Infrared Fingerprint Engineering: A Molecular‐Design Approach to Long‐Wave Infrared Transparency with Polymeric Materials

Optical technologies in the long‐wave infrared (LWIR) spectrum (7–14 μm) offer important advantages for high‐resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR‐transparent organic materials is that nearly all organic molecules absorb in this spectral window which lies within the so‐called IR‐fingerprint region. We report on a new molecular‐design approach to prepare high refractive index polymers with enhanced LWIR transparency. Computational methods were used to accelerate the design of novel molecules and polymers. Using this approach, we have prepared chalcogenide hybrid inorganic/organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co‐monomers.     

新型聚(甲基)丙烯酸酯/盐透明材料的制备及其性能

聚(甲基)丙烯酸酯具有优异的透光性、耐光性和耐候性,广泛用作光学塑料.研制高折射率、高耐热性、低吸湿性的透明高分子材料是近年来光学塑料研究和开发的重点之一.本文介绍了新型聚(甲基)丙烯酸酯/盐透明高分子材料的主要制备方法,即新型单体合成-聚合法、共聚法、共混-聚合法和有机-无机纳米杂化法,并系统地总结了各方法的特点以及所制备的材料的性能,展示了目前应用最为广泛的新型单体合成-聚合法和有机-无机纳米杂化法的潜在的应用前景.     

Tantalum(V) nitride inverse opals as photonic structures for visible wavelengths

The development of materials with a complete photonic band gap at visible wavelengths is believed to have the potential to lead to new control over long-lived emissive excited states, single molecule lasers, and nearly lossless nanoscale waveguides. In this work we move toward that goal with the synthesis of an inverse opal thin film of Ta3N5 produced through atomic layer deposition. The highly regular architecture achievable by atomic layer deposition is combined with an unusually high refractive index and transparency in at least part of the visible spectrum. The result is a material that represents the closest example to date of a photonic crystal with a band gap at optical wavelengths.     

Synthesis of silyl-functionalized oligothiophene-based polymers with bright blue light-emission and high refractive index

In this paper, we report the synthesis of partially conjugated polymers with a silyl-group-substituted oligothiophene and a short alkyl chain in the main chain by hydrosilylation polymerization and describe their optical properties such as luminescence and refractive index. The obtained polymers are found to have good solubility and processability. Moreover, the high steric hindrance of the silyl-group can inhibit the π-π interaction and intermolecular aggregation of the polymers. Hence, the emission of the obtained polymers was similar to that of the corresponding silyl-group-substituted oligothiophene. The polymers exhibit intense light blue fluorescence under UV irradiation and a high refractive index in the visible light region.     

高折射率聚合物-无机纳米光学杂化材料的设计与制备及其应用

传统的高折射率聚合物光学材料,可以通过向聚合物中引入一些芳香环,含硫基团以及除氟以外的其他卤素原子来提高聚合物光学材料的折射率,但是就目前的研究现状来看,这类纯聚合物光学材料的折射率一般都低于1.8.而将具有高折射率的无机纳米粒子引入到聚合物中,所制备的聚合物-无机纳米光学材料的折射率能够达到1.8以上.而且这类高折射率聚合物-无机纳米光学杂化材料同时具有高分子光学材料和无机材料的双重优点,具有广泛的应用前景.鉴于当前高折射率聚合物-无机纳米光学杂化材料发展之迅速和其研究与开发的重要性,并结合目前国内外的研究现状,本文就高折射率聚合物-无机纳米光学杂化材料的设计、制备方法及其相关应用做一个比较系统的介绍,同时对这类材料在未来研究中所应注意的问题也提出了相应的看法.     

高折射率有机/无机纳米杂化透明膜层材料的制备与性质研究

采用溶胶-凝胶法,将钛酸酯和硅烷偶联剂(KH-560)进行共水解,经涂膜、固化,制备了一系列含有无机二氧化钛纳米相的无机/有机杂化膜层材料,通过不同方法对杂化膜层的微结构、光学、机械和热性质进行了表征.结果表明,所得到的有机/无机纳米复合膜层,在可见光范围内的透过率均在90%以上,同时具有较好的耐热性和较高的折射率(nd=1.47~1.73),并且膜层与基材的附着性好,铅笔硬度达到4~5H.     

