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1.
We synthesized two novel organic nonlinear optical chromophores—chiral S(+)‐N‐[p‐(4‐nitrostyryl) phenyl] prolinol and non‐chiral [p‐(4‐nitrostyryl) phenyl] piperdine—as potential laser‐active dyes for photonic applications. Both materials show good optical transmittance in the telecommunication frequency region, desirable solubility in acrylic polymer optical fiber matrices, and attractive fluorescence properties that are advantageous for laser‐gain materials and devices. Subsequently, these two chromophores were incorporated into poly(methyl methacrylate) and poly(ethyl methacrylate) and drawn into polymer optical fibers. The relevant properties of these organic dye‐doped fibers have been studied, revealing essential attributes of laser‐active characteristics. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1794–1801, 2001  相似文献   

2.
The effects of cucurbit[n]uril on the dissolution and the photophysical properties of nonionic conjugated polymers in water are described. For this purpose, a fluorine‐based polymer, namely, poly[9,9‐bis{6(N,N‐dimethylamino)hexyl}fluorene‐co‐2,5‐thienylene (PFT) was synthesized and characterized by spectroscopic techniques including 1D and 2D NMR, UV–vis, fluorescent spectroscopy, and matrix‐assisted laser desorption mass spectrometry (MALDI‐MS). For the first time, it was demonstrated that a nonionic conjugated polymer can be made soluble in water through an inclusion complex formation with CB8. The structure of the complex was elucidated by NMR experiments including 1H and selective 1D‐NOESY. This complex emits green and is highly fluorescent with fluorescent quantum yield of 35%. In contrast, CB6 or water‐soluble CB7 although they are chemically identical to CB8 do not have any effect on the dissolution and photophysical properties of PFT. By preparing a protonated version of PFT, the optical properties of PFT in methanol, protonated PFT and PFT@CB8 in water have been studied and compared. It was also observed that the morphology of the polymer PFT was affected by the presence of CB8. Thus CB8‐assisted self‐assembly of polymer chains leads to vesicles formation; these structures were characterized by DLS, AFM, SEM, and TEM fluorescent optical microscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

3.
In this paper, relationships between the scattering domain parameters (size and shape) and the light‐shielding properties of thermotropic systems with fixed domains (TSFD) are established. Specific focus is given to the effect of additive type on the formation of scattering domain size. Various functional layers are prepared by a variation of thermotropic additives. Scattering domains are investigated applying high resolution Atomic Force Microscopy (AFM) in a phase imaging mode. Thermotropic layers formulated with additive types exhibiting a short chain length display roughly spherical scattering particles with dimensions between 0.5 and 3 µm and a moderate reduction in hemispheric solar transmittance along with a significant increase in diffuse solar transmittance above the switching threshold. Additive types with long‐chain molecules develop anisotropic scattering domains resembling distorted disks with a diameter up to 50 µm and a thickness between 100 and 400 nm. Disk‐like scattering features yield enhanced light‐shielding properties. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

4.
The layer‐by‐layer (LBL) assembly technique is an attractive method to make functional multilayer thin films and has been applied to fabricate a wide range of materials. LBL materials could improve optical transmittance and mechanical properties if the film components were covalently bonded. Covalently bonded nanocomposite multilayer films were prepared by employing hydrophilic aliphatic polyisocyanate (HAPI) as the reactive component, to react with Laponite and polyvinyl alcohol (PVA). FT‐IR spectra suggested that HAPI reacted with Laponite and PVA at ambient temperature rapidly. Ellipsometry measurement showed that the film thickness was in linear growth. The influences of HAPI on the optical, mechanical and thermal properties of the films were investigated by UV‐Vis spectroscopy, tensile stress measurement, DSC and TGA. The obtained results showed that the optical transmittance and mechanical strength were enhanced when the film components were covalently bonded by HAPI. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 545–551  相似文献   

