Droplet-size distribution gradient induced by laser curing in polymer dispersed liquid crystals

We have studied the morphology and electro-optical properties of polymer dispersed liquid crystals prepared by polymerization-induced phase separation (PIPS) under high intensity UV laser curing. The results have shown that localized high intensity curing generates a gradient of the droplet size distribution outside the directly irradiated area as a consequence of the non-uniform spatial distribution of the scattered intensity. Such a distribution of the droplet size reflects in a peculiar electro-optical behaviour that could find potential application in optical devices. Both shape and spatial extent of the droplet size gradient are affected by the spatial velocity of polymerization which in turn strongly depends on the intensity of the curing laser beam. This dependence has also been experimentally investigated.     

Studies on the electro-optical and the light-scattering properties of PDLC films with the size gradient of the LC droplets

Polymer dispersed liquid crystal (PDLC) films with the size gradient of the LC droplets were prepared based on the epoxy/acrylate hybrid polymer matrix. The ultraviolet (UV) intensity gradient was induced by the UV-absorbing dye over the thickness of the samples. Taking advantage of the difference between the epoxy monomers and acrylate monomers in polymerisation rates and the UV intensity gradient, the gradient distribution of the LC droplet size was formed in PDLC films. The effect of the size gradient of the LC droplets on the electro-optical and the light-scattering properties of PDLC films was investigated. The results showed that due to the size gradient distribution of the LC droplets, PDLC films could exhibit the strong light scattering in the UV-visible-near infrared (VIS-NIR) region. Consequently, it provides a potential approach for modulating NIR light transmittance.     

Anomalous Lehmann Rotation of Achiral Nematic Liquid Crystal Droplets Trapped under Linearly Polarized Optical Tweezers

Continuous rotation of a cholesteric droplet under the heat gradient was observed by Lehmann in 1900. This phenomenon, the so-called Lehmann effect, consists of unidirectional rotation around the heat flux axis. We investigate this gradient heat effect using infrared laser optical tweezers. By applying single trap linearly polarized optical tweezers onto a radial achiral nematic liquid crystal droplet, trapping of the droplet was performed. However, under a linearly polarized optical trap, instead of stable trapping of the droplet with slightly deformed molecular directors along with a radial hedgehog defect, anomalous continuous rotation of the droplet was observed. Under low power laser trapping, the droplet appeared to rotate clockwise. By continuously increasing the laser power, a stable trap was observed, followed by reverse directional rotation in a higher intensity laser trap. Optical levitation of the droplet in the laser beam caused the heat gradient, and a breaking of the symmetry of the achiral nematic droplet. These two effects together led to the rotation of the droplet under linearly polarized laser trapping, with the sense of rotation depending on laser power.     

PREPARATION OF POLYMER DISPERSED LIQUID CRYSTALS USING PHOTOPOLYMERIZATION

2-Hydroxycthyl methacrylate (HEMA) and styrene copolymers are prepared by photopolymerization. The electro-optical behavior and microstructure of the polymer dispersed liquid crystal films are investigated by using He-Ne laser andscanning electron microscopy, respectively. With increasing E7 content in the copolymer, droplet size increased, thresholdvoltage decreased,     

Laser photophoretic migration with periodic expansion-contraction motion of photo-absorbing microemulsion droplets in water

When the water-in-oil (w/o) microemulsion droplets including the Co(III)-pyridylazo complex as the photo-absorber were irradiated with a continuous-wave Ar(+) ion laser (514.5 nm), we have observed unexpected phenomenon that photo-absorbing microemulsion droplets in water repeated the expansion and the sudden contraction during the laser photophoretic migration. The period of the expansion-contraction cycle was inversely proportional to both the concentration of the complex and the irradiated laser power and was independent of the initial size of the droplet. The mechanism of the periodic motion of the droplet was investigated by local temperature measurement and Raman microscope spectroscopy. It was suggested that the first step was the phase separation of the bicontinuous microemulsion droplet into the normal w/o microemulsion outer phase and the aqueous inner phase in the droplet, which was caused by the laser-induced temperature gradient inside the droplet. Subsequently, an expansion of the inner aqueous phase was induced by the percolation of the external water by thermo-osmosis, which was caused by the laser-induced temperature gradient between the inside and the outside of the microemulsion liquid membrane of the droplet. When the liquid membrane became thinner to a critical thickness, the inner aqueous phase was released and the droplet shrank into the original size. The proposed mechanism can give an account of the unique cyclical motion.     

