The effect of the size of polymer chain on the energy transfer between chromophores bound to the ends of the chain

The dependence of the luminescence quantum yield of linear polymer molecules that contain chromophores at the ends on the number of units of polymer chain is studied. Numerical calculations for the dipole-dipole energy transfer between chromophores show that an increase in the chain length by a factor of 2 leads to a several-fold increase in the luminescence quantum yield depending on the ratio of the Förster radius to the radius of polymer coil. An approximate formula is derived for the adequate analysis of the dependence at the Förster radius that is significantly less than the radius of polymer coil. The dependence of the luminescence quantum yield of linear polymer molecules on the length of the statistical segment (unit) at a constant total length of the chain is also studied.     

Gamma-ray irradiation effect on the absorption and luminescence spectra of Nd:GGG and Nd:GSGG laser crystals

Laser crystals Nd³⁺:Gd₃Ga₅O₁₂ (Nd:GGG) and Nd³⁺:Gd₃Sc₂Ga₃O₁₂ (Nd:GSGG) were grown by Czochralski method. The influence of gamma-ray irradiation on their absorption and luminescence spectra has been investigated. Two additional absorption (AA) bands induced by gamma-ray irradiation appear in the spectra of Nd:GGG crystal while only a very weak AA band appears for the Nd:GSGG crystal. This indicated that Nd:GSGG crystal has stronger ability to resist the color center formation by irradiation. The intensity of the excitation and emission spectra of Nd:GGG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, a luminescence strengthening effect was observed in Nd:GSGG crystal after exposure to the same irradiation dose. The results showed that the Nd:GSGG crystal is a promising candidate used under radiation environments such as in outer space.     

The influence of optical bleaching on lifetimes and luminescence intensity in the slow component of optically stimulated luminescence of natural quartz from Nigeria

The intensity of optically stimulated luminescence may be decreased to a slow or medium component of its decay curve by optical bleaching, that is, by prolonged exposure of the luminescent sample to stimulating light. In this paper, we report on the influence of irradiation and measurement temperature on luminescence lifetimes as well as on the effect of measurement temperature on luminescence intensity in annealed natural quartz from Nigeria. Measurements were carried out in the slow component region using time-resolved optical stimulation at 470 nm on samples annealed at 500 and 600 °C. Luminescence lifetimes were determined from the resultant time-resolved luminescence spectra by analysing the portion of each spectrum after the stimulating light pulse of duration 11 μs. In preparatory tests, the influence of the duration of optical bleaching on lifetimes was investigated. It was found that lifetimes in samples annealed at 500 °C are independent of the duration of optical bleaching, whereas lifetimes in quartz annealed at 600 °C are affected, decreasing towards a constant value with duration of bleaching. Concerning measurements in the slow-component region, lifetimes were found to decrease with irradiation dose for samples annealed at either 500 or 600 °C. The temperature dependence of lifetimes in both sets of quartz is similar with lifetimes constant at about 36 μs between 20 and 120 °C, but decreasing consistently from then on to about 5 μs at 200 °C, the maximum measurement temperature used in experiments. The luminescence intensity was observed to typically go through a peak as the stimulation temperature was increased from 20 to 200 °C, following a brief initial decrease, a change better exemplified in the quartz annealed at 600 °C. The initial decrease in luminescence intensity is attributed to the dominance of optical stimulation over thermal stimulation. On the other hand, the subsequent change of luminescence intensity with temperature is discussed as evidence of thermal assistance to optical stimulation, initially with activation energy of 0.27±0.07 eV and of thermal quenching subsequently with activation energy equal to 0.93±0.23 eV for samples annealed at either 500 or 600 °C. The temperature dependence of lifetimes is explained as showing increased thermal effect on lifetimes with activation energy values within 0.83±0.01 eV. On the other hand, the influence of irradiation on lifetimes is accounted for in terms of an energy band model for quartz consisting of three luminescence centres and one non-radiative recombination centre.     

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability,mechanical properties and surface resistivity

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20 mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00 mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time.     