5.
The degradation of poly(fluoroalkyl acrylate)s with long perfluoroalkyl groups, especially with perfluorooctyl group, leads to the release of biopersistent perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS). To find the environmentally friendly substitutes, a series of nonbiopersistant fluorinated polymers containing perfluorohexyl groups in the side chains have been synthesized and characterized. This study was then focused on the role played by the main chain and spacer group located in the side chain between the backbone and the fluorinated segment and, in particular, on the properties of poly[2‐[[[[2‐(perfluorohexyl)]‐sulfonyl]methyl]amino]ethyl] acrylate (PC6SA), methacrylate (PC6SMA) and poly[(perfluorohexyl)ethyl] methacrylate (PC6MA). Surface properties and bulk organization of fluorinated side chains of those polymers were investigated by contact angles, differential scanning calorimetry, optical polaring microscopy, and wide‐angle X‐ray scattering. Results were compared with those obtained with poly[(perfluorohexyl) ethyl] acrylate (PC6A). They all had very low surface free energies. Surprisingly, with the same perfluoalkyl chain, PC6SA and PC6SMA with a N‐methylsulfonamide spacer group were found to be organized in a liquid crystalline lamellar structure, whereas PC6A and PC6MA were found to be amorphous. This was mainly attributed to the steric term and polarity of N‐methylsulfonamide group that tended to facilitate the orientation of the perfluorinated segments in smectic phases. PC6SA, PC6SMA, and PC6MA had rich dynamic water repellency because of the low surface molecular mobility. This phenomenon relates to the crystallization of side chains or high glass transition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2584–2593, 2010  相似文献   

6.
Fiber‐structure‐development in the poly(ethylene terephthalate) fiber drawing process was investigated with online measurements of wide‐angle and small‐angle X‐ray scattering with both a high‐luminance X‐ray source and a CO2‐laser‐heated drawing system. The intensity profile of the transmitted X‐ray confirmed the location of the neck‐drawing point. The diffraction images had a time resolution of several milliseconds, and this still left much room for improvement. Crystal diffraction appeared in the wide‐angle X‐ray images almost instantaneously about 20 ms after necking, whereas a four‐point small‐angle X‐ray scattering pattern appeared immediately after necking. With the elapse of time after necking, the four‐point scattering pattern changed into a meridional two‐point shape. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1090–1099, 2005  相似文献   

7.
OPTICAL AND THERMAL CHARACTERIZATION OF NATURAL (Sepia officinalis) MELANIN   总被引:2,自引:0,他引:2  
Abstract The optical properties and the thermal diffusivity of natural cuttlefish ( Sepia officinalis ) melanin have been measured. The optical absorption and scattering properties of melanin particles were determined at 580 nm and 633 nm, using photometric and photothermal techniques. For the photometric studies, the absorption and the transport scattering coefficients were determined from the measurements of diffuse reflectance and transmittance. The scattering anisotropy was obtained from an additional measurement of the total attenuation coefficient and independently obtained by goniometry. For photothermal studies, pulsed photothermal radiometry was used to deduce the absorption and transport scattering coefficients via a model based on optical diffusion theory. Pulsed photothermal radiometry was also used to provide the thermal diffusivity of solid melanin pressed pellets.  相似文献   

8.
We have investigated the effect of antiplasticization on the stress‐optical behavior of polycarbonate (PC) containing terphenyls (tPh) and di(2‐ethylhexyl)adipate (DEHA). Addition of the three tPhs (p‐, o‐, and m‐tPh) and DEHA at contents of 5–10 wt % increases the tensile storage modulus (E' ) of PC owing to the antiplasticization effect. In particular, p‐tPh increases E' more than the other additives, suggesting that the rod‐like shape matches the free volume of PC in the glassy state. The three tPh isomers improve the glassy birefringence of PC while DEHA does not change the glassy birefringence, which corresponds to the polarizability anisotropy. The stress‐optical coefficient, a ratio of stress and birefringence, of PC decreases with increasing additive content in order of p‐tPh ? o‐tPh > m‐tPh = DEHA. This result is agreement with a restricted rotational motion of additive molecule in PC, which is observed in dynamic mechanical and birefringence data. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1837–1842  相似文献   

9.
Solid polymer electrolyte (SPE) systems based on interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices, with lithium perchlorate as guest salt, were prepared. These electrolytes were presented as free‐standing films, and their thermal and electrochemical properties were characterized by conductivity and electrochemical stability measurements. The properties of the interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices as the electrolyte component of a solid‐state electrochromic device are reported and the results obtained suggest that this electrolyte provides an encouraging performance in this application. The most conducting electrolyte composition of this SPE system is the formulation designated as SPE2‐0PC (5.01 × 10?4 S cm?1 at about 57°C). The lowest decomposition temperature was registered with the SPE6‐15PC composition (233°C). The average transmittance in the visible region of the spectrum was above 41% for all the samples analyzed. After coloration the device assembled with 71 wt% PC presented an average transmittance of 15.71% and an optical density at 550 nm of 0.61. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

