Diffusion kinetics investigations of Nano Ag-doped holographic polymer dispersed liquid crystal gratings

ABSTRACT

In this paper, we use multicomponent mutual diffusion method to derive a one-dimensional non-local diffusion dynamic model to describe the diffusion kinetics of a dynamic holographic polymer dispersed liquid crystal grating (H-PDLC) doped with nano-silver. The physical mechanism of diffusion between monomer and liquid crystal, monomer and nano-silver particles is analysed using this model. Using coupled-wave theory, the H-PDLC’s diffraction efficiency curve with the expose time are simulated due to the vivid changing of effective refractive index modulation caused by the movement of concentration of each component with the expose time. Correspondingly, in the experiment, the diffraction efficiency of the grating is measured in real time, which shows the improvement for the holographic properties because of nano-silver doped H-PDLC. The simulation results have a good agreement with experimental data by fitting the corresponding parameters of the model. In addition, through comparing with simulation and experimental results with doping different concentrations of nano-silver particles, the recipe and diffraction characteristics of H-PDLC grating can be improved. Thus, the diffusion Kinetics model can be used to optimise the phase separation of the PDLC grating, and finally to improve the opto-electrical properties of H-PDLC gratings.     

适用于高空间频率透射式全息聚合物分散液晶光栅的材料研究

提出了适用于空间频率为3000 lp/mm的透射式全息聚合物分散液晶(HF-THPDLC)光栅的材料体系,并在反应动力学方面进行了深入的分析.为了能够得到高衍射效率并具有良好表面形貌的HF-THPDLC 光栅,首先确定了体系的平均官能度,使得预聚单体和液晶的扩散时间、液晶的成核时间以及于聚合物的凝胶时间达到最佳匹配状态...     

Flow-induced grating from cholesteric mixtures

In this work we present a new technique for obtaining large diffraction gratings (some cm) by means of a simple filling of cells having a planar treatment of their inner surfaces. A homogeneous mixture, composed of a cholesteric liquid crystal and a nematic liquid crystal monomer, was used. During the filling process, the flow induces a phase separation between the cholesteric liquid crystal and the liquid crystal monomer and, at the same time, the latter is oriented planar to the surfaces of the cell. Phase separation produces alternate arrays constituted by the cholesteric liquid crystal and the nematic liquid crystal monomer. Successive UV polymerization of these films yields a permanent grating. We have investigated the transmitted and first order diffracted beam efficiency for films obtained at different temperatures. The morphology of the films was studied by using an optical microscope equipped with crossed polarizers and by electron microscopy in order to control the shape of the arrays and the alignment of the oriented polymer.     

Flow-induced grating from cholesteric mixtures

In this work we present a new technique for obtaining large diffraction gratings (some cm) by means of a simple filling of cells having a planar treatment of their inner surfaces. A homogeneous mixture, composed of a cholesteric liquid crystal and a nematic liquid crystal monomer, was used. During the filling process, the flow induces a phase separation between the cholesteric liquid crystal and the liquid crystal monomer and, at the same time, the latter is oriented planar to the surfaces of the cell. Phase separation produces alternate arrays constituted by the cholesteric liquid crystal and the nematic liquid crystal monomer. Successive UV polymerization of these films yields a permanent grating. We have investigated the transmitted and first order diffracted beam efficiency for films obtained at different temperatures. The morphology of the films was studied by using an optical microscope equipped with crossed polarizers and by electron microscopy in order to control the shape of the arrays and the alignment of the oriented polymer.     

聚硅氧烷侧链液晶高分子的合成与表征

研究以对－烯丙氧基苯甲酸对－氰基苯酚酯为单体的聚硅氧烷侧链液晶高分子的合成方法。首先利用Williamson反应生成醚、羧酸酰化、酯化反应得到单体,然后利用硅氢化反应将单体接枝到聚甲基氢硅氧烷上得到目标产物。用IR,NMR及热台偏光显微镜等方法对单体和聚合物进行了结构表征和液晶行为分析。优化了对－烯丙氧基苯甲酸对－氰基苯酯为单体的聚硅氧烷侧链液晶高分子的合成工艺条件,提高了产率。样品表征结果证明单体和聚合物均呈现近晶液晶相,为特殊功能材料提供了原料。     

