Starch-iodine films respond to water vapor

Starch-iodine indicator films were found to have useful spectroscopic properties for the detection of water vapor. The large colorimetric response of these easily prepared films was easily detected by the absorption of 632.8 nm HeNe laser light, using a planar integrated optical waveguide (IOW) platform. The detection limit of a prototype sensor was found to be below 5% relative humidity (RH), with response times of the order of seconds.     

Porous polymer films and honeycomb structures based on amphiphilic dendronized block copolymers

Fabrication of honeycomb patterned films from our synthesized amphiphilic dendronized block copolymer by "on-solid surface spreading" method and "on-water spreading" method was reported for the first time in this paper. The comparison of the two methods indicated honeycomb-patterned films with smaller size, and larger surface density of micropores can be fabricated by spreading on water but with lower regular arrangement. Furthermore, several influencing factors on the formation of the honeycomb structure and the different morphologies, such as the concentration of the copolymer solution and the relative humidity in the atmosphere and the substrates, were investigated. The results showed that comparably high relative humidity from 80% to 95% was needed, and the mica plate as a spreading substrate was suitable to form orderly porous films for such a copolymer. The best ordered pattern could be formed from the copolymer with concentration of 1.00 mg/mL at the relative humidity of 85% using a mica plate. Besides, strong periodicity, regularity, and a large, defect-free area were notable, which made this structure extremely interesting for applications for templated molecular objects formed via intramolecular metal or metal oxide synthesis.     

Vertically aligned dense carbon nanotube growth with diameter control by block copolymer micelle catalyst templates

We have grown a dense array of vertically aligned carbon nanotubes (CNTs) with a controlled distribution of diameters by using block copolymer micelles to form and pattern catalyst particles. The block copolymer poly(styrene-block-acrylic acid) (PS16500-PAA4500) was dissolved in toluene to form micelles and then loaded with FeCl3. The metal-loaded micelles were spin-coated on Si and then thermally treated to remove the polymer. Using this process, we produced surfaces patterned with iron oxide catalyst particles with particle densities ranging from 1400 microm(-2) to 3800 microm(-2) and a size distribution of (6.9 +/- 0.8) nm. CNT growth by thermal chemical vapor deposition was then performed on these samples. The low-density catalyst sample produced unaligned, low-density CNTs, whereas the high-density catalyst sample produced vertically aligned, dense CNTs about 10 microm in length. Transmission electron microscopy revealed that the CNTs typically had double and triple graphitic layers with normally distributed diameters of (4.5 +/- 1.1) nm. For comparison, CNTs grown from the standard approach of blanket Fe films had a wide distribution of diameters between 6 and 21 nm. This catalyst preparation approach dramatically sharpens the size distribution of CNTs, compared to standard approaches, and provides a simple means of controlling the areal density of CNTs.     

Electrical and humidity characterization of m-NA doped Au/PVA nanocomposites

The Meta-Nitroaniline (m-NA) doped (by varying weight percentage (wt. %)) gold/polyvinyl alcohol (Au/PVA) nanocomposites were synthesized using gold salt and hydrazine hydrate (HH) by in situ process. The composite was coated on ceramic rods having two end electrodes by drop casting method for studying their electrical behavior at different relative humidity (RH) levels, ranging from 4 to 95% RH at room temperature. The optimized wt. % was used to prepare coatings of various thicknesses (20-40 μm) of the films. As the humidity decreases, the resistance increases. The low humidity sensing characteristic can be tailored by varying wt. % of m-NA and thicknesses of the nanocomposite films. The resistive-humidity sensor shows two regions of sensitivity having highest sensitivity for lower RH. The sensor response and recovery time is about 6-10 s and 52 s respectively. The dynamic range of variation of the resistance allows a promising use of the films as a humidity sensor. The material was characterized by X-ray diffraction (XRD) and impedance spectroscopy at 60% RH.     

A Novel Thin Film Resistive Humidity Sensor Based on Soluble Conjugated Polymer:(propionic acid)-co-(propargyl alcohol)

In recent years, humidity sensors have found wide applications in industrial and agricultural production, process control, household electric appliances, etc., therefore the research on humidity sensitive materials has attracted more and more attentions, and many polymers, including polymer electrolytes, conjugated polymers have been investigated as sensing materials1-3. However the doped conjugated polymers in general were insoluble and can not be used to prepare thin film humidity sensors, wh…     

Fabrication of an ammonia gas sensor using inkjet-printed polyaniline nanoparticles

