A temperature and pH double sensitive cholesteric polymer film from a photopolymerizable chiral hydrogen-bonded assembly

In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal (Ch-LC) monomers mixture containing a photopolymerizable chiral H-bonded assembly (PCHA). The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased, which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film. Additionally, the selective reflection band (SRB) of the cholesteric polymer film in solution with pH > 7 showed an obvious red shift with increasing pH values. While the SRB of the cholesteric polymer film in solutions with pH = 7 and pH < 7 hardly changed. This pH sensitivity in solutions with pH > 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by―OH and―K + ions in the alkaline solution. In contrast, it couldn’t happen in the neutral and acidic solutions. The cholesteric polymer film in this study can be used as optical/photonic papers, optical sensors and LCs displays, etc.     

Solvent-responsive structural colored balloons

The structural colored balloons (SCBs) consisting of polymer microcapsules showed several structural colors developed by optical thin-layer interference. The SCBs were prepared using a mixture of low- and high-molecular-weight polystyrene to give solvent responsiveness. When the surrounding solvent was transferred from water to the acetone/water mixture using a flow cell, the SCBs swelled at first and shrunk subsequently. The gradual color change of the SCBs was observed along with the size change. The color change accompanying the size change was successfully reproduced by assuming that the total amount of polymer in the thin film does not change. The swelling rate was rationalized by the diffusion of solvent through the shell polystyrene film to the inside of the balloons.     

Monitoring spatial distribution of ethanol in microfluidic channels by using a thin layer of cholesteric liquid crystal

Monitoring spatial distribution of chemicals in microfluidic devices by using traditional sensors is a challenging task. In this paper, we report utilization of a thin layer of cholesteric liquid crystal for monitoring ethanol inside microfluidic channels. This thin layer can be either a polymer dispersed cholesteric liquid crystal (PDCLC) layer or a free cholesteric liquid crystal (CLC) layer separated from the microfluidic device by using a thin film of PDMS. They both show visible colorimetric responses to 4% of ethanol solution inside the microfluidic channels. Moreover, the spatial distribution of ethanol inside the microfluidic channel can be reflected as a color map on the CLC sensing layers. By using this device, we successfully detected ethanol produced from fermentation taking place inside the microfluidic channel. These microfluidic channels with embedded PDCLC or embedded CLC offer a new sensing solution for monitoring volatile organic compounds in microfluidic devices.     

Poly (N-Isopropylacrylamide) microgel-based optical devices for humidity sensing

Optical sensors for environmental humidity have been constructed from poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgels. The devices were constructed by first depositing a monolithic layer of pNIPAm-co-AAc microgels on a Au-coated glass substrate followed by the addition of another Au layer on top. The resultant assembly showed visual color, and exhibited multipeak reflectance spectra. We found that the thickness of the device's microgel layer depended on environmental humidity, which corresponded to a change in the device's optical properties. Specifically, at low humidity the microgel layer was collapsed, while it absorbed water from the atmosphere (and swelled) as the humidity increased. Additionally, we investigated how the deposition of the hygroscopic polymer poly (diallyldimethylammonium chloride) (pDADMAC) onto the microgel layer (prior to final Au layer deposition) influenced the devices humidity response. We found that the devices were more sensitive to humidity as the number of pDADMAC layers in the device increased. Finally, we evaluated the device performance at various temperatures, and found that the sensitivity was enhanced at low temperature, although the response was more linear at elevated temperature.     

