PDMS) membrane for reversible bonding of the two glass substrates. These two glass substrates can be reused after thoroughly cleaning and the PDMS membrane can be replaced conveniently, which could effectively decrease the time and cost of chip manufacturing. The normally closed microvalves/pumps were used to automatically control all processes of the on-chip DNA SPE without cross-contamination and leakage, enabling the processing of multiple samples in parallel without changing the microvalve control module. Using the microchip device with integrated microvalves/pumps, automated, programmable, and simultaneous λ-DNA extractions from different samples could be attained, even from complex solutions such as human blood, and the silica-deposited open-channel columns could be reused stably and reliably. Results have demonstrated that most of the eluted λ-DNA was recovered in the second 2 µL of elution buffer with high-purity suitable for successful polymerase chain reaction amplification, making it possible for further integration into microfluidic devices for fully functional and high-throughput genetic analysis.     

Determination of chromium in the surface nano-layer covering the Zn-based anti corrosion coating of steel sheets using a laser-induced breakdown spectrometry

A method was proposed for the determination of Cr in a thin surface nanolayer deposited on top of a micrometrical Zn-based anticorrosive coating of steel sheets using laser-induced breakdown spectrometry (LIBS). Optimization of the LIBS parameters was performed with respect to the statistical parameters of regression, these being the coefficient of determination (R ²), akaike information criterion and mean-squared prediction error. These were calculated for curves describing the relationship between the Cr surface concentration and the intensity of LIBS signal. The most critical parameter of analysis appears to be the focal spot diameter. When its value was 200 μm and corresponding energy density (fluence) had value of 413.8 J/cm², the intensity–concentration relationship revealed a negative slope. This phenomenon was caused by the difference in total ablated volume for samples with a different content of Cr in the surface layer. This phenomenon was not observed for higher values of the focal spot diameter (400 and 500 μm) and lower values of fluence (103.5 and 66.2 J/cm²). A range of calibration obtained under optimal conditions (focal spot diameter of 400 μm; single pulse mode, laser pulse energy of 130 mJ) was 11–21 mg/m² and the limit of detection was 0.7 mg/m². The recovery values calculated from the results of the proposed LIBS method and the standard ED XRF method ranged from 99.2 to 101%.     

A Glass/PDMS Hybrid Microfluidic Chip Embedded with Integrated Electrodes for Contactless Conductivity Detection

A new glass/PDMS hybrid chip for contactless conductivity detection is reported. This chip consists of a glass substrate with microchannels and a PDMS cover sheet embedded with a small integrated electrode plate. In the region of detection, electrodes are insulated from the microchannel by a formed PDMS membrane about 100 μm in thickness. Without any modification, this glass/PDMS chip is suitable for contactless conductivity detection with good properties, such as excellent heat-dissipation, stable electroosmotic flow, high separation efficiency, satisfactory sensitivity, simple construction and high degree of integration. Its feasibility and performance had been demonstrated by analyzing inorganic ions and amino acids in mixtures, and alkaloids in traditional Chinese medicine. The limits of detection reached micromole per liter (μmol L^?1) levels. This microchip could be promising for mass production due to its stability, reproducibility, ease of fabrication and low cost.     

Influence of substrate chemistry and the network homogeneity of ultra‐thin cross‐linked polymer films cured at their surface on the main relaxations temperatures probing by microthermal analysis