This work details the fabrication and performance of a sensor for ammonia gas analysis which has been constructed via the inkjet-printed deposition of polyaniline nanoparticle films. The conducting films were assembled on interdigitated electrode arrays and characterised with respect to their layer thickness and thermal properties. The sensor was further combined with heater foils for operation at a range of temperatures. When operated in a conductimetric mode, the sensor was shown to exhibit temperature-dependent analytical performance to ammonia detection. At room temperature, the sensor responded rapidly to ammonia (t₅₀ = 15 s). Sensor recovery time, response linearity and sensitivity were all significantly improved by operating the sensor at temperatures up to 80 °C. The sensor was found to have a stable logarithmic response to ammonia in the range of interest (1-100 ppm). The sensor was also insensitive to moisture in the range from 35 to 98% relative humidity. The response of the sensor to a range of common potential interferents was also studied.     

pH值与湿度的光纤传感器研究

本文采用溶胶凝胶法和包埋法分别将对pH值和湿度敏感的指示剂修饰在光纤纤芯表面,制成了具有较宽检测范围的光纤pH传感器和光纤湿度传感器。通过X射线能谱仪(EDX)对所制备的pH和湿度敏感膜的表面成分进行了分析,并采用光功率计对敏感膜进行了光学检测。结果表明:当pH值在4.5~13的范围内变化时,光输出功率与pH值近似呈线性变化规律;当相对湿度(RH)在25%~80%的范围内变化时,光输出功率与RH值近似呈线性变化规律,并且二者在其检测范围内均具有良好的可逆性。     

Novel hybrid optical sensor materials for in-breath O(2) analysis

This study focuses on the optimisation and characterisation of novel, ORganically MOdified SILicate (ORMOSIL)-based, hybrid sensor films for use in the detection of O(2) on a breath-by-breath basis in human health monitoring applications. The sensing principle is based on the luminescence quenching of the O(2)-sensitive ruthenium complex [Ru(ii)-tris(4,7-diphenyl-1,10-phenanthroline)], which has been entrapped in a porous sol-gel film. The detection method employed is that of phase fluorometry using blue LED excitation and photodiode detection. Candidate sensor films include those based on the organosilicon precursors, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane and phenyltriethoxysilane. While it has been established previously by the authors that these films exhibit a stable, highly sensitive response to O(2), this study focuses on selecting the material most suited for use in a breath monitor, based on the sensitivity, response time and humidity sensitivity of these films. Key parameters to be optimised include the O(2) sensitivity of the film and the film polarity, i.e. the degree of hydrophobicity. These parameters are directly linked to the precursors used. In this study a n-propyltriethoxysilane-derived O(2) sensor platform was selected as the optimum material for in-breath O(2) analysis due to its short response time, negligible humidity interference and suitable O(2) sensitivity in the relevant range in addition to its compatibility with a single-point calibration strategy.     

A Morphological Transition of Inverse Mesophases of a Branched‐Linear Block Copolymer Guided by Using Cosolvents

We report here a strategy for influencing the phase and lattice of the inverse mesophases of a single branched‐linear block copolymer (BCP) in solution which does not require changing the structure of the BCP. The phase of the self‐assembled structures of the block copolymer can be controlled ranging from bilayer structures of positive curvature (polymersomes) to inverse mesophases (triply periodic minimal surfaces and inverse hexagonal structures) by adjusting the solvent used for self‐assembly. By using solvent mixtures to dissolve the block copolymer we were able to systematically change the affinity of the solvent toward the polystyrene block, which resulted in the formation of inverse mesophases with the desired lattice by self‐assembly of a single branched‐linear block copolymer. Our method was also applied to a new solution self‐assembly method for a branched‐linear block copolymer on a stationary substrate under humidity, which resulted in the formation of large mesoporous films. Our results constitute the first controlled transition of the inverse mesophases of block copolymers by adjusting the solvent composition.     

Evaluation of co-polyaniline nanocomposite thin films as humidity sensor

Spin coated films of Co-Polyaniline nanocomposite are evaluated for their transmission properties using He-Ne laser for humidity sensing. The thickness (17-29 microm) of the films is varied by multiple deposition of Co-Polyaniline nanocomposite on a glass substrate. The samples exhibit typically two to three regions in their sensitivity curve when tested in the relative humidity (RH) range of 20-95%. The sensitivity ranges from 0.1 mV/%RH to 12.26 mV/%RH for lower to higher thickness. The sensors show quick response of 8s (20-95%RH), and a recovery time of 1 min (95-20%RH) with good repeatability, reproducibility and low hysteresis effect. The sensitivity of the sensor increases with humidity and thickness. Material characterization is done by X-ray diffraction (XRD), scanning electron micrograph (SEM) and Fourier transform infra-red spectroscopy (FTIR).     