High Refractive Index Films Prepared from Titanium Chloride and Methyl Methacrylate via a Non-Aqueous Sol–Gel Route

Poly(methylmethacrylate)/silica/titania films were prepared via a nonaqueous sol–gel route at ambient temperature, followed by spin-coating and multistep baking. The acrylic monomers used were methyl methacrylate (MMA) and 3-(trimethoxysilyl)propyl methacrylate (MSMA). Silicic acid and titanium(IV) chloride were used as the precursors of the inorganic component. FTIR results indicated the successful bonding between TiO₂ and SiO₂. TEM images suggested the silica/titania particles were well dispersed in the Poly(methyl methacrylate) (PMMA) matrix with the particles size smaller than 40 nm in our study. The refractive index and extinction coefficient were also studied. The refractive index of the hybrid increased with increasing the titania content, and the hybrid films showed high optical transparency in visible region.     

Organocatalyzed Photocontrolled Radical Polymerization of Semifluorinated (Meth)acrylates Driven by Visible Light

Fluorinated polymers are important materials that are widely used in many areas. Herein, we report the development of a metal‐free photocontrolled radical polymerization of semifluorinated (meth)acrylates with a new visible‐light‐absorbing organocatalyst. This method enabled the production of a variety of semifluorinated polymers with narrow molar‐weight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides. The high performance of “ON/OFF” control and chain‐extension experiments further demonstrate the utility and reliability of this method. Furthermore, to streamline the preparation of semifluorinated polymers, a scalable continuous‐flow approach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties.     

Effect of pH on the properties of nanocrystalline CuO thin films deposited by sol-gel process

Nanocrystalline cupric oxide thin films were prepared using the sol-gel method. Three sols with different pH were performed in order to evaluate the pH effect on the morphology and optical properties of the films. XRD pattern confirmed the nanocrystalline monoclinic CuO phase formation. The influences of pH on surface morphology of films were investigated by scanning electron microscopy (SEM). It was observed that grains size increases by increasing the pH of the sol. UV-Vis spectrum measurement showed low transparency of the films in the visible region. Optical constants such as extinction coefficient, refractive index and optical band gap were evaluated from these spectra by using the Pointwise Unconstrained Minimization Approach (PUMA). The band gap of the films varies from 2.20 to 1.98 eV for various pH of sol.     

Ultrafast Optical Responsive SWNT/Polymer Thin Films in Guided Wave Mode Geometry

Single walled carbon nanotubes (SWNT) having good optical and electrochemical properties were solublized by aromatic polymers. The polymer-wrapped SWNT film cast from solution showed transient bleaching with a time constant of recovery less than 1 ps in both the visible and optical telecommunication wavelength region. Polymer thin film containing SWNT was assembled into the guided wave mode geometry with a low refractive index polymer.     

Effect of dopant structure on refractive index and glass transition temperature of polymeric fiber‐optic materials

Graded‐index plastic optical fibers, composed of doped polymers, have advantages over conventional glass optical fibers, but need to be developed further for practical application. Here, a variety of aromatic sulfide dopants were synthesized, and their effects on the refractive indexes and glass transition temperatures (T_g) of poly(methyl methacrylate) and methyl 2‐chloroacrylate/2,2,2‐trichloroethyl methacrylate copolymers were studied. While polymers containing large dopants exhibited relatively high refractive indices, their T_g values were low, making these materials unsuitable for graded‐index plastic optical fiber applications. Six dopants yielded polymers that exhibited higher T_g values than the conventionally used (diphenyl sulfide)‐doped polymer. The dopant dibenzothiophene, in particular, yielded polymers with the highest refractive indexes and T_g values, and polymers containing (phenylthio)benzene dopants also performed well. Copyright © 2013 John Wiley & Sons, Ltd.     