10.
Summary: In this paper spectroscopic techniques were adapted and applied to characterize the optical and morphological properties of thermotropic resins. Thermotropic films were prepared by variation of resin base and thermotropic additives. By UV/Vis/NIR spectroscopy the solar optical properties, the switching temperature, the switching process and the residual transmittance in the opaque state were determined. To control the sample temperature from ambient to 100 °C a conventional UV/Vis/NIR spectrophotometer equipped with an Ulbricht-sphere was adapted by a heating stage. Additive content, distribution and scattering domain size were characterized by Differential Scanning Calorimetry, Attenuated Total Reflectance spectroscopy and microscopic techniques. For the investigated film types hemispheric solar transmittance values ranging from 80 to 87% and 75 to 85% were obtained in the clear and the scattering state, respectively. The diffuse solar transmittance values increased significantly from 14 to 40% below the switching temperature to 36 to 70% at elevated temperatures. The thermotropic resins exhibit a steep and rapid switching process with switching temperatures between 45 and 70 °C. The materials with the best switching properties are characterized by distinct differences in refractive index between the components, a uniform additive distribution and scattering domains with diameters below 1000 nm.  相似文献   

11.
Two neutral precursor conjugated copolymers based 2,7‐diethynylfluorene and 3,6‐diethynylcarbazole units in the main chain ( PFC and PF2C ) were prepared by Hay coupling polymerization. Their cationic copolymers ( CPFC and CPF2C ) were prepared by the methylation of their diethylpropylamino groups with CH3I. For comparison, neutral conjugated homopolymers of 2,7‐diethynylfluorene ( PF ), 3,6‐diethynylcarbazole units ( PC ) and their cationic polymers ( CPF and CPC ) were also prepared with the same method. A comparative study on the optical properties of cationic polymers CPFC and CPF2C in DMF and DMF/H2O showed that they underwent water‐induced aggregation. The spectral behaviors of CPFC and CPF2C with calf thymus DNA showed that a distinct fluorescent quenching took place with minute addition of CT DNA (3.3 × 10?13 M). The results showed that the polymers would be promising biosensor materials for sensitive detection of DNA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4168–4177, 2010  相似文献   

12.
A new multi‐variable‐measurement approach for characterizing and correlating the nanoscale and microscale morphology of crystal‐amorphous polymer blends with melt‐phase behavior is described. A vertical small‐angle light scattering (SALS) instrument optimized for examining the scattering and light transmitted from structures ranging from 0.5 to 50 μm, thereby spanning the size range characteristic of the initial‐to‐late stages of thermal‐phase transitions (e.g., melt‐phase separation and crystallization) in crystal‐amorphous polymer blends, was constructed. The SALS instrument was interfaced with differential scanning calorimetry (DSC), and simultaneous SALS/DSC/transmission measurements were performed. We show that the measurement of transmitted light and SALS under HV (cross‐polarized) optical alignments during melting can be used to reliably measure the thermodynamic (e.g., crystal melting and melt‐phase separation temperatures) and structural variables (e.g., crystalline fraction within the superstructures and volume fraction of superstructures) necessary for describing the multiphase behavior of crystal‐amorphous blends in one combined measurement. We also evaluate the orientation correlations of crystalline volume elements within the superstructures. Our results indicate that simultaneous measurement of transmitted light can provide a reliable estimate of the total scattering from density and orientation fluctuations and the melt‐phase separation temperature of polymer blends. For solution‐cast poly(?‐caprolactone)/poly(D,L‐lactic acid) blends, our multivariable measurements during melting provide the parameters necessary to generate a crystal–liquid and liquid–liquid phase diagram and characterize the solid‐state morphology. This opens up the challenge to explore use of our vertical SALS instrument as a rapid and convenient method for developing structure–property relationships for crystal‐amorphous polymer blends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2714–2727, 2002  相似文献   