Tris(2,2′‐bipyridyl)ruthenium(II) Electrogenerated Chemiluminescence Sensor Based on Platinized Carbon Nanotube–Zirconia–Nafion Composite Films

Mesoporous films of platinized carbon nanotube–zirconia–Nafion composite have been used for the immobilization of tris(2,2′‐bipyridyl)ruthenium (II) (Ru(bpy)₃²⁺) on an electrode surface to yield a solid‐state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt–CNT–zirconia–Nafion exhibit much larger pore diameter (3.55 nm) than that of Nafion (2.82 nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia–Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt–CNT–zirconia–Nafion gave a linear response (R²=0.999) for TPA concentration from 3.0 nM to 1.0 mM with a remarkable detection limit (S/N=3) of 1.0 nM, which is much lower compared to those obtained with the ECL sensors based on other types of sol‐gel ceramic–Nafion composite films such as silica–Nafion and titania–Nafion.     

Investigation of conductometric humidity sensors

Sensors for determining humidity in air have been described and investigated. Sensing film of the devices was prepared from polyvinylalcohol and graphitized carbon black disperse phase. The composition, thermal treatment and design of sensing films were investigated and optimized. An optimized humidity sensor has better metrological parameters as compared with its prototype (response time approximately 45 s, detection limit 0.17%, slope 6.25 +/- 0.05 Theta/R.H., standard deviation of measurement 0.15%, standard deviation of analytical signal in the graduation equation 8.29Theta). Such construction of sensors have prospects in analytical practice.     

Optochemical sensor for determining ozone based on novel soluble indigo dyes immobilised in a highly permeable polymeric film

An optochemical ozone sensor is described that has been manufactured by immobilisation of novel soluble indigo derivatives in permeable transparent polymeric films of polydimethylsiloxane–polycarbonate copolymer. From a number of investigated indigo derivatives, 4,4,7,7-tetraalkoxyindigo 9 has been selected for optimal sensitivity and specificity of ozone detection. A linear calibration for ozone can be obtained in the range between 0.01 and 0.5 ppm. The limit of quantitation is 0.03 ppm, and the accuracy exceeds 8%. It takes about 134 s to measure the relatively low occupational exposure concentration of 0.1 ppm. A reduction of the sensor response time could be achieved through application of double-sided coated sensors instead of single-sided variants. The stability of the sensors and the effect of external parameters like relative humidity (RH), temperature and gas flow on the sensor response have been investigated. The sensor response is affected by varying the gas flow or temperature; however, humidity in the range between 0 and 90% RH does not affect sensor response. The indigo derivative 9 remained stable inside the polymeric film and no chemical reaction, crystallisation or leaching occurred during 10 months of observation. Proper choice of indicator dye and polymeric material and successful application of kinetic evaluation method for the exposure experiments determine the desired features of the sensor.     

Carbon nanotubes with small and tunable diameters from poly(ferrocenylsilane)-block-polysiloxane diblock copolymers

Iron-containing nanostructures produced from various self-assembled poly(ferrocenylsilane)-block-polysiloxane thin films are catalytically active for the initiation and growth of high density, small diameter carbon nanotubes (CNTs). Moreover, the tube diameter and density can be tuned by adjusting the chain lengths of the block copolymer. Iron-containing nanostructures from poly(ferrocenylmethylethylsilane)-b-poly(methylvinylsiloxane) polymer with 25 repeat units of an iron-containing segment and 265 repeat units of a non-iron-containing segment are able to produce CNTs with diameters around or less than 1 nm. Lithographically selective growth of CNTs across a large surface area has been demonstrated using this polymer system. Under the same growth condition, it has been found that the yield of defect-free CNTs varies with the size of the catalytically active nanostructures, which are dictated by the chain lengths of the two blocks. This result indicates that, for a specific-sized catalyst nanocluster, a unique set of growth conditions is required for synthesizing high yield, defect-free CNTs. This finding further addresses the importance of using uniform-sized catalyst-containing nanostructures for consistently achieving high-yield and high-quality CNTs with a minimum number of defects and amount of amorphous carbon.     

Synthesis and solution behavior of carbon nanotubes decorated with amphiphilic block polyelectrolytes

The aqueous solubilization of carbon nanotubes (CNTs) with the aid of a block copolymer possessing one polyelectrolyte block (namely polystyrene-b-sodium (sulfamate/carboxylate polyisoprene)) is reported. The solubilization protocol, based on the co-dissolution of the copolymer and the CNTs, leads to the formation of supramolecular assemblies on the side walls of the tubes. Electron microscopy as well as infrared spectroscopy and thermogravimetric analysis were employed as meaningful probes to identify the adsorption of the polymer onto the surface of CNTs and the composition of the final hybrid material. Viscosity measurements on solutions of the copolymer decorated CNTs indicate that the polyelectrolyte effect, which is observed in the case of net polymers, is preserved in a lesser extent in the case of the copolymer/CNTs dispersions.     