Angle-independent responsive organogel retroreflective structural color film for colorimetric sensing of humidity and organic vapors

The angle dependence of photonic crystals (PCs) dramatically limits their practical applications in the colorimetrical sensing of humidity and volatile organic compound (VOC) vapors. In addition, it is challenging for inverse opal PCs to colorimetrically distinguish between vapors with similar refractive indices. Different from the mechanism of PC-based sensors, here, we report an angle-independent polyacrylamide (PAAm) organogel structural color film based on the mechanisms of retroreflection, total internal reflection (TIR) and interference with a shape similar to a single-sided “egg waffle”. During the process of responding to humidity and VOC vapors, the color of the film remains angle-independent in the normal angle range of 0° to 45° under coaxial illumination and observation conditions. At the same time, the film can colorimetrically distinguish between vapors with similar refractive indices, such as methanol and ethanol, which is mainly due to the differences in their polarity and solubility parameters. The film shows good stability, reversibility and selectivity when exposed to vapors. A colorimetric sensor with a new response mechanism is proposed and has the potential to effectively distinguish between vapors with similar refractive indices. Furthermore, this responsive retroreflective structural color film (RRSCF) provides a universal strategy to develop targeted angle-independent structural color sensors by selecting optimized materials.     

多孔聚乙烯醇缩甲醛凝胶力学行为对含水量变化的敏感性

通过成孔剂法制备具有连通孔结构的聚乙烯醇缩甲醛凝胶(PVFM) ,研究其在吸水膨胀脱水收缩过程中力学行为对含水量变化的响应性.实验表明多孔PVFM具有很快的吸水 脱水速度,吸水80s内就可达到最大的平衡膨胀应力,干燥4h内其膨胀应力可降低95 % ;同时还发现多孔PVFM在脱水干燥过程中出现明显的体积回弹和膨胀应力回复现象,而且压缩模量在一定范围内随含水量的减少反而降低,分析表明这些与PVFM的多孔结构、弹性网络的状态有密切关系.     

New Approaches to Chemical Sensing‐Sensors Based on Polymer Swelling

Abstract

Although there is an extensive literature on polymer swelling, only in recent years has work been performed to exploit this phenomenon for chemical sensing. The lifetime of most sensors based on polymer swelling is limited by delamination of the polymer film. Swelling and shrinking introduce a shear force at the sensor/polymer interface that eventually severs the covalent bonds holding the polymer layer onto the substrate. This is a problem for any sensor configuration that involves immobilization of a swellable layer on a rigid substrate. Recently, sensor platforms have been developed to address this problem. Furthermore, coupling polymer swelling to optical, magneto, and electrochemical transduction technologies has greatly increased the scope of applications for sensors based on swellable polymers.     

Kinetics and equilibria associated with the absorption and desorption of water and lithium chloride in an ethylene—vinyl alcohol copolymer

Sorption and desorption equilibria and kinetics for LiCl and H₂O in an ethylene—vinyl alcohol copolymer film containing 70 mole percent vinyl alcohol were investigated at 25°C. The swelling behavior of water in the polymer was characterized by vapor and liquid sorption experiments over a range of water activities. p]The effects of LiCl content on the water sorption kinetics and equilibria in the films are presented and discussed. The kinetics and mechanism of LiCl sorption have also been studied. The amount of salt sorbed into the polymeric films increases linearly with the salt concentration in the external aqueous solutions. Both the rate and the amount of sorbed water increase significantly as the LiCl content increases. p]The desorption of LiCl, previously sorbed into the polymer, was characterized for different salt loadings. The rate of fractional salt release is independent of LiCl concentration in the film. Initially, the salt release is controlled by the nearly constant-rate absorption of water. The salt release, at long times, lags behind the swelling-controlled water uptake, indicating that the salt release is not completely controlled by the water sorption and that diffusion in the swollen polymer matrix contributes significantly to the long term elution of LiCl. Independent thermal analysis experiments suggest the formation of a metal salt—poly(ethylene—vinyl alcohol) complex.     