Thin 200‐nm epoxy–amine mixtures were cured on silicon wafers with different surface chemistry to quantify the effect of the chemistry on the glass transition temperature evolution in ultra‐thin thermosetting films. Two surface treatments were investigated: the first one only consisted in the activation of the silanols groups at the silicon surface, whereas the second one consisted in the grafting 3‐aminopropyltrimethoxysilane (APTMS) monolayer on the silicon wafers. The epoxy films were deposited on these chemistry modified wafers by spin coating a toluene solution of DGEBA–amine mixture at stoichiometric ratio. The same cure processing was used for both samples. Thin films were analysed not only using microthermal and thermomechanical analysis to determine the relaxation transitions temperatures of these films but also using FTIR in infrared reflection absorption spectroscopy mode to determine the curing rate of these networks. It was found that all these thin films showed two different glass transitions, the first one at 96 °C and was independent of the surface treatments, whereas the second one increasing from 142 °C for the oxidised wafers surface to 167 °C for the aminosilane grafted on the silicon wafer. The substrate chemistry extent on the film network structure, the interfacial bonds and interactions are discussed. This work also illustrates the interest in using microthermal analysis to obtain relevant temperature glass transition of thin film at sub‐micrometre scale, strongly dependant of local structure and chemistry composition. Copyright © 2009 John Wiley & Sons, Ltd.     

Microfabricated glucose biosensor with glucose oxidase entrapped in sol-gel matrix

A microfabricated glucose biosensor based on an amperometeric hydrogen peroxide electrode has been developed. A sol-gel layer with 5 A pore size and 2 mum thickness was used as the glucose oxidase entrapping matrix. The sol-gel matrix formed over the silicon-based sensor has good mechanical and chemical stability, and the ability to entrap a large amount of enzyme. The miniaturized electrode sensing system is composed of platinum as both working and counter electrodes and silver as a reference electrode. Nafion(R) coating was applied as the interference limiting layer. A series of technologies, such as standard photolithography, electron beam evaporation and image reverse lift-off were utilized for mass production allowing 143 electrodes to be produced at the same time. The effect of oxidable interferences was <10% of the background value of the sensor response. Calibration tests of a series of individual sensors manufactured from the same silicon wafer and dip coated in the same conditions, showed a highly reproducible response characteristics (linear range up to 500 mg dl(-1) and mean sensitivity of 0.54+/-0.14 nA mg(-1) dl(-1) (n=10)).     

Area-selective formation of macropore array by anisotropic electrochemical etching on an n-Si(100) surface in aqueous HF solution

A photoassisted anodization process to fabricate arrays of uniform and straight macropores at selected areas of a Si wafer surface was developed. The front- and backside surfaces of n-type Si(100) wafers were coated with a thin Si(3)N(4) layer, and the frontside layer was micro-patterned using photolithography and reactive ion etching to form an array of microscopic openings at selected areas. The inverted pyramid-shape micropits were formed at these openings by anisotropic etching using aqueous KOH solution; these pits act as the initiation sites for the anodization to form macropores. The electrochemical etching was carried out in aqueous HF solution under illumination from the backside of the wafer, on which Au/Cr electric contact was formed following removal of the Si(3)N(4) layer. To improve the uniformity of the formation condition of the macropores at the selected area, holes were area-selectively generated by controlling the illumination condition during the anodization. For this, micropatterns were formed on the Au/Cr layer at the backside surface, which were aligned to those at the frontside surface. The parameters, such as HF concentration, current density, and wafer thickness, i.e., hole diffusion length, were optimized, and the arrays of uniform and high-aspect-ratio macropores were formed at the selected area of the domain at the silicon surface.     

Polyethylene glycol assisted direct deposition of rutile TiO2 nanocrystals on transparent conducting oxide substrate for dye-sensitized solar cell applications

Rutile TiO₂ nanocrystals having rectangular faces were directly deposited on fluorine-doped tin oxide coated glass substrates. Using polyethylene glycol-400 as the surfactant, we succeeded in growing a porous rutile layer having maximum thickness of 4.8 μm and containing nanocrystals with lateral dimensions of at least 30 nm. We observed that polyethylene glycol not only controlled the sizes of the nanocrystals but also enhanced the rate of deposition. The nanocrystals had rutile structure and the film was strongly textured with preferential orientation along {002} direction. The dye adsorption properties of the nanocrystalline films depended on their microscopic surface areas which were determined by the sizes of the nanocrystals. A dye-sensitized solar cell, fabricated with a 4.8 μm thick nanocrystalline rutile thin film photoanode, exhibited a light-to-electricity conversion efficiency of 5.02 % under 1.0 sun illumination. The internal resistance, interface capacitance and electron lifetime of dye sensitized solar cell were estimated by electrochemical impedance spectroscopy and an electron lifetime of 0.19 s was recorded.     