NMR Study of the Kinetics of Butane and Hexane Adsorption from Vapor Phase by Porous Glasses

The kinetics of butane and hexane sorption from vapor phase by porous glasses is studied by the pulsed NMR technique. The sorption process is revealed to proceed in two stages: monomolecular adsorption and capillary condensation. The rate of adsorption is limited by the rate of adsorbate transfer to the adsorbent surface, with the latter rate being described by the classical diffusion flux. It is shown that ultramicropores are filled simultaneously with the formation of a monolayer. The relative content of molecules in such pores is estimated. At the stage of monomolecular adsorption and at the initial stage of capillary condensation, when the adsorption proceeds from the vapor phase of butane-hexane or butane-deuterated hexane mixtures, butane molecules are predominantly sorbed and followed by their partial displacement by hexane molecules. The rate of the capillary condensation of butane from the mixture is 15–18-fold lower than that from the vapor phase of butane alone which is explained by a decrease in the gradient of chemical potential. It is shown that, when adsorption occurs from a nonequilibrium butane-hexane mixture, anomalous kinetic curves are observed because the driving force of adsorption changes in the course of establishing equilibrium in the liquid phase.     

Effect of graphene doping of holographic polymer‐dispersed liquid crystals

Doping a polymer matrix with a minute amount of graphene (0.05–0.25%) had significant effects on the grating formation kinetics and electro‐optical performance of a holographic polymer‐dispersed liquid crystal. Low graphene contents (≤0.1%) reduced the viscosity and induced rapid diffusion, curing, grating formation, and high diffraction efficiency with a diffraction overshoot of 0.05%. Conversely, high graphene contents increased the compound viscosity, and the entire process proceeded slowly. Graphene increased the polymer conductivity and local electric field, reduced the operating voltage from 65 to 25–50 V, and increased the contrast ratio from 7 to 8–23 with a concomitant decrease in rise time. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Kinetics and selectivity of the copper-catalysed oxidative coupling of 4-(2′,6′-dimethylphenoxy)-2,6-dimethylphenol

The kinetics of the copper/N-methylimidazole catalysed oxidative coupling reaction with the C–O coupled dimer of 2,6-dimethylphenol (DMP or monomer), viz. 4-(2′,6′-dimethylphenoxy)-2,6-dimethylphenol (dimer), as the substrate have been studied. The reaction was found to obey Michaelis–Menten kinetics. The dimer is more easily oxidised than the monomer, but the formation of a copper–substrate complex is more difficult. The reaction rates are higher than in the case of the monomer, and the amounts of diphenoquinone (DPQ) formed are much lower. With the dimer as the substrate, the order of the reaction in copper is 2, confirming that the formation of a dinuclear copper complex is an important step in the reaction mechanism. The amount of DPQ formed is proportional to the initial amount of the dimer. A slight, but clear preference for the dimer over the monomer as the substrate has been observed from experiments with mixtures of monomer and dimer. The amount of DPQ formed decreases exponentially with an increase in the fraction of dimer in the mixture, which can be ascribed mainly to a statistical effect.     

Diffusion properties of liquid crystal-based microemulsions

Microscopic diffusion processes in thermotropic 5CB liquid crystals (LC) with imbedded surfactant-stabilized water microemulsions are studied using pulsed field gradient nuclear magnetic resonance (PFG NMR). The experiments are performed in a temperature range around the isotropic-nematic transition temperature of the LC. The temperature dependence of the diffusivities of the liquid crystal and surfactant molecules remains almost unchanged in the whole temperature range studied. With varying water content, the diffusivities of the surfactant molecules are found to be almost invariable, indicating that the surfactant diffusivities remain essentially unaffected by whether a microemulsion is formed or the surfactant molecules diffuse as individual species. At the same time, the formation of the microemulsion is found to be crucial for the macroscopic separation of the mixture into LC- and surfactant-rich phases.     