Water sorption properties of carbonized layers produced by controlled B<Superscript>+</Superscript> bombardment of thin polyimide and polysulfone films

Thin polyimide (PI) and polyethersulfone (PES) films are widely used as functional layers for microelectronic sensors. Ion implantation modifies the layer structure and morphology of these polymers and hence results in new mechanical and optical properties. However, ion-modified layers also show a change in sensitivity to moisture uptake under specific conditions. This is important for developing humidity sensors. Therefore, the water sorption ability of such modified polymer layers is studied by spectroscopic ellipsometry under definite relative humidity conditions (1–95%). Swelling data were obtained by fitting procedures based on changes of effective layer thickness and optical constants due to water uptake. Irradiation doses from 0.5 to 5×10¹⁵ B⁺ cm^–2 at an energy of 180 keV were used for polymer modification. At irradiation doses from 0.5 to 0.7×10¹⁵ B⁺ cm^–2, the maximum out-of-plane swelling is reached. At higher doses >2×10¹⁵ B⁺ cm^–2, the swelling decreases and corresponds to values of the pure polymer layers. The wetting properties of the layer surfaces determined by contact angle measurements are important to explain this behavior.     

Interfacial effects on moisture absorption in thin polymer films

Moisture absorption in model photoresist films of poly(4-hydroxystryene) (PHOSt) and poly(tert-butoxycarboxystyrene) (PBOCSt) supported on silicon wafers was measured by X-ray and neutron reflectivity. The overall thickness change in the films upon moisture exposure was found to be dependent upon the initial film thickness. As the film becomes thinner, the swelling is enhanced. The enhanced swelling in the thin films is due to the attractive nature of the hydrophilic substrate, leading to an accumulation of water at the silicon/polymer interface and subsequently a gradient in concentration from the enhancement at the interface to the bulk concentration. As films become thinner, this interfacial excess dominates the swelling response of the film. This accumulation was confirmed experimentally using neutron reflectivity. The water rich layer extends 25 +/- 10 A into the film with a maximum water concentration of approximately 30 vol %. The excess layer was found to be polymer independent despite the order of magnitude difference in the water solubility in the bulk of the film. To test if the source of the thickness dependent behavior was the enhanced swelling at the interface, a simple, zero adjustable parameter model consisting of a fixed water rich layer at the interface and bulk swelling through the remainder of the film was developed and found to reasonably correspond to the measured thickness dependent swelling.     

温度敏感水凝胶包覆长周期光纤光栅传感器研究

以N-异丙基丙烯酰胺(NIPAM)为单体、N,N'-亚甲基双丙烯酰胺(MBAA)为交联剂、安息香二甲醚(DMPA)为引发剂,利用紫外光引发聚合制备了一系列温度敏感性聚(N-异丙基丙烯酰胺)(PNIPAM)水凝胶,并对其性能进行了测定.结果表明,PNIPAM水凝胶的平衡膨胀比随着交联程度的变化而改变.当交联程度适当时,水凝胶可具有最大的溶胀比.在此研究基础上,利用浸渍提拉法在长周期光纤光栅(LPFG)包层外制备了PNIPAM水凝胶薄膜包覆层.研究了得到的LPFG传感器对温度和湿度的响应性,该类型传感器表现出对温度的灵敏响应性.     

Thin films composed of multiwalled carbon nanotubes, gold nanoparticles and myoglobin for humidity detection at room temperature.

Optically transparent and electrically conductive nanocomposite thin films consisting of multiwalled carbon nanotubes (MWCNTs), gold nanoparticles (GNPs) and myoglobin molecules that glue GNPs and MWCNTs together are fabricated for the first time on glass substrates from aqueous solution. The nanocomposite thin film is capable of varying its resistance, impedance or optical transmittance at room temperature in response to changes in ambient humidity. The conductometric sensitivity to relative humidity (RH) of the nanocomposite thin film is compared with those of the pure and Mb-functionalized MWCNT layers. The pure MWCNT layer shows a small increase in its resistance with increasing RH due to the effect of p-type semiconducting nanotubes present in the film. In contrast, a four times higher sensitivity to RH is observed for both the nanocomposite and Mb-functionalized MWCNT thin films. The sensitivity enhancement is attributable to swelling of the thin films induced by water absorption in the presence of Mb molecules, which increases the inter-nanotube spacing and thereby causes a further increase of the film resistance. A humidity change as low as DeltaRH=0.3 % has been readily detected by conductometry using the nanocomposite thin film.     