Highly refractive polymer resin derived from sulfur‐containing aromatic acrylate

New sulfur‐containing polymers with high‐refractive indices and low birefringences have been developed as UV‐curable high‐refractive polymer resins. The polymers derived from 2,7‐bis[(2‐acryloylethyl)sulfanyl]thianthrene (2,7‐BAST) and 4,4′‐bis[(acryloyloxyethylthio)diphenylsulfide (4,4′‐BADS) were prepared by photopolymerization under UV irradiation. Transparent UV‐cured films were obtained in both cases. Both polymers showed good thermal stability, such as a 5% weight‐loss temperature at 355 °C under nitrogen and glass transition temperatures (T_g) in the range of 94–143 °C. They also showed high‐refractive indices of 1.6531 and 1.6645 at 632.8 nm and low birefringences of 0.0039 and 0.0069 in addition to high transparency in the visible region. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2604–2609, 2010     

New Ti?PTMO and Zr?PTMO ceramer hybrid materials prepared by the sol gel method: Synthesis and characterization

New transparent flexible hybrid network “ceramer” materials have been synthesized by incorporating triethoxysilane capped polytetramethylene oxide with highly reactive titanium isopropoxide or zirconium n-propoxide without adding chelating agents. Both of these types of ceramer materials display high transparency while the zirconium systems show considerable transparency in the UV region. The titanium systems exhibit higher refractive index than the corresponding zirconium materials of equal alkoxide content.     

High refractive index hyperbranched polyvinylsulfides for planar one‐dimensional all‐polymer photonic crystals

We report on the growth and characterization of one‐dimensional (1D) planar all‐polymer photonic crystals (PhC) with high dielectric contrast (Δn = 0.3) prepared by spin coating using hyperbranched polyvinylsulfide polymers (HB‐PVS) as high refractive index material and cellulose acetate as low refractive index material. Solution processable HB‐PVS show a near ultraviolet absorption inducing an increased refractive index in the visible‐near infrared (n = 1.68, λ = 1000 nm). HBPVS:Cellulose Acetate Distributed Bragg Reflectors show a very clear fingerprint of the photonic band gap possessing the expected polarized dispersion properties as a function of the incidence angle. Moreover, engineered microcavities tuned on the weak fluorescence spectrum of the HB‐PVS show directional fluorescence enhancement effects due to spectral redistribution of the emission oscillator strength. The combination of all these properties testifies the high optical quality of the obtained photonic structures thus indicating HB‐PVS as an interesting material for the preparation of such PhC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 73–80     

Thermal and optical properties of novel polyurea/silica organic–inorganic hybrid materials

Current optical polymeric materials for advanced fiber laser development are susceptible to degradation due to the heat generated in high power usage. A suitable replacement light stripping material was explored to overcome this problem by examining optical and physical properties such as transmission/absorption, refractive index, thermal conductivity, and thermal stability. The synthesis and characterization of two new polyurea/silica ORMOSILs (ORganically MOdified SILicates) suitable for high temperature (up to 300 °C) optical applications are reported herein. A one-pot, room temperature synthesis is based upon commercially available bis-isocyanates and an amino-silane. These materials exhibit the combined traits of both glass and polymer by displaying optical clarity over a wide range of wavelengths stretching from the edge of the UV (250 nm) to well into the NIR (2,000 nm), refractive indices in the visible spectrum (n = 1.50–1.63), thermal conductivities of 0.26 ± 0.09 W/mK (ORMOSIL-A) and 0.27 ± 0.07 W/mK (ORMOSIL-B), and thermal stabilities up to 300 °C. The hybrid materials were found to be easily processed into films but thick casts (>2 mm) were subject to increased rates of cracking and longer curing times. Although this is typical of sol–gel chemistries, the organic constituents of ORMOSILs reduce this effect as compared to purely inorganic sol–gels. The effect of thermal aging on the materials’ properties will also be presented as well as a comparison of these materials and the current state of the art light stripping material.     