二阶非线性光学聚氨酯对电光效应的共振增强

二阶非线性光学聚合物是最有希望实现在电光器件方面应用的材料之一.该类材料的非线性光学系数很高,响应速度快,与半导体材料的相容性较好,且比有机和无机晶体的制备更方便.目前所用的电光调制器多为光传输型,高光学活性的极化聚合物一般光学损耗较大,尤其是其吸收波段更大,使得调制器只能在其透明波段内使用,否则,传输型波导器件由于这种损耗将无法使用.     

An Image-Based Technique for Measuring Droplet Size Distribution: The Use of CNN Algorithm

A challenging task in measuring droplet size is the ability to perform in-situ droplet size distribution analysis on multiphase fluids in their native states in the undisturbed environment. In this study, an inline two-dimensional low cost–high accuracy technique is presented for continuous measurement of spherical or non-spherical droplets in emulsions using image processing. The characteristic of the droplets is evaluated and the describe drop size distributions in different ranges is determined. This droplet size determination algorithm is based on both cellular neural networks and linear matrix inequality. Our main work focuses on the performance of the proposed methodology for exploring the dynamical evolution of such droplet size distributions by in-situ measurement. Moreover, the results were compared with those obtained using laser diffraction analyzer technique. It was proved that this method can efficiently characterize the quality of dispersed phase by determining droplet size distribution.     

Effects of crosslinking agent/diluents/thiol on morphology of the polymer matrix and electro-optical properties of polymer-dispersed liquid crystal

To study effects of the crosslinking agent/diluents/thiol on morphology of the polymer matrix and the electro-optical properties of polymer-dispersed liquid crystal (PDLC) films, samples were prepared by ultraviolet (UV)-initiated polymerisation. Due to the interaction between thiol–acrylate reaction and acrylate monomers polymerisation, the sample compositions were the foremost determinant to the microstructures which in turn played an essential role on the electro-optical properties of the PDLC films. With the increasing content of the crosslinking agent, the LC droplet size decreased, while the thiol had a contrary effect on the LC droplet size. It was demonstrated that the superior properties of the low-driven voltage (37.2 V), the high contrast ratio (148.2), the short response time (14.9 ms) and the high saturation transmittance (86.6%) could benefit from a novel microstructure which had a dense surface and meshes with microspheres attached. It was of great significance for the optimisation and the potential applications of the PDLC films.     

The effect of polymerizable surfactants on morphology and electro-optical of PDLCs films based on epoxy acrylate system

Polymer dispersed liquid crystals (PDLCs) have been extensively studied for various excellent electro-optical applications. The anchoring interaction of liquid crystals (LCs) molecules on the surface of the polymer cavity surrounding an LCs droplet has a crucial effect on the electro-optical performance of the PDLCs. The effect of polymerizable surfactants on the electro-optical properties of PDLCs films was studied in detail. The active double bonds were polymerized with prepolymer to stabilize the performance of polymer matrix. The experimental results showed that polymerizable surfactants could effectively reduce the driving voltage. The speed of polymerization was monitored by real-time transmittance. The electro-optical properties of PDLC films were measured by Polarimeter (PerkinElmer Model 341). The driving electric field was reduced from 3.9 V/μm to about 2.8 V/μm for doping undec-10-enoic acid at curing temperature 80?°C. The surfactants containing polymerizable functional groups, polarity, and alkyl chain weakened the surface anchoring between LCs droplets and polymer interface. The morphologies of PDLCs films were also investigated by polarizing optical microscopy (POM) and Fourier transform infrared (FTIR) images. The LC droplets were encapsulated by polymerizable surfactant according to FTIR images.     

Study on the electro-optical properties of polyimide-based polymer-dispersed liquid crystal films

The reflectivity control device, initially developed for attitude control, is utilised to control the solar sail orbit by switching the states between absorption and specular reflection. Actually, the major parts of the device are the polymer-dispersed liquid crystal (PDLC) films. Here, PDLC films based on polyimide (PI) as polymer matrix and a low molecular weight LC can be prepared by the thermally induced phase separation (TIPS) method. The influences of cooling rate and the content of LC on the size and uniformity of LC droplets dispersed in a polymer matrix by a TIPS process were investigated. It was found that a fast cooling rate gave smaller droplet sizes and hence a more uniform distribution as compared to the ones produced under a slow cooling rate. If the LC content was increased, the droplet size would be increased. Furthermore, the effect of LC droplet size on the electro-optical properties of the PI-based PDLC films was discussed, such as transmittance, threshold voltage, driving voltage and contrast ratio (CR).     

