High-diffraction-efficiency Fresnel lens based on annealed blue-phase liquid crystal–polymer composite

We demonstrated a relatively simple and effective method to fabricate a periodically isolated polymer wall of blue-phase liquid crystal Fresnel lens (BPLCFL) by employing a single-masking process of the ultraviolet (UV) irradiation, leading to excellent photopolymerisation-induced phase separation between blue -phase liquid crystal (BPLC) molecules and UV-curable monomers. Nevertheless, some uncured monomers would inherently reside in the BPLC-rich area and slightly inhibit the BPLC molecules realigned under the external electric field. To enhance the optical properties of the polymer-wall BPLCFL considerably, a novel technique for fabricating a pure BPLC zone is proposed that successfully expels the residual monomers from the BPLC volume using a thermal annealing process. Experimental results show that the maximum diffraction efficiency reaches ~36%, which approaches the theoretical limit of ~41%. Consequently, the annealing technique to purify phase-separated composite films has a strong potential to construct the BPLCFL in light of polarisation-free applications.     

Switchable polarisation-independent blue phase liquid crystal Fresnel lens based on phase-separated composite films

A simple method for fabricating a polarisation independent blue-phase liquid crystal Fresnel lens (BPLCFL) is demonstrated by utilising the photo-polymerisation-induced phase separation. The BPLC/polymer binary Fresnel zones is obtained well by periodic UV illumination with phase separation of the BPLC molecules and UV-curable pre-polymer mixture. The diffraction efficiency can be controlled when applying a uniform electric field which modulates the phase difference between even and odd Fresnel zones. Experimental results show that the maximum diffraction efficiency reaches 24.3%, which is close to the measured diffraction efficiency of the used Fresnel zone-plate mask of 25%. We also characterise the tunable lens performance at different applied voltages.     

Low-voltage blue-phase liquid crystal display with diamond-shape electrodes

We propose a new electrode configuration, called diamond-shape in-plane switching, to lower the operation voltage of polymer-stabilised blue-phase liquid crystal (BPLC) displays (BPLCDs). The electrode structure is modified from conventional protruded IPS, where the strip protrusion is changed to diamond shape. By optimising the electrode gap and diamond length, we are able to obtain peak transmittance over 75% at 15 V. It enables single thin-film transistor (TFT) driving, and more importantly, this is based on an industrially proven BPLC material. That means good long-term stability, adequate TFT charging time for high-resolution displays and sub-millisecond response time and acceptable voltage-holding ratio for field sequential displays can be achieved simultaneously. Our device design helps accelerate the emergence of the long-awaited BPLCDs.     

Morphology,electro-optical and dielectric properties of polymer network liquid crystals in visible wavelengths

The correlations among electrical, optical properties and polymer morphologies of polymer network liquid crystals (PNLCs) constructed with various curing parameters are investigated. The experimental results indicate that high UV curing intensity, low curing temperature and high monomer-dopant concentration reduce the sizes of liquid crystal (LC) domains, thereby decreasing field-off response time and light scattering and increasing phase retardation of the PNLC cells. Photoinitiator concentration affects the LC domain size as well. For instance, increase in photoinitiator concentration results in the acceleration of polymerisation and thus decreases LC domain size. This effect increases driving voltages of the PNLC cells. Notably, excessive amounts of photoinitiator increases the LC domain size of the PNLC cell. Furthermore, dielectric measurement reveals that decrease in the LC domain size generally increases the dielectric relaxation frequency of the PNLC cells. When the LC domain size is small enough, the dielectric relaxation frequency of the PNLC cell is further dominated by the monomer concentration owing to the increased densities of polymer networks that facilitate the alignment of LC molecules.     

Auto‐Initiating Performance of Styrene on Surface Photografting Polymerization

Investigating the surface photografting polymerization of styrene (St), it was found that in the absence of photoinitiator and at high temperatures, a remarkable amount of St‐grafted polymer is formed. The initiation performance of St was further confirmed by surface photografting polymerization of acrylic acid, where St was used as the photoinitiator. This finding is useful to investigate the reaction mechanism of aromatic compounds under UV radiation and develop photoinitiator‐free polymerization systems.     