预辐射接枝四氟乙烯-乙烯共聚物湿敏膜的制备及特性研究

利用2 MeV电子加速器, 在常温下采用预辐照引发接枝的方法, 在四氟乙烯-乙烯共聚物(ETFE)上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS), 制备了一种含羧酸基团和磺酸基团的接枝膜. 傅里叶变换红外光谱(FTIR)分析结果证明了磺酸基团和羧酸基团的成功引入, 并对接枝膜的热力学和化学特性进行了研究. 结果表明, 随着接枝率的增加, 接枝膜的结晶度逐渐降低, 接触角逐渐减小, 接枝膜的亲水性逐渐增强. 利用制备的接枝膜构建了电阻型湿度传感器, 并测定了传感器的电学特性. 在相对湿度(RH)从5%变化到98%时, 传感器电阻线性变化范围接近4个数量级, 具有响应速度快(吸附<1 min, 解吸<2 min), 湿滞小(<2%RH)的特点.     

Highly sensitive optical humidity probe

A highly sensitive optical humidity probe based on reflectance measurements has been developed using Nafion^®-crystal violet (CV) films. This sensor can be used to calibrate relative humidity (RH) in the range 0-0.25% with a detection limit (blank signal + 3σ_b, where σ_b = the standard deviation (S.D.) of the blank signal) of 0.018% RH (∼4.37 ppm) and exhibited low hysteresis. The sensor films were fully reversible in dry nitrogen and reversal times were shown to be dependent on exposure time and % RH. The response to 1% RH was highly reproducible (S.D. = 1.67%, number of samples (n) = 5). Hydrogen chloride gas did not interfere with the response of the sensor to RH but did reduce sensor reversal times. This sensor displayed sufficient sensitivity that it could be used to detect ppm levels of moisture in process gases such as nitrogen and HCl.     

Graphene Oxide/Carbon Nanocoil Composite for High-performance Humidity Sensor

Designing a humidity sensor with high performance to quick and accurate detect relative humidity (RH) is important in various applications. Consideration must be given to both the high response and the quick reversibility. Here, based on Quartz Crystal Microbalance (QCM) sensing platform, we utilized commercial graphene oxide as a sensing material, and added commercial carbon nanocoil to block the stacking of graphene oxide layers. The fabricated novel sensor possessed super high response (4618 Hz/97 % RH) and quick reversibility (2 s). This work not only expands the application of commercial carbon materials, but also achieves the development of high-performance humidity sensor with commercial potential.     

Fluorescent Optosensor for Humidity Measurements in Air

A fiber‐optic sensor for relative‐humidity (RH) monitoring in environmental samples is described based on the adiabatic photoreaction that produces an intramolecular charge‐transfer excited state, which is the basis of the sensor response. The sensitive membranes are obtained immobilizing a highly fluorescent dye, 4‐[2‐(pyrazin‐2‐yl)‐1,3‐oxazol‐5‐yl]benzenamine (pzoxba; formerly called appzox), in hydroxypropylcellulose (HPC). The composition of the sensing films was optimized to a final ratio pzoxba/HPC of 1.8⋅10⁻⁵ mol g⁻¹ with a 100‐μm membrane thickness. The optode response spans from 1.68 to 100% RH, with a detection limit of 0.56% (Table 2). Typical response times (t₉₀) to 0 – 100% relative humidity are 1 – 2 min, the relative standard deviation for repeated measurements being 0.77 – 1.8%. The optode is insensitive to typical organic vapor interferents of commercial capacitive sensors (see Table 3) as well as to molecular oxygen, an important quencher of other luminescence‐based optical sensors. The proposed optode was successfully applied and validated for continuous monitoring of the relative humidity level in environmental samples.     

Conformational change in an isolated single synthetic polymer chain on a mica surface observed by atomic force microscopy

The random coil conformation of an isolated conventional synthetic polymer chain was clearly imaged by atomic force microscopy (AFM). The sample used was a poly(styrene)-block-poly(methyl methacrylate) diblock copolymer. A very dilute solution of the copolymer with benzene was spread on a water surface. The structure thus formed on water was subsequently transferred and deposited onto mica at various surface pressures and observed under AFM. The AFM images obtained with films deposited at a low surface pressure (<0.1 mN/m) showed a single polystyrene (PS) block chain aggregated into a single PS particle with a single poly(methyl methacrylate) (PMMA) block chain emanating from the particle. Immediately after the deposition, the single PMMA block chain aggregated to form a condensed monolayer around the polystyrene particles. However, after exposing the deposited film to highly humid air for 1 day, the PMMA chains spread out so that the single PMMA block chain could be identified as a random coil on the substrate. The thin water layer formed on the mica substrate in humid air may enable the PMMA block chain to be mobilized on the substrate, leading to the conformational rearrangement from the condensed monolayer conformation to an expanded and elongated coil. The elongation of the PMMA chain was highly sensitive to the humidity; the maximum elongation was obtained at 79% relative humidity. The elongation was a slow process and took about 20 h.