Luminescence of different modifications of crystalline silicon dioxide: Stishovite and coesite

Luminescence of very small samples of single crystals of coesite and stishovite has been studied. The spectra were detected under ionizing radiation (X-ray and electron beam) and the decay kinetics of cathodoluminescence in the range of time from 10 ns to 3 ms was measured. The coesite luminescence possesses a broad band at 3 eV with exponential decay about 680 μs at 80 K. The nature of this luminescence was explained as a self-trapped exciton creation in tetrahedron framework. The stishovite luminescence possesses two bands—blue (2.8 eV) and UV (4.7 eV). The UV band intensity grows more than 20 times with irradiation dose from initial level. This shows that the corresponding luminescence centers could be induced by the radiation. The decay of the UV band possesses a fast and a slow component. The determination of the fast decay parameters is beyond the capabilities of our apparatus (less than 10 ns), whereas the slow decay of the UV is non-exponential and takes place in the range of hundreds of microsecond. The blue band decay kinetics can be well approximated by power law ∼t⁻², which may correspond to recombination of defects created by radiation. The stishovite single crystal luminescence is very similar to that of germanium dioxide single crystal of rutile structure. The nature of the stishovite luminescence is explained as recombination of defects created by irradiation in octahedron-structured lattice.     

姜黄素在丙烯酰胺聚合物中的发光特性研究

以丙烯酰胺为功能单体、乙二醇二甲基丙烯酸酯为交联剂 ,在聚合之前的溶液体系中均匀混入荧光分子姜黄素 ,制备了具有光致发光性能的块状聚合物 ,并将此聚合物粉碎为 4 0～ 75 μm直径的粉末。姜黄素在此聚合物中与其在乙醇溶液中相比 ,其荧光发射光谱有明显的蓝移现象。用同样方法制备的含有罗丹明 6G、四碘荧光素、荧光桃红的丙烯酰胺聚合物也有类似的现象 ,初步认为此蓝移现象的机理可能是聚合物的三维空间网状结构对于荧光分子的隔离效应导致其接近于单分子发光所致     

Increased porous morphology and thermal degradation of electron beam-irradiated PVDF-HFP/LiCLO4 polymer electrolyte

The effect of 8?MeV energy electron beam radiation at 40, 80 and 120?kGy dosage on surface morphology and thermal properties of lithium perchlorate-doped poly (vinylidene fluoride-co-hexafluoropropylene) polymer electrolyte films have been studied. The field emission scanning electron microscopic image shows small-porous structured morphology for unirradiated film, but it changed drastically into large and deep porous structure as well as the size of spherulites is reduced for 120?kGy confirming the influence of irradiation on morphology. The atomic force microscope reveals the significantly changed surface roughness of unirradiated film from 116.8 to 123.4?nm with a hill-like pattern morphology for 120?kGy confirming the increased amorphousity after irradiation. The thermal study confirmed that the decrease in the melting point of unirradiated film 160.86–155.24°C for 120?kGy doses is attributed to the formation of defects by the chain scissioning process resulting in the degradation of polymer electrolytes at high dose.     

Time dependence of the luminescence from a polymer membrane swollen in water: Concentration and isotopic effects

The effect of UV irradiation of the surface of a Nafion polymer electrolyte membrane swollen in water in the pump grazing incidence geometry has been experimentally investigated. The photoluminescence from the Nafion surface has been measured in the spectral range characteristic of this polymer. The photoluminescence signal from a polymer with a variable isotopic composition is found to be sensitive to swelling in water. The spectral absorption lines of dry and water-swollen Nafion samples are characterized. It is shown that the luminescence centers in the polymer are sulfonic acid groups located on the ends of perfluorovinyl ether groups, which form the teflon base. Measurements of the temporal dynamics of the luminescence of these groups have revealed an informationally important and significant dependence of the luminescence parameters on the degree of Nafion swelling. A pronounced and nontrivial dependence of these parameters on the content of heavy isotope D₂O in water is also found.     