Improvements in morphological and electro‐optical properties of polymer‐dispersed liquid crystal grating using a highly fluorine‐substituted acrylate monomer

To improve the morphological and electro‐optical properties of a polymer‐dispersed liquid crystal (PDLC) grating, a type of highly fluorine‐substituted acrylate monomer was added to the prepolymer mixture. The morphologies of the PDLC gratings were investigated using atom force microscopy and scanning electron microscopy. The grating had a very clear polymer/LC interface after addition of 3.9 wt % of fluorine‐substituted monomer. The LC droplets in this case were much larger than the sample without fluorinated monomer. This phenomenon indicated that an almost complete phase separation had occurred. However, as the content of fluorine‐substituted monomer increased, the morphologies of gratings became less defined and the volumes of LC droplets were smaller. The diffraction efficiency (DE) decreased with increasing of fluoride content and the V ₉₀ increased simultaneously, which may be ascribed to the blurry interface and the small LC droplets. The highest DE (90%) and lowest V ₉₀ (70 V) were obtained simultaneously under the condition of 3.9 wt % fluoride added in the prepolymer. In addition, it was also found that the fluorine‐substituted monomer may disorder the alignment of LCs in the grating.     

Structure of polymer networks in liquid crystals studied by 13C NMR

We report on 13C NMR measurements above and below the clearing temperature of the liquid crystal 4-n-hexyloxyphenyl 4-methoxybenzoate constrained to an oriented, low concentration polymer network. The network is obtained by UV-irradiation of the reactive monomer 1,4-di-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene which is in admixture with the liquid crystal. The characterization of orientational order of the mixtures before UV-radiation, and hence before polymerization, reveals the high order of the components at the polymerization temperature. The chosen geometry explains the LC director orientation only by the aligned network. Above the nematic-isotropic transition a strong pretransitional order is detected. Fast molecular translational diffusion averages the order over dimensions smaller than 1 mum. The Landau-de Gennes theory predicts a relation between pretransitional order and the lateral dimension of the LC regions. The experimental data are successfully explained by pore diameters of 35 and 98 nm for concentrations of 20 and 8 mol% of monomer, respectively. The results support the model of nearly cylindrical shaped liquid crystal domains surrounded by thin walls of crosslinked network.     

Polymer nanostructure development of fluorinated and aliphatic monoacrylates in smectic liquid crystals via photopolymerization

To develop viable polymer stabilized liquid crystal systems, it is crucial to understand the factors that affect polymer nanostructure evolution. This work examines the influence of the photopolymerization of aliphatic and fluorinated monoacrylate monomer within a room temperature smectic liquid crystal (LC). Additionally, the effect of LC order on polymerization kinetics, monomer and polymer organization, and the effect of the polymer on LC properties have been examined. Through this work, insight has been gained regarding the impact that the introduction of a fluorinated monoacrylate monomer has on polymerization kinetics, LC organization, and monomer/polymer segregation and organization within a polymer/LC system. Fluorinated moieties lower the surface energy of the monomer to enhance segregation between the smectic layers of the LC as compared with an analogous aliphatic monomer. Additionally, the enhanced segregation significantly increases the polymerization rate in the smectic phase and drives the continued segregation of the fluorinated polymer during and after polymerization. Fluorination also leads to the formation of an ordered polymer nanostructure if polymerized in ordered LC phases. This ordering is particularly evident when the fluorinated monomer is polymerized in the smectic phase in which the monomer is organized between the smectic layers of the LC. In addition, the ordered polymer structure found with the fluorinated monomer in the smectic phase leads to continued birefringence above the clearing point of the LC due to surface interactions between the LC and the ordered fluorinated polymer. The continued birefringence offers an exceptional opportunity to examine how factors such as polymer molecular mass and UV light intensity affect the overall polymer morphology of these polymer/LC systems. As the initiator concentration and UV light intensity are decreased, longer polymer chains form lattice-type morphologies; whereas, shorter polymer chains form smoother morphologies that more closely mirror the texture of the LC smectic phase.     