掺盐MEBA-co-KH570共聚物的湿敏性能

采用甲基丙烯酸二甲氨基乙酯的溴代丁烷季铵盐和硅烷偶联剂KH570的共聚物作为感湿聚合物,并向该聚合物中掺杂LiCl、CaCl2、FeCl33种不同的盐类,制备了高分子电阻型湿敏元件,系统研究了聚合物浓度、无机盐的种类和浓度对元件湿敏性能的影响。结果表明,在33%～95%RH湿度范围内,元件显示出较高的灵敏度(b为-0.043 8～-0.038 8)和较好的线性(R为-0.994 8～-0.981 6),且阻抗随聚合物浓度的增加而下降,但响应变慢;掺杂LiCl和CaCl2可使元件阻抗变小,掺杂FeCl3却使元件阻抗增大;在1×10-2mol/L的最佳LiCl掺杂浓度下,元件具有最好的灵敏度(b=-0.044 6)和最短的脱湿时间(20 s)。     

In situ study of the thermoresponsive behavior of micropatterned hydrogel films by imaging ellipsometry

A patterned hydrogel was immobilized on a polymer substrate by low-pressure argon plasma treatment using a masking technique. The polymer sample showed a thermoresponsive aggregation behavior in the region of 35-37 degrees C. The micropatterned, thermoresponsive hydrogel film has been characterized with imaging ellipsometry. The characterization was carried out on the dry film as well as on a swollen sample in water. The thermoresponsive behavior was studied in deionized water by temperature-dependent measurements in a solid-liquid cell. Through imaging ellipsometry, it was possible to distinguish the different regions of interest on a micrometer scale and to follow the swelling of the hydrogel part as a function of the temperature. It was possible to visualize the swelling as 3D profiles of Delta at various temperatures. Long-term changes of the sample could also be detected, which cannot be picked up by conventional ellipsometry.     

Photoinduced hyper-reflective cholesteric liquid crystals enabled via surface initiated photopolymerization

A structured polymer was synthesized by surface initiated photopolymerization in the presence of a cholesteric liquid crystal (CLC). The templated helical polymer (traversing 2/3 the cell thickness) was backfilled with an opposite handedness, photoresponsive CLC mixture yielding a photo-induced, large contrast, hyper-reflective (R > 99%) CLC film.     

Photochemically and Thermally Driven Full‐Color Reflection in a Self‐Organized Helical Superstructure Enabled by a Halogen‐Bonded Chiral Molecular Switch

Supramolecular approaches toward the fabrication of functional materials and systems have been an enabling endeavor. Recently, halogen bonding has been harnessed as a promising supramolecular tool. Herein we report the synthesis and characterization of a novel halogen‐bonded light‐driven axially chiral molecular switch. The photoactive halogen‐bonded chiral switch is able to induce a self‐organized, tunable helical superstructure, that is, cholesteric liquid crystal (CLC), when doped into an achiral liquid crystal (LC) host. The halogen‐bonded switch as a chiral dopant has a high helical twisting power (HTP) and shows a large change of its HTP upon photoisomerization. This light‐driven dynamic modulation enables reversible selective reflection color tuning across the entire visible spectrum. The chiral switch also displays a temperature‐dependent HTP change that enables thermally driven red, green, and blue (RGB) reflection colors in the self‐organized helical superstructure.     

Electro‐optical cells using a cellulose derivative and cholesteric liquid crystals

A cellulose derivative/liquid crystal composite‐type electro‐optical cell using a commercial cholesteric liquid crystal (CLC) was investigated. The electro‐optical properties of the system were examined, i.e. the dependence on applied voltage of the reflected wavelength and the minimum and maximum transmissions. A thin film of the CLC was dispersed with a cross‐linked cellulose film of 25 µm thickness. In the voltage dependence of the reflected wavelength it was verified that there is a hysteresis in the reflected wavelength. The variation of the reflected wavelength with temperature was also determined. The results are analysed in the framework of similar systems described in the literature for CLC dispersed in a polymer matrix.     