Luminescence kinetics of linear polymer molecules with chromophores regularly distributed along the chain

An analytical expression for luminescence kinetics of a polymer chain in the static regime is obtained for the case when the rotational motion of monomers, leading to the formation of excimers (traps of excitations), is frozen. The conditions are found when the inhomogeneous broadening of the chromophore spectra and the conformation motion of the polymer chain should be taken into account.     

Enhanced radiation hardness of ZnO nanorods versus bulk layers

It is shown that ZnO nanorods grown by MOCVD exhibit enhanced radiation hardness against high energy heavy ion irradiation as compared to bulk layers. The decrease of the luminescence intensity induced by 130 MeV Xe⁺²³ irradiation at a dose of 1.5 × 10¹⁴ cm^–2 in ZnO nanorods is nearly identical to that induced by a dose of 6 × 10¹² cm^–2 in bulk layers. The change in the nature of electronic transitions responsible for luminescence occurs at an irradiation dose around 1 × 10¹⁴ cm^–2 and 5 × 10¹² cm^–2 in nanorods and bulk layers, respectively. High energy heavy ion irradiation followed by thermal annealing is also effective on the quality of ZnO nanorods grown by electrodeposition. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoluminescence and absorption spectra of CdSe quantum dot-doped glass irradiated by X-rays

Thermally stimulated luminescence (TSL) of aluminoborosilicate glass doped with CdSe nanoparticles (28 and 47 Å) has been studied after exposure to ionizing radiation; the intense TSL peaks were observed at temperatures 150 and 85 °C, respectively. The optical absorption spectra, as well as TSL of the irradiated samples containing CuBr nanoparticles (44 Å) were also measured. In the case of CuBr, TSL was observed neither before nor after irradiation. The dependence of TSL intensity on irradiation time indicates that glass activated by CdSe nanoparticles shows promise as a dosimetric material.     

Luminescence properties of biotite relevant to dating and dosimetry

Biotite mineral grains from granitic rocks were subjected to luminescence studies with optical and thermal stimulation. Moderate thermoluminescence (TL) signals and weak optically stimulated luminescence (OSL) with blue-green light stimulation were detected after 50 Gy beta irradiation. No detectable infrared-stimulated luminescence (IRSL) was observed for natural and laboratory beta-irradiated samples. TL peaks at 118, 300, 360 and 480 °C can be identified from laboratory-irradiated samples. The 360 °C TL peak saturates at a higher dose than quartz, but shows significant anomalous fading after 80 days stored at room temperature. The potentials and problems for biotite used as a natural dosimeter are discussed.     

Luminescence imaging of biological subjects during X-ray irradiations lower energy than Cerenkov-light threshold

It is commonly thought that UV or visible-light luminescence imaging of biological subjects during X-ray irradiation at the energy below 120 keV is impossible because the secondary electrons produced in this energy range do not emit Cerenkov light. Contrary to this consensus, we found UV or visible-light luminescence imaging of the subjects were possible with X-ray irradiations of this energy range. We placed one of the biological subjects in a black box; visible-light luminescence images were measured with a high-sensitivity, cooled charge coupled device (CCD) camera during X-ray irradiation at energy below 120 keV. We also conducted the imaging of air without subjects during irradiation of the same X-ray. The biological subjects emitted visible-light luminescence, and the imaging was possible with the irradiation of the X-ray below 120 keV. The luminescence images were observed in only the X-ray irradiated areas. Also air luminescence images could be obtained and the intensity of the luminescence measured from the images was proportionally increased with the exposure dose. UV or visible-light luminescence imaging of biological subjects was possible during X-ray irradiations lower energy than the Cerenkov-light threshold. The phenomenon was different from general X-ray fluorescence because wavelength of the luminescence is UV or visible-light. The luminescence imaging method is promising for estimating the irradiated area with X-ray, which could be used for interventional radiology (IVR). Also air luminescence imaging would be applied to the exposure dose distribution measurements for X-ray of diagnostic X-ray systems.     