Polymer nanostructure development of fluorinated and aliphatic monoacrylates in smectic liquid crystals via photopolymerization

To develop viable polymer stabilized liquid crystal systems, it is crucial to understand the factors that affect polymer nanostructure evolution. This work examines the influence of the photopolymerization of aliphatic and fluorinated monoacrylate monomer within a room temperature smectic liquid crystal (LC). Additionally, the effect of LC order on polymerization kinetics, monomer and polymer organization, and the effect of the polymer on LC properties have been examined. Through this work, insight has been gained regarding the impact that the introduction of a fluorinated monoacrylate monomer has on polymerization kinetics, LC organization, and monomer/polymer segregation and organization within a polymer/LC system. Fluorinated moieties lower the surface energy of the monomer to enhance segregation between the smectic layers of the LC as compared with an analogous aliphatic monomer. Additionally, the enhanced segregation significantly increases the polymerization rate in the smectic phase and drives the continued segregation of the fluorinated polymer during and after polymerization. Fluorination also leads to the formation of an ordered polymer nanostructure if polymerized in ordered LC phases. This ordering is particularly evident when the fluorinated monomer is polymerized in the smectic phase in which the monomer is organized between the smectic layers of the LC. In addition, the ordered polymer structure found with the fluorinated monomer in the smectic phase leads to continued birefringence above the clearing point of the LC due to surface interactions between the LC and the ordered fluorinated polymer. The continued birefringence offers an exceptional opportunity to examine how factors such as polymer molecular mass and UV light intensity affect the overall polymer morphology of these polymer/LC systems. As the initiator concentration and UV light intensity are decreased, longer polymer chains form lattice-type morphologies; whereas, shorter polymer chains form smoother morphologies that more closely mirror the texture of the LC smectic phase.     

Kinetic method by using calorimetry to mechanism of epoxy-amine cure reaction

A Mangelsdorf's approach to modeling the epoxy-amine cure kinetics has been developed. Analysis of the data by means of Mangelsdorf's approach makes it possible not only to determine the reaction rate constant and the heat of epoxy ring opening, but also to elucidate the reaction mechanism. However, to model the kinetic curves obtained by the calorimetric method for the complicated reaction should be derived an equation expressing the rate of change of the heat with time, as a function of the reaction rate and the extent of conversion. In a detailed examination the thermokinetic data, we found that glassy state transition is kinetically feasible. Using data available in literature, the kinetic model for epoxy-amine cure reaction was developed. Our treatment of glass formation is based on the picture of the reaction system as a miscible mixture of two structurally different liquids. This approach is similar to that presented by Bendler and Shlesinger as a Two-Fluid model. In the application of this model to reaction kinetics, we believe the explanation of glass structure formation lies in the splitting of the homogeneous mixture into two liquid phases.     

不同醇对聚合物分散液晶光聚合动力学及其电光特性的影响

以丙烯酸-2-乙基己酯(EHA)、二甲基丙烯酸乙二酯(EDMA)/季戊四醇四丙烯酸酯(PETTA)为混合单体、液晶P0616A为液晶相、Irgacure 184为光引发剂,通过UV光引发制备了聚合物分散液晶(PDLCs),研究了不同烷基链长醇,即乙醇(EtOH)、正丁醇(nBA)、正己醇(nHA)、正辛醇(nOA)和正十四醇(nTA)对体系光聚合动力学及其PDLCs液晶相变温度及电光特性的影响.结果表明引入醇分子显著加快了丙烯酸酯/液晶复合体系的光聚合反应速率,提高了单体的最终转化率,其中以正丁醇体系最为明显.随着醇分子烷基链的增长,体系的转化率趋于降低,但依然明显高于不含醇的体系.醇分子的加入降低了PDLCs中液晶相的TNI,且随着醇分子烷基链长的增长,PDLCs液晶相的TNI总体上呈降低的趋势.醇分子的加入增加了PDLCs液晶微区中向列相液晶的含量,而含正丁醇和正十四醇的体系液晶微区中向列相液晶低于其它3个含醇体系.醇分子的加入明显降低了PDLCs的阈值电压和饱和电压以及对比度.结合体系的光聚合速率和单体转化率,正丁醇是改善PDLCs性能的最佳选择.     