13.
The poly(N‐vinylcarbazole)‐grafted MWNTs (MWNT‐PVK) hybrid materials were synthesized in the presence of S‐1‐Dodecyl‐S′‐(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate (DDAT)‐covalently functionalized multiwalled carbon nanotubes (MWNT‐DDAT) as reversible addition–fragmentation chain transfer (RAFT) agent. Incorporation of the PVK moieties onto the MWNTs surface can considerably improve the solubility and processability of MWNTs. For all MWNT‐PVK hybrid materials, they are soluble in some common organic solvents such as toluene, THF, chloroform, DMF and others. In contrast to the UV/Vis spectrum of DDAT‐PVK, which was synthesized by use of DDAT as RAFT agent under the same synthetic condition, in the visible region, the absorption spectrum of MWNT‐PVK exhibited a typical electronic absorption characteristics of solubilized carbon nanotubes, in which the absorbance decreases gradually in the range of 350–600 nm. At the same level of linear transmission the MWNT‐PVK with 79.2% PVK moieties in the material structure possesses best optical limiting performance in comparison with the other MWNT‐PVK composites, MWNTs and C60. The significant NLO responses manifest the MWNT‐PVK materials suitable candidate for viable optical limiting devices. Light scattering, originating from the thermal‐induced microplasmas and/or microbubbles, is responsible for the optical limiting. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3161–3168, 2010  相似文献   

14.
True model linear poly(styrene‐b‐dimethylsiloxane) PS‐b‐PDMS copolymers were synthesized by using sequential addition of monomers and anionic polymerization (high‐vacuum techniques), employing the most recent experimental procedures that allow the controlled polymerization of each monomer to obtain blocks with controlled molar masses. The model diblock copolymers obtained were analyzed by using different techniques, such as size‐exclusion chromatography, 1H NMR, Fourier transform infrared spectroscopy, small angle X‐rays scattering (SAXS), and wide angle X‐rays scattering (WAXS). The PS‐b‐PDMS copolymers obtained showed narrow molar mass distribution and variable PDMS content, ranging from 2 up to 55 wt %. Compacted powder samples were investigated by SAXS to reveal their structure and morphology changes on thermal treatment in the interval from 30 to 200 °C. The sample with the highest PDMS content exhibits a lamellar morphology, whereas two other samples show hexagonally packed cylinders of PDMS in a PS matrix. For the lowest PDMS content samples, the SAXS pattern corresponds to a disordered morphology and did not show any changes on thermal treatment. Detailed information about the morphology of scattering domains was obtained by fitting the SAXS scattering curves. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3119–3127, 2010  相似文献   

15.
Electro‐optic side‐chain polymers have been synthesized by the post‐functionalization of methacrylate isocyanate polymers with novel phenyl vinylene thiophene vinylene bridge (FTC) nonlinear optical chromophores. For this application, FTC‐based chromophores were modified in their electronic donor structure, exhibiting much larger molecular hyperpolarizabilities compared with the benchmark FTC. Of these new chromophores, absorption spectra, hyper‐Rayleigh scattering experiment, and thermal analysis were carried out to confirm availability as effective nonlinear optical units for electro‐optic side‐chain polymers. The electro‐optic coefficients (r33) of obtained polymers were investigated in the process of in situ poling by monitoring the temperature, current flow, poling field, and electro‐optic signal. Compared with the nonsubstituted analogue, benxyloxy modified FTC chromophore significantly achieved higher nonlinear optical property, exhibiting molecular hyperpolarizability at 1.9 μm of 4600 × 10?30 esu and an r33 value of 150 pm/V at the wavelength of 1.31 μm. Synthesized electro‐optic polymers showed high glass transition temperature (Tg), so that the temporal stability examination exhibited >78% of the electro‐optic intensity remaining at 85 °C over 500 h. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

16.
Novel and well‐defined amphiphilic dendrimer‐star copolymer poly(ε‐caprolactone)‐block‐(poly(2‐(2‐methoxyethoxy)ethylmethacrylate‐co‐oligo(ethylene glycol) methacrylate))2 with Y‐shaped arms were synthesized by the combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The investigation of thermal properties and the analysis of crystalline morphology indicate that the high‐branched structure of dendrimer‐star copolymers with Y‐shaped arms and the presence of amorphous P(MEO2MA‐co‐OEGMA) segments together led to the complete destruction of crystallinity of the PCL segments in the dendrimer‐star copolymer. In addition, the hydrophilicity–hydrophobicity transition of the dendrimer‐star copolymer film can be achieved by altering the external temperatures. The amphiphilic copolymers can self‐assemble into spherical nanomicelles in water. Because the lower critical solution temperature of the copolymers can be adjusted by varying the ratio of MEO2MA and OEGMA, the tunable thermosensitive properties can be observed by transmittance, dynamic laser light scattering, and transmission electron microscopy (TEM). The release rate of model drug chlorambucil from the micelles can be effectively controlled by changing the external temperatures, which indicates that these unique high‐branched amphiphilic copolymers have the potential applications in biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