Infrared-infrared double resonance spectroscopy of cyanoacetylene in helium nanodroplets

Infrared-infrared double resonance spectroscopy is used as a probe of the vibrational dynamics of cyanoacetylene in helium droplets. The nu1 C-H stretching vibration of cyanoacetylene is excited by an infrared laser and subsequent vibrational relaxation results in the evaporation of approximately 660 helium atoms from the droplet. A second probe laser is then used to excite the same C-H stretching vibration downstream of the pump, corresponding to a time delay of approximately 175 micros. The hole burned by the pump laser is narrower than the single resonance spectrum, owing to the fact that the latter is inhomogeneously broadened by the droplet size distribution. The line width of the hole is characteristic of another broadening source that depends strongly on droplet size.     

Oil droplet size determination in complex flavor delivery systems by diffusion NMR spectroscopy

Droplet size distribution of flavor oils in two different solid flavor delivery systems were determined with pulsed field gradient NMR spectroscopy: yeast encapsulation system, a spray dried flavor encapsulation system based on empty yeast cells, and glassy encapsulation system, an extruded solid water soluble carbohydrate delivery system. The oil droplet sizes are limited by the yeast cell walls in the yeast encapsulation system and the size distribution is unimodal according to images from transmission electron microscopy. The droplet size determination with diffusion NMR is based on the Murday and Cotts theory of restricted diffusion of liquids in geometrical confinements. Good fits of the diffusion data could be obtained by applying a unimodal, log-normal size distribution model and average droplet sizes of about 2 μm were found that correspond approximately to the inner diameter of the yeast cells. Scanning electron microscopy images showed a multimodal droplet size distribution in the glassy extruded delivery systems. To fit the NMR data a bimodal log-normal distribution function with five independent fitting parameters was implemented that yielded consistent and robust results. The two size populations were found in the micron and sub-micron range, respectively. The method was sufficiently accurate to depict variation of droplet size distributions in glassy encapsulation systems of different formulation.     

Thermal behaviour of switchable nematic emulsions

We have investigated the electro-optical performance of switchable nematic emulsions as a function of temperature. The electro-optical properties of nematic emulsions are highly dependent on temperature because several parameters such as droplet size, number density, viscosity, surface free energy, elastic constant, refractive indices, dielectric anisotropy, and liquid crystal/monomer solubility are affected by temperature. In particular, both ON state transmittances and decay times show a decreasing behaviour with increasing temperature. On the contrary, the OFF state transmittances increase, and the rise times do not change in an appreciable way.     

Laser ablation solid sampling: vertical spatial emission intensity profiles in inductively coupled plasma

Spectral emission intensity in the inductively coupled plasma (ICP) was measured versus height above the load coil during laser ablation solid-sample introduction. The laser-beam pulse width, power density, and wavelength, and the sample composition are know to effect the particle size distribution of the ablated mass. Ceramic and metal samples were ablated using nanosecond and picosecond pulses, and provided similar emission intensity profiles for common elements, indicating that changes in the particle size distribution are not manifested in the vertical spatial emission profile. The gas environment in the ablation chamber also influences the particle size distribution as well as the ablation interaction. Gas composition will influence the spatial emission intensity profile because of changes in the excitation characteristics of the ICP. A preliminary study using noble gases in the ablation interaction was conducted by keeping the spatial profile constant, maintaining a constant total gas composition to the ICP.     

Thermal behaviour of switchable nematic emulsions

We have investigated the electro-optical performance of switchable nematic emulsions as a function of temperature. The electro-optical properties of nematic emulsions are highly dependent on temperature because several parameters such as droplet size, number density, viscosity, surface free energy, elastic constant, refractive indices, dielectric anisotropy, and liquid crystal/monomer solubility are affected by temperature. In particular, both ON state transmittances and decay times show a decreasing behaviour with increasing temperature. On the contrary, the OFF state transmittances increase, and the rise times do not change in an appreciable way.     

Evaporation of ethanol/water droplets: examining the temporal evolution of droplet size, composition and temperature

The evolving size, composition, and temperature of evaporating ethanol/water aerosol droplets 25-57 microm in radius are probed by cavity enhanced Raman scattering (CERS) and laser induced fluorescence. This represents the first study in which the evolving composition of volatile droplets has been probed with spatial selectivity on the millisecond time scale, providing a new strategy for exploring mass and heat transfer in aerosols. The Raman scattering intensity is shown to depend exponentially on species concentration due to the stimulated nature of the CERS technique, providing a sensitive measure of the concentration of the volatile ethanol component. The accuracy with which we can determine droplet size, composition, and temperature is discussed. We demonstrate that the CERS measurements of evolving size and composition of droplets falling in a train can be used to characterize, and thus avoid, droplet coagulation. By varying the surrounding gas pressure (7-77 kPa), we investigate the dependence of the rate of evaporation on the rate of gas diffusion, and behavior consistent with gas diffusion-limited evaporation is observed. We suggest that such measurements can allow the determination of the vapor pressures of components within the droplet and can allow the determination of activity coefficients of volatile species.     