Characterization of Optical Properties in Water-in-Oil Emulsion

There have been few studies on the factors that determine the overall appearance of emulsions. Optical properties are quite important in determining the perceived quality of emulsion-based products. The overall appearance of an emulsion is determined by the way that it interacts with electromagnetic radiation in the visible region of the spectrum, for example, reflection, transmission, adsorption, and scattering. These interactions are principally determined by the characteristics of emulsion droplets (size, concentration, and refractive index). The present study aims at characterizing the optical properties and rheological behaviors of water-in-oil emulsions, especially macroemulsions. There is a decrease in the absorbance spectra as increasing glycerin ratio in aqueous phase because the difference of refractive index between oil phase and aqueous phase decreased, which improved the transparency of water-in-oil emulsion. The absorbance of linear and branched surfactant emulsions were smaller than that of alkyl modified branched surfactant emulsion. Moreover the transparency of emulsions prepared with linear and branched surfactants was much clearer than that of alkyl modified branched surfactant emulsion. The absorbance spectra also showed that low polar oil attributed to the more transparent emulsion, compared with high polar or nonpolar oil. However, these kinds of oils were not helpful to prepare transparent emulsion because the appearance of these emulsions was translucent or opaque, even if polyols in aqueous phase was 30 wt%.     

Photochemically-induced refractive index and fluoresence patterning on polymer films

The molecular design for large photo-induced refractive index changes in transparent visible light region was proposed and realized with norbornadiene polymers and poly(vinyl cinnamate). The patterning of pure refractive-index contract on their transparent films was made with near-field scanning optical microscopy (NSOM). Reversible fluorescence patterning on polymer films is also presented by using controlled energy transfer from a fluorescent pyromethene to a photochromic diarylethene.     

Optical Polymer Having a High Refractive Index and High Abbe Number Prepared by Radical Polymerization Using 2,5-BiS(2-Thia-3-Butenyl)-1,4-Dithiane

Abstract

Novel poly(vinylsulfide)s were prepared by addition polymerization using 2,5-bis(2-thia-3-butenyl)-1,4-dithiane (TBD) with a radical initiator for an optical polymer having a high refractive index (n_D) and Abbe number (v). Homopolymerization of TBD (72.9% conversion) and copolymerization with acrylonitrile or acrylates having nonpolar groups (50.4–81.3% conversion according to the comonomers used) in a limited composition range yielded hard and transparent polymers suitable for application in optics. The methacrylates used yielded no polymeric product as a result of the copolymerization. The obtained polymers had T_g, n_D and v ranging between 41.0–124.0°C, 1.678–1.546 and 34.1–43.8, respectively, except that poly(TBD) did not exhibit T_g below 200°C, and it had the highest n_D Most of the polymers have higher n_D and v than those of other conventional optical polymers and moreover, their values are comparable to those of flint glasses. The copolymerizability of TBD and the group contribution to n_D and v are discussed based on the Q-e scheme and on the Lorentz-Lorenz equation, respectively. This work shows that TBD serves as a useful material for the preparation of polymers having high n_D and v along with a T_g of more than 100°C, and that the polymers thus obtained are promising optical materials.

     

Sustainable polymer materials for flexible light control and thermal management

The urgency of the global energy and climate crises demands quick development of energy-saving and temperature regulating technologies. Efficient thermal management by selective control of visible and infrared light is possible with advanced optical materials. Already, garments are being functionalized with such materials and may significantly reduce indoor heating and cooling costs, for which a huge (~10% in the United States) amount of energy is consumed. The ability to harness light also enables other technologies including dynamic camouflage and photoactivated self-decontaminating surfaces. Although much focus has been placed on carbon and inorganic nanomaterials for these applications, this perspective investigates optically active polymer materials as arguably more benign alternatives for flexible devices. Passive and dynamic control of light for heating and cooling using polymers is covered, as well as a discussion comparing conjugated polymers with commonly used nanomaterials.     

高折射率环氧和环硫型光学树脂的研究进展

环氧树脂;环硫化合物;高折射率环氧和环硫型光学树脂的研究进展