17.
Abstract— Time-resolved transmittance was used to extract in vivo optical properties of leaves of green plants experimentally. In time-resolved transmittance measurements an ultrashort light pulse is directed onto the surface of the object and the transmitted light is measured with a time resolution in the range of picoseconds. A table-top terawatt laser was used to generate 200 fs light pulses at 790 nm with a repetition rate of 10 Hz. The light pulses were focused through a cuvette filled with water to produce white light pulses and optical filters were placed in the beam path to select the wavelength of the light focused onto the leaf surface. The time profiles of the light transmitted through the leaves was recorded with a streak camera having a time resolution of about 2.5 ps. Results from Crassula falcata and Phaseolus vulgaris studied at 550, 670 and 740 nm are reported. The three selected wavelength regions represent medium, high and a low absorption of light, respectively. A library of curves was generated using Monte Carlo simulation, and the absorption and scattering coefficients were extracted by comparison of experimental curves with this library. Our results suggest that in the case of the thin (200 μm) Phaseolus leaves and certainly in the case of the thick (4 mm) Crassula leaves, light scattering plays an important role in light transport through the leaf and should also affect light flux in these leaves.  相似文献   

18.
Single‐walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ‐benzyl‐L ‐glutamate) (PBLG) by ring‐opening polymerizations of γ‐benzyl‐L ‐glutamic acid‐based N‐carboxylanhydrides (NCA‐BLG) using amino‐functionalized SWCNTs (SWCNT‐NH2) as initiators. The SWCNT functionalization has been verified by FTIR spectroscopy and transmission electron microscopy. The FTIR study reveals that surface‐attached PBLGs adopt random‐coil conformations in contrast to the physically absorbed or bulk PBLGs, which exhibit α‐helical conformations. Raman spectroscopic analysis reveals a significant alteration of the electronic structure of SWCNTs as a result of PBLG functionalization. The PBLG‐functionalized SWCNTs (SWCNT‐PBLG) exhibit enhanced solubility in DMF. Stable DMF solutions of SWCNT‐PBLG/PBLG with a maximum SWCNTs concentration of 259 mg L?1 can be readily obtained. SWCNT‐PBLG/PBLG solid composites have been characterized by differential scanning calorimetry, thermogravimetric analysis, wide/small‐angle X‐ray scattering (W/SAXS), scanning electron microscopy, and polarized optical microscopy for their thermal or morphological properties. Microfibers containing SWCNT‐PBLG and PBLG can also be prepared via electrospinning. WAXS characterization reveals that SWCNTs are evenly distributed among PBLG rods in solution and in the solid state where PBLGs form a short‐range nematic phase interspersed with amorphous domains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2340–2350, 2010  相似文献   

19.
The first part of a series of two, this paper analyzes the degradation of pure and filled PTFE under high energy UV radiation. The polymer morphology is first investigated using differential scanning calorimetry, highlighting the respective nucleating efficiency of TiO2 and CaF2 during polymer crystallization. Then, the various polymers are exposed to excimer laser radiation and observed under an optical microscope. The results indicate that the degradation is closely connected with microstructural parameters. In pure PTFE, scattering by crystallites and reflection on piles of lamellae control the nature and extent of the degradation. In filled PTFE, nature and concentration of fillers are the most important features governing degradation. When absorbing particles are added to PTFE, the damage is restricted to the surface and photothermal processes can modify the degradation from heterogeneous to ablative, depending on the filler content. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2057–2067, 1998  相似文献   

20.
Today, solid‐state nuclear magnetic resonance (NMR) is one of the most powerful and versatile tools for elucidating the structures and dynamics of molecular, macromolecular, and supramolecular systems. It provides information on molecular and collective phenomena over large length scales and timescales and is particularly suited to handle noncrystalline materials. This report describes how developments in solid‐state NMR were triggered by the possibilities that became available about 30 years ago by neutron scattering and synchrotron radiation. Close analogies between NMR spectroscopy and scattering are pointed out to emphasize that the two approaches nicely complement each other. Specific examples applying the new NMR techniques to amorphous polymers and supramolecular systems are described. The findings are related to the mechanical properties of polymers as well as specific functions such as photoconductivity and proton conductivity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5031–5044, 2004  相似文献   

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