Thermophoresis in Nanoliter Droplets to Quantify Aptamer Binding

Biomolecule interactions are central to pharmacology and diagnostics. These interactions can be quantified by thermophoresis, the directed molecule movement along a temperature gradient. It is sensitive to binding induced changes in size, charge, or conformation. Established capillary measurements require at least 0.5 μL per sample. We cut down sample consumption by a factor of 50, using 10 nL droplets produced with acoustic droplet robotics (Labcyte). Droplets were stabilized in an oil–surfactant mix and locally heated with an IR laser. Temperature increase, Marangoni flow, and concentration distribution were analyzed by fluorescence microscopy and numerical simulation. In 10 nL droplets, we quantified AMP‐aptamer affinity, cooperativity, and buffer dependence. Miniaturization and the 1536‐well plate format make the method high‐throughput and automation friendly. This promotes innovative applications for diagnostic assays in human serum or label‐free drug discovery screening.     

共聚焦拉曼测量中激光焦点在球形液滴中的穿透深度

针对在共聚焦拉曼测量中激光在球形液滴中的聚焦问题建立理论模型, 推导出激光焦点在球形液滴中的穿透深度公式, 将激光焦点在球形液滴中的实际穿透深度和拉曼平台的垂直移动距离关联起来. 研究表明, 平台移动距离和激光焦点移动距离是非线性的, 激光焦点分别聚焦于液滴上表面和球心处时, 激光焦点的移动距离等于平台移动距离, 而当激光焦点在液滴上表面和液滴球心之间时, 激光焦点的移动距离大于平台移动距离. 并利用此结论初步获得MgSO₄球形液滴胶态结构的空间分布信息. 发现MgSO₄液滴在低湿度下形成的胶态结构是具有一定厚度的壳状结构, 且其厚度与液滴所处环境的相对湿度有关.     

Monte carlo simulation of macromolecular ionization by nanoelectrospray

Electrospray ionization (ESI) is commonly used in macromolecular mass spectrometry, yet the dynamics of macromolecules in ESI droplets are not well understood. In this study, a Monte Carlo based model was developed, which can predict the efficiency of electrospray ionization for macromolecules, i.e., the number of macromolecular ions produced per macromolecules electrosprayed. The model takes into account ESI droplet evaporation, macromolecular diffusion within the droplet, droplet fissions, and the statistical nature of the ESI process. Two idealized representations of macromolecular analytes were developed, describing cluster prone, droplet surface inactive macromolecules and droplet surface active macromolecules, respectively. It was found that surface active macromolecules are preferentially ionized over surface inactive cluster prone macromolecules when the initial droplet size is large and the analyte concentration in solution is high. Simulations showed that ESI efficiency decreases with increasing initial droplet size and analyte molecular weight, and is influenced by analyte surface activity, the properties of the solvent, and the variance of the droplet size distribution. Model predictions are qualitatively supported by experimental measurements of macromolecular electrospray ionization made previously. Overall, this study demonstrates the potential capabilities of Monte Carlo based ESI models. Future developments in such models will allow for more accurate predictions of macromolecular ESI intensity.     

Measurement of monodisperse droplet desolvation in an inductively coupled plasma using droplet size dependent peaks in Mie scattering intensity

The periodic fluctuations in the Mie scattering intensity as a function of droplet diameter due to constructive and destructive interference of light reflected/diffracted from the droplet surface and light transmitted/refracted through the droplet were used to measure the desolvation rate of isolated water droplets in an inductively coupled plasma. The approach is applicable to study the desolvation of isolated, monodisperse droplets and does not require measurements as a function of wavelength or scattering angle. Use of a near forward scatter angle provides high intensity signals. Among the limitations of this measurement technique is the need to identify the absolute droplet diameter at one time during desolvation either by another droplet size measurement technique or by matching the pattern of Mie scattering intensity as the droplet evaporates to the theoretical intensity pattern. The results show that the droplet desolvation rate is not affected by the addition of 0.1 M NaCl to the sample even though the initial emission occurs earlier in time than when the sample does not contain a high matrix concentration. The measured droplet desolvation rates are higher than those reported by two previous publications but further measurements are needed to confirm the preliminary results reported here.