One-dimensional model for simulating blue-phase liquid crystal display

We proposed a one-dimensional model for simulating some performances of blue-phase liquid crystal (BPLC) and polymer-stabilised blue-phase liquid crystal (PSBPLCD). The one-dimensional model treats liquid crystal arrangement of BPLC as cholesteric liquid crystal with high and uniform tilt angle to simulate the Bragg reflection of BPLC. The simulated results agree quite well with the experimental results. The elastic and dynamical equations are formed to calculate the effective elastic parameters and the response times of PSBPLCD. The effective elastic parameter is a constant for low electric field and decreases with the increasing of electric field. The varied effective elastic parameter means the varied restoring force of liquid crystal under the electric field. The dynamical equations are proposed to calculate response times, and the response mechanism of BPLCD is discussed by researching the difference between the decay times from equation and experiment. The sub-millisecond response time results from the weak anchoring of polymer network or the increasing of rotational viscosity of PSBPLC with high-concentration monomer, and the reason of 10 µs response time is the strong anchoring and small amount of chiral dopant and monomer.     

Unique Curing Properties through Living Polymerization in Crosslinking Materials: Polyurethane Photopolymers from Vinyl Ether Building Blocks

Photopolymers with unique curing capabilities were produced by combining living cationic polymerization with network formation and restricted polymer motion. A vinyl ether diol was synthesized as a functional building block and reacted with isophorone diisocyanate to form a highly functionalized vinyl ether polyurethane as a model system with high crosslinking ability. When using a cationic photoinitiator, fast polymerization is observed upon short UV irradiation. Curing proceeds in the absence of light and under ambient conditions without oxygen inhibition. Cationic active sites become trapped dormant species upon network‐induced vitrification and surprisingly remain living for several days. The polymerization can be reactivated by additional UV irradiation and/or raised temperature. The curing behavior was studied in detail by using UV and FT‐NIR coupled rheology and photo‐DSC to simultaneously study spectroscopic and mechanical information, as well as thermal effects.     

A novel epoxy methacrylate resin containing phthalazinone moiety for UV coatings

A novel phthalazinone modified epoxy acrylate resin for the high temperature resistant ultravioet (UV) curable coating was synthesized. The methacrylated epoxy resins obtained were utilized to UV radiation curing by taking 2.5% (wt%) of photoinitiator in combination with 20% (wt%) of diluent, and generated the interpenetraring polymer networks. The cured film had good thermal and chemical stability.     

Impact of co-doping concentration in copolymer network liquid crystals

ABSTRACT

The impact of varying the co-doping concentration of a mesogenic and a non-mesogenic monomer in the reactive mixtures used to create a copolymer network LCs was investigated. Use of copolymer has been found to improve the response properties in the obtained liquid crystal composites. The polymer network in the studied copolymer network LCs was examined by scanning electron microscopy and the response times in various samples were investigated. Samples were prepared with various reactive mixtures, each of which had a constant concentration of mesogenic monomer, various concentrations of non-mesogenic monomer, and the same amount of photoinitiator. These reactive mixtures were filled in home assembled test cells with planar alignment and then exposed to UV light. With increasing concentration of the non-mesogenic monomer, the response properties of the resulting copolymer network LC were improved. Usually, if the overall polymer content in a polymer network LC is increased, the threshold voltage is also increased. However, both threshold voltages and response times were lowered and the response properties were thus improved in the studied copolymer network LCs. This unexpected behavior could be traced back to inducing a grainy polymer morphology of the copolymer network by using a non-mesogenic monomer.     

Synthesis of gradient polymer by using polysiloxane‐based photoinitiator

This paper reported a polysiloxane‐based photoinitiator (184‐AC‐Si), which was synthesized basing on traditional photoinitiator 1‐hydroxy‐cyclohexyl phenyl ketene (184) and polysiloxane. Its structure was confirmed by Hydrogen‐1 nuclear magnetic resonance (¹H NMR), real‐time infrared spectroscopy and gel permeation chromatography (GPC). Ultraviolet (UV) absorption spectra of 184‐AC‐Si showed a red‐shifted maximum absorption compared with 184. The kinetics of photopolymerization was studied by real‐time infrared spectroscopy. More importantly, because of the polysiloxane‐based photoinitiator had good ability to float up, which could be proved by X‐ray photoelectron spectroscopy, mapping energy dispersive spectroscopy, UV absorption, and GPC measurements, a convenient and simple method for preparing gradient polymer initiated by 184‐AC‐Si was successfully developed. Copyright © 2011 John Wiley & Sons, Ltd.     