Preparations and optical properties of ordered arrays of submicron gel particles: interconnected state and trapped state

Two types of thermosensitive opal-structured hydrogel systems, "interconnected" and "trapped" gel particle arrays, were newly developed by extremely simple methods using silica colloidal crystal as a template. Although both systems diffract visible light following Bragg's law combined with Snell's law, the temperature dependences of their optical properties were quite different. The "interconnected" array exhibited a reversible change in the peak values of the reflection spectra, mainly determined by the swelling ratio of the hydrogel, as a function of the water temperature. Since the swelling ratio is dominant over the peak value, we can observe water temperature through the color of the interconnected type of gel membrane. The "trapped" array revealed a reversible change in the peak intensity of the reflection spectra with the change in temperature, whereas no change in the peak position was observed. We can interpret this phenomenon in the following ways. As the rise in temperature causes a decrease in the water content of the NIPA gel particles, the gel particles becomes stickier on the cavity wall of polystyrene PPM. This may induce a disturbance in the ordered array of the gel particles and form many layers of rough surfaces in the inverse opal structure of the PPM. This situation may lead to the stronger diffused reflection of light from the gel particles, resulting in the decrease in peak intensity at higher temperatures.     

On the origins of sudden adhesion loss at a critical relative humidity: examination of bulk and interfacial contributions

The origins for abrupt adhesion loss at a critical relative humidity (RH) for polymeric adhesives bonded to inorganic surfaces have been explored using a model poly(methyl methacrylate) (PMMA) film on glass. The interfacial and bulk water concentrations within the polymer film as a function of D 2O partial pressure were quantified using neutron reflectivity. Adhesion strength of these PMMA/SiO 2 interfaces under the same conditions was quantified using a shaft loaded blister test. A drop in adhesion strength was observed at a critical RH, and at this same RH, a discontinuity in the bulk moisture concentration occurred. The moisture concentration near the interface was higher than that in the bulk PMMA, and at the critical RH, the breadth of the interfacial water concentration distribution as a function of distance from the SiO 2/PMMA interface increased dramatically. We propose a mechanism for loss of adhesion at a critical RH based upon the interplay between bulk swelling induced stress and weakening of the interfacial bond by moisture accumulation at the PMMA/SiO 2 interface.     

Humidity effect on the monolayer-protected gold nanoparticles coated chemiresistor sensor for VOCs analysis

Two gold-thiolate monolayer-protected nanoparticles were synthesized and used as interfacial layers on chemiresistor sensors for the analysis of violate organic compounds (VOCs). Toluene, ethanol, acetone and ethyl acetate were chosen as the target vapors. Both the resistance and capacitance were measured as the function of analyte concentrations. The effect of humidity on the sensor sensitivity to VOCs was investigated. The sensitivity decreases with humidity increasing, depending on the hydrophobicity of the target compounds. Less effect was observed on the higher hydrophobic compounds. While the relative humidity (RH) increased from 0 to 60%, the sensitivity to acetone decreased by 39 and 37%, respectively on the Au-octanethiol (C₈Au) and Au-2-phenylethanethiol (BC₂Au) coated sensors, while the sensitivity to toluene decreased by 12 and 14%, respectively. These results show that the sensors coated with hydrophobic compounds protected-metal nanoparticles can be employed in high humidity for hydrophobic compounds analysis. The resistance responses to VOCs are rapid, reversible, and linear, while the capacitance response is not sensitive and consequently not applicable for VOCs analysis. The response mechanism was also discussed based on the sensor response to water vapor. The capacitance response is not sensitive to the film swelling in dry environment.