低热固相反应的反应机理研究(Ⅰ)——冷融熔机理和冷溶熔机理的模型

本文提出了低热固相反应的冷融熔机理和冷溶熔机理,其中冷融熔机理主要针对于不含结晶水的反应体系,冷溶熔机理主要针对于含结晶水的反应体系,并对低热固相反应动力学提出冷融熔/冷溶熔、扩散、反应、成核、生长的五步机理。两种机理都避开了分子在固相晶格中的扩散,从而对低热固相反应的扩散问题进行了有效的解释,并给出了低热固相反应的热力学和动力学判据。     

Cobalt Ferrite from Citrate Precursor by Self-Propagating Combustion Reaction

A Mangelsdorf's approach to modeling the epoxy-amine cure kinetics has been developed. Analysis of the data by means of Mangelsdorf's approach makes it possible not only to determine the reaction rate constant and the heat of epoxy ring opening, but also to elucidate the reaction mechanism. However, to model the kinetic curves obtained by the calorimetric method for the complicated reaction should be derived an equation expressing the rate of change of the heat with time, as a function of the reaction rate and the extent of conversion. In a detailed examination the thermokinetic data, we found that glassy state transition is kinetically feasible. Using data available in literature, the kinetic model for epoxy-amine cure reaction was developed. Our treatment of glass formation is based on the picture of the reaction system as a miscible mixture of two structurally different liquids. This approach is similar to that presented by Bendler and Shlesinger as a Two-Fluid model. In the application of this model to reaction kinetics, we believe the explanation of glass structure formation lies in the splitting of the homogeneous mixture into two liquid phases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and helical twisting property of polymerizable chiral dopant with temperature-dependent solubility in liquid crystal

In this study,right-handed dicinnamate isosorbide was synthesized via the esterification reaction between optically active isosorbide and cinnamate.The chiral dopant was characterized by FT-IR,~1H NMR,elemental analysis,SEM,UV absorption spectrum.After dissolving in a nematic liquid crystal mixture,the chiral dopant exhibited a temperature-dependent solubility in the chiral nematic liquid crystal mixture.Meanwhile,a relatively high value of helical twisting power of the polymerizable chiral dopant was de...     

Tracing the reactive melting of glass-forming silicate batches by in situ 23Na NMR

The kinetics of the reaction of batches of powdered quartz and sodium carbonate was studied by in situ (23)Na nuclear magnetic resonance (NMR) spectroscopy using a laser-heated probe. We show for the first time that the technique allows one to study solid-state reactions at high temperatures with good time resolution and without the risk of quenching artifacts. The reaction is controlled by solid-state Na(+) diffusion across the grain interface. Independent of the batch composition, the first reaction product is crystalline sodium metasilicate, Na(2)SiO(3), even if the temperature is high enough for much of the composition space between silica and metasilicate to be above the equilibrium liquidus. Fast Na(+) diffusion allows the reaction front to cross the grain interface and form the solid product before liquid intermediate equilibrium products can be formed. This purely solid-state reaction slows down as the thickness of the interface increases; the reaction is more deceleratory than published models suggest. If excess quartz is present, it reacts in a second step involving a liquid film wetting the excess grains. Once this reaction has started, it pulls the reaction into the thermodynamic regime, which leads to an increase even in the rate of the first step leading to intermediate solid metasilicate.     

丙烯酸酯/液晶复合体系的光聚合动力学

采用光差示扫描量热分析,研究了以2, 4, 6-三甲基苯甲酰基-二苯基氧化膦(TPO)为光引发剂、丙烯酸异辛酯(EHA)和三羟甲基丙烷三甲基丙烯酸酯(TMPTA)为单体、液晶为P0616A的丙烯酸酯/液晶复合体系在-40~80℃的光聚合动力学。研究表明：丙烯酸酯/液晶复合体系光聚合的自动加速现象非常显著,聚合反应速率和表观动力学常数在聚合过程中均存在最大值。随着反应温度的提高,体系的最终转化率、最大聚合反应速率(Rpmax)均明显提高,当反应温度高于20℃后,其增长均趋于平缓。随着体系中液晶含量的增加,体系的Rpmax呈下降趋势,体系的聚合反应转化率随时间的增长速率较慢,但是最终转化率差别不大,均接近80%。随着UV光强的增高,体系的Rpmax和最终转化率均明显提高, 体系的阈值光强约为4 mw/cm2。而随着体系平均官能度的增加,体系的Rpmax和最终转化率则呈下降的趋势。