Photoinduced miniemulsion polymerization

This study describes the radical photopolymerization of acrylate monomers in miniemulsion. Starting from nanosized acrylate droplets (<100 nm) which encapsulate a type I radical photoinitiator (BAPO), UV irradiation led after a few minutes to the formation of polymer nanoparticles of similar size. The present study deals with the kinetics aspects of this reaction and the colloidal properties of the resulting polymer dispersions. Real-time Fourier transform near-infrared spectroscopy in transmission was implemented to follow continuously the fast photopolymerization process. In addition, the spatial resolution of the photoinduced process allowed the online monitoring of the evolution of the miniemulsion size during the UV irradiation through dynamic light scattering.     

Microfluidic preparation of dual stimuli-responsive microparticles and light-directed clustering

We present a simple fabrication of photo- and thermoresponsive microparticles with a narrow size distribution in the PDMS-based microfluidic device. The monodisperse water-in-oil (W/O) droplets of poly(N-isopropylacrylamide-co-spironaphthoxazine methacryloyl) (PNIPA-SPO) were formed at the T-junction channel of the device by adjusting the flow conditions of two immiscible solutions. Subsequently, the droplets were polymerized downstream of the channel under 365 nm UV irradiation in the presence of 2,2'-diethoxyacetophenone (DEAP, photoinitiator) and N,N'-methylenebisacrylamide (MBA, monomer and cross-linker). Being photosensitive, the polymerized microparticles progressively change their color when subjected to UV-vis irradiation. Above the LCST of the copolymer, the microparticles exhibited volume shrinkage accompanied by color deterioration. In addition, the UV light-driven clustering of the PNIPA-SPO copolymer was observed within the W/O droplet in the absence of photoinitiator, which contributed to variable microstructures from Janus to acorn-like and snowman-like morphologies. This work is the first attempt to unveil the photocontrolled asymmetric particle morphology by using the photoresponsive polymer.     

Thermogravimetric analysis of thermal stability of poly(methyl methacrylate) films modified with photoinitiators

Films of poly (methyl methacrylate) (PMMA) were prepared by the addition of photoinitiator to the polymer. The influence of five organic photoinitiators on thermal stability of poly(methyl methacrylate) was studied by thermogravimetric analysis. Next, the PMMA films doped with these photoinitiators were UV irradiated and investigated in terms of changes in their thermal stability. It was found that the photoinitiators had accelerated thermal degradation of non-irradiated PMMA films due to the action of free radicals coming from the additives’ thermolysis. For UV-irradiated specimens, the effect of photoinitiator on PMMA thermal stability depended on the chemical structure of organic compound modifying the polymer. In general, thermal stability of irradiated samples was higher in the presence of additives. Thermal destruction of modified PMMA can be explained by the formation of resonance structures in aromatic photoinitiators and consumption of energy in dissipation processes.     

Rapid Photocrosslinkable Thermoresponsive Injectable Polyphosphazene Hydrogels

Rapidly photocrosslinkable and thermosensitive polyphosphazene polymers have been prepared to overcome the limitations associated with long UV exposure. Short UV exposure on the thermosensitive gels under mild conditions leads to quick photocrosslinking of the acrylate groups in the polymer network, and results in a dual crosslinked network with enhanced mechanical strength. The accelerated photocrosslinking can be attributed to the high reactivity of the acrylate double bond and hydrophobic interactions in the polymer network. The effects on the degree of photocrosslinking of the UV light intensity and the concentration of the photoinitiator were studied. In vitro and in vivo photocrosslinkings were accomplished within 120 and 180 s of exposure times, respectively. The degradation rate of the polymers depended on the degree of acrylate substitution in the polymer network. These results demonstrate that the injectable hydrogels with desired mechanical properties and degradation rates can be created in situ under mild photocrosslinkable conditions, and the dual crosslinkable acrylated poly(organophosphazenes) may hold great promise for biomedical delivery applications of biological molecules, cells, and drugs.