A Glass/PDMS Hybrid Microfluidic Chip Embedded with Integrated Electrodes for Contactless Conductivity Detection

A new glass/PDMS hybrid chip for contactless conductivity detection is reported. This chip consists of a glass substrate with microchannels and a PDMS cover sheet embedded with a small integrated electrode plate. In the region of detection, electrodes are insulated from the microchannel by a formed PDMS membrane about 100 μm in thickness. Without any modification, this glass/PDMS chip is suitable for contactless conductivity detection with good properties, such as excellent heat-dissipation, stable electroosmotic flow, high separation efficiency, satisfactory sensitivity, simple construction and high degree of integration. Its feasibility and performance had been demonstrated by analyzing inorganic ions and amino acids in mixtures, and alkaloids in traditional Chinese medicine. The limits of detection reached micromole per liter (μmol L⁻¹) levels. This microchip could be promising for mass production due to its stability, reproducibility, ease of fabrication and low cost.

     

Parylene to silicon nitride bonding for post-integration of high pressure microfluidics to CMOS devices

High pressure-rated channels allow microfluidic assays to be performed on a smaller footprint while keeping the throughput, thanks to the higher enabled flow rates, opening up perspectives for cost-effective integration of CMOS chips to microfluidic circuits. Accordingly, this study introduces an easy, low-cost and efficient method for realizing high pressure microfluidics-to-CMOS integration. First, we report a new low temperature (280 °C) Parylene-C wafer bonding technique, where O(2) plasma-treated Parylene-C bonds directly to Si(3)N(4) with an average bonding strength of 23 MPa. The technique works for silicon wafers with a nitride surface and uses a single layer of Parylene-C deposited only on one wafer, and allows microfluidic structures to be easily formed by directly bonding to the nitride passivation layer of the CMOS devices. Exploiting this technology, we demonstrated a microfluidic chip burst pressure as high as 16 MPa, while metal electrode structures on the silicon wafer remained functional after bonding.     

Phase separation of gas–liquid and liquid–liquid microflows in microchips

Phase separation of gas–liquid and liquid–liquid microflows in microchannels were examined and characterized by interfacial pressure balance. We considered the conditions of the phase separation, where the phase separation requires a single phase flow in each output of the microchannel. As the interfacial pressure, we considered the pressure difference between the two phases due to pressure loss in each phase and the Laplace pressure generated by the interfacial tension at the interface between the separated phases. When the pressure difference between the two phases is balanced by the Laplace pressure, the contact line between the two phases is static. Since the contact angle characterizing the Laplace pressure is restricted to values between the advancing and receding contact angles, the Laplace pressure has a limit. When the pressure difference between the two phases exceeds the limiting Laplace pressure, one of the phases leaks into the output channel of the other phase, and the phase separation fails. In order to experimentally verify this physical picture, microchips were used having a width of 215 μm and a depth of 34 μm for the liquid–liquid microflows, a width of 100 μm and a depth of 45 μm for the gas–liquid microflows. The experimental results of the liquid–liquid microflows agreed well with the model whilst that of the gas–liquid microflows did not agree with the model because of the compressive properties of the gas phase and evaporation of the liquid phase. The model is useful for general liquid–liquid microflows in continuous flow chemical processing.     