     

Effect of photoinitiator on photopolymerization of inorganic–organic hybrid polymers (ORMOCER®)

Inorganic–organic hybrid polymers have been developed and tested for evaluation in optical and electrical applications. Although hybrid inorganic–organic polymers can be synthesized by sol–gel chemistry at first, the physical properties of hybrid inorganic–organic polymers are changed during thin film-making processes, that is, photocuring and thermal curing. To investigate the effect of photoinitiator on the material properties during processing, a model system containing methacrylic groups as organically polymerizable units was selected. The conversion of CC double bond of methacrylic groups depending on some kinds of photoinitiator quantities was characterized by Fourier transform infrared spectroscopy. It was confirmed to correlate the degree of CC double bond conversion with the refractive indices. Thermodynamically, the enthalpy of the photopolymerization of hybrid polymer was investigated by UV–DSC. UV–DSC spectra showed the exothermic nature of photopolymerization of ORMOCER® to be in dependence of photoinitiator quantities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1979–1986, 2004     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

Temperature dependent light transmission-light scattering switching of (homeotropic liquid crystalline polymer network/liquid crystals/chiral dopant) composite film

A (photo-polymerizable liquid crystal (LC) monomer/LCs/chiral dopant/photoinitiator) mixture with a smectic A (SmA)-chiral nematic (N*) phase transition was sandwiched between two ITO glass substrates which were not subjected to any surface orientation treatment. When an electric field-induced homeotropically oriented SmA phase of the mixture was irradiated with UV light, an oriented liquid crystalline polymer (LCP) network was formed upon photo-polymerization of the LC monomer. Then, a (homeotropically oriented LCP network/LCs/chiral dopant) composite with a SmA-N* phase transition was prepared. A focal-conic texture appeared in the heat-induced N* phase of the composite upon heating from the transparent state of the homeotropically oriented SmA phase; the focal-conic texture exhibited strong light scattering. Upon cooling the composite to the SmA phase, this phase was again homeotropically oriented due to the strong intermolecular interaction between the LC molecules and the homeotropically oriented LCP network. Thus, the transparent state of the SmA phase and the light scattering state of the N* phase occurred reversibly upon cooling and heating, accompanied by the thermal SmA-N* phase transition.     

壳聚糖/聚乙烯醇共混超细纤维的制备及紫外光交联研究

用静电纺丝法制备壳聚糖/聚乙烯醇的共混超细纤维,采用扫描电镜考察了纺丝液浓度、共混物配比、喷丝口内径对纤维形貌的影响.此外,为减少壳聚糖/聚乙烯醇纤维膜的溶胀变形,在上述体系中加入可光交联的单体二缩三乙二醇双甲基丙烯酸酯(TEGDMA)、引发剂2-羟基-2-甲基-1苯基丙酮(1173),对电纺纤维进行紫外光交联.结果表明,当壳聚糖与聚乙烯醇质量比为8:2的共混体系中加入占混合溶液质量分数4%的TEGDMA、0.12%的1173作为交联剂时,所得的无纺布纤维直径比较均一,平均约为200 nm,经光交联处理后其耐水性能得到提高.     

Synthesis of a photoactive gemini surfactant and its use in AGET ATRP miniemulsion polymerisation and UV curing

A novel photoactive gemini surfactant was easily synthesised in high yields. The multi-functional molecule can be used as a gemini surfactant, a benzophenone type photoinitiator, and as an ATRP initiator. Poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)-block-poly(allyl methacrylate) (PMMA-b-PAMA) were prepared using the photoactive gemini surfactant as an ATRP initiator under soap-free miniemulsion polymerisation conditions. Kinetic results of the miniemulsion polymerisation of methyl methacrylate (MMA) indicate that the reaction has controlled/living characteristics. UV curing was performed by irradiation of the linear PMMA-b-PAMA polymer, in which PMMA-b-PAMA containing a benzophenone moiety functioned as a macromolecular photoinitiator.     

树枝状醚酰胺多官能团(甲基)丙烯酸酯低聚物的合成及其紫外光固化性能的研究

合成了树枝状(甲基)丙烯酸化醚酰胺低聚物,采用拉曼光谱、光-差热分析和动态力学热分析方法对其紫外光固化动力学和固化膜热机械性能进行了研究.结果表明,这种树枝状低聚物在紫外光照下双键转化率可达80%以上,且其最大反应速率、固化膜的软化温度和玻璃化转变温度随双键浓度的增大而提高.