Preparation and nonlinear optical properties of Au nanoparticles doped TiO2 thin films

Nano-sized noble metal nanoparticles doped dielectric composite films with large third-order nonlinear susceptibility due to the confinement and the enhancement of local field were considered to be applied for optical information processing devices, such as optical switch or all optical logical gates. In this paper, sol–gel titania thin films doped with gold nanoparticles (AuNPs, ~10 nm in average size) were prepared. AuNPs were firstly synthesized from HAuCl₄ in aqueous solution at ~60 °C, using trisodium citrate as the reducing agent, polyvinylpyrrolidone as the stable agent; then the particle size and optical absorption spectra of the AuNPs in aqueous solutions were characterized by transmitting electron microscopy and UV–Vis–NIR spectrometry. Sol–gel 2AuNPs–100TiO₂ (in %mol) thin films (5 layers, ~1 μm in thickness) were deposited on silica glass slides by multilayer dip-coating. After heat-treated at 300–1,000 °C in air, the AuNPs–TiO₂ thin films were investigated by X-ray diffraction, scanning electron microscopy and atomic force microscopy. The nonlinear optical properties of the AuNPs–TiO₂ thin films were measured with the Z-scan technique, using a femtosecond laser (200 fs) at the wavelength of 800 nm. The third-order nonlinear refractive index and nonlinear absorption coefficient of 2AuNPs–100TiO₂ films were at the order of 10^?12 cm²/W, and the order of 10^?6 cm/W, respectively, and the third-order optical nonlinear susceptibility χ⁽³⁾ was ~6.88 × 10^?10 esu.     

Multi-channel PMMA microfluidic biosensor with integrated IDUAs for electrochemical detection

A novel multi-channel poly(methyl methacrylate) (PMMA) microfluidic biosensor with interdigitated ultramicroelectrode arrays (IDUAs) for electrochemical detection was developed. The focus of the development was a simple fabrication procedure and the realization of a reliable large IDUA that can provide detection simultaneously to several microchannels. As proof of concept, five microchannels are positioned over a large single IDUA where the channels are parallel with the length of the electrode finger. The IDUAs were fabricated on the PMMA cover piece and bonded to a PMMA substrate containing the microfluidic channels using UV/ozone-assisted thermal bonding. Conditions of device fabrication were optimized realizing a rugged large IDUA within a bonded PMMA device. Gold adhesion to the PMMA, protective coatings, and pressure during bonding were optimized. Its electrochemical performance was studied using amperometric detection of potassium ferri and ferro hexacyanide. Cumulative signals within the same chip showed very good linearity over a range of 0–38 μM (R ²?=?0.98) and a limit of detection of 3.48 μM. The bonding of the device was optimized so that no cross talk between the channels was observed which otherwise would have resulted in unreliable electrochemical responses. The highly reproducible signals achieved were comparable to those obtained with separate single-channel devices. Subsequently, the multi-channel microfluidic chip was applied to a model bioanalytical detection strategy, i.e., the quantification of specific nucleic acid sequences using a sandwich approach. Here, probe-coated paramagnetic beads and probe-tagged liposomes entrapping ferri/ferro hexacyanide as the redox marker were used to bind to a single-stranded DNA sequence. Flow rates of the non-ionic detergent n-octyl-β-d-glucopyranoside for liposome lysis were optimized, and the detection of the target sequences was carried out coulometrically within 250 s and with a limit of detection of 12.5 μM. The robustness of the design and the reliability of the results obtained in comparison to previously published single-channel designs suggest that the multi-channel device offers an excellent opportunity for bioanalytical applications that require multianalyte detection and high-throughput assays.

Mass spectrometric analysis of nanoscale sample volumes extracted from open microchannels after sample preconcentration applied on amyloid beta peptides

A new instrumental concept for extraction of nanovolumes from open microchannels (dimensions 150 μm?×?50 μm, length 10 mm) manufactured on silicon microchips has been used in combination with a previously developed method for preconcentrating proteins and peptides in the open channels through electromigration. The extracted nanovolumes were further analyzed using nanoelectrospray ionization (nESI) or matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) directly or with subsequent enzymatic protein digestion in a nanodroplet prior to the MS analysis. Preconcentration of the samples resulted in a 15-fold sensitivity increase in nESI for a neurotensin solution, and using MALDI-MS, amyloid beta (Aβ) peptides could be detected in concentrations down to 1 nM. The method was also successfully applied for detection of cell culture Aβ.