Confinement-induced differences between dielectric normal modes and segmental modes of an ion-conducting polymer

Dielectric measurement in the range 0.1 Hz to 1 MHz were used to study the motions of polymers and ions in an ion-conducting polymer, polypropylene oxide containing small quantities (on the order of 1%) of lithium ions (LiClO₄), confined as a sandwich of uniform thickness between parallel insulating mica surfaces. In the dielectric loss spectrum, we observed three peaks; they originated from the normal mode of the polymer, segmental mode of the polymer, and ion motions. With decreasing film thickness, the peak frequencies corresponding to the normal mode and ion motion shifted to lower frequencies, indicating retardation due to confinement above 30 nm. This was accompanied by diminished intensity of the dielectric normal-mode relaxation, suggesting that confinement diminished the fluctuations of the end-to-end vector of the chain dipole in the direction between the confining surfaces. On the contrary, the segmental mode was not affected at that thickness. Finally, significant retardation of the segmental mode was observed only for the thinnest film (14 nm). The different dynamical modes of the polymer (segmental and slowest normal modes) respond with different thickness and temperature dependence to confinement. Received 31 August 2001 and Received in final form 30 October 2001     

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t _r. The conformation can be described with two parameters only: , the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: is always smaller than (the deformation ratio of the whole sample). In the isotropic phase, has a constant value, while pincreases as tr. This latter behavior is not that expected for non-entangled chains, in which p varies as t _r ^1/2 (Rouse model). In the nematic phase, decreases as a stretched exponential function of t _r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain. Received 5 May 1999 and Received in final form 18 October 1999     

Luminescence kinetics of linear polymer molecules with chromophores randomly distributed along the chain

Luminescence kinetics of chromophores randomly attached to an isolated flexible polymer chain is studied. In the static case, when the polymer chain does not change its conformation during the donor excited-state lifetime, analytical equations are derived for the luminescence kinetics of both ideal and nonideal polymer chains. The conditions are formulated when the inhomogeneous broadening should be taken into account. For the dynamic case, the diffusion and hopping mechanisms of the polymer motion are studied.     

Luminescence kinetics of chromophores attached to the ends of a flexible polymer chain

We studied the effect of the size of a polymer molecule, of the type of its motion in solution, and of the homogeneous and inhomogeneous broadening of its spectra on the luminescence kinetics of chromophores attached to the ends of a polymer chain.     

Variational theory for a single polyelectrolyte chain

Variational methods are applied to a single polyelectrolyte chain. The polymer is modeled as a Gaussian chain with screened electrostatic repulsion between all monomers. As a variational Hamiltonian, the most general Gaussian kernel, including the possibility of a classical or mean polymer path, is employed. The resulting self-consistent equations are systematically solved both for large and small monomer-monomer separations along the chain. In the absence of screening, the polymer is stretched on average. It is described by a straight classical path with Gaussian fluctuations around it. If the electrostatic repulsion is screened, the polymer is isotropically swollen for large separations, and for small separations the polymer correlation function is calculated as an analytic expansion in terms of the monomer-monomer separation along the chain. The electrostatic persistence length and the electrostatic blobsize are inferred from the crossover between distinct scaling ranges. We perform a global analysis of the scaling behavior as a function of the screening length and electrostatic interaction strength , where is the Bjerrum length and A is the distance of charges along the polymer chain. We find three different scaling regimes. i) A Gaussian-persistent regime with Gaussian behavior at small, persistent behavior at intermediate, and isotropically swollen behavior at large length scales. This regime occurs for weakly charged polymers and only for intermediate values of the screening length. The electrostatic persistence length is defined as the crossover length between the persistent and the asymptotically swollen behavior and is given by and thus disagrees with previous (restricted) variational treatments which predict a linear dependence on the screening length .ii) A Gaussian regime with Gaussian behavior at small and isotropically swollen behavior at large length scales. This regime occurs for weakly charged polymers and/or strong screening, and the electrostatic repulsion between monomers only leads to subfluent corrections to Gaussian scaling at small separations. The concept of a persistence length is without meaning in this regime. iii) A persistent regime , where the chain resembles a stretched rod on intermediate and small scales. Here the persistence length is given by the original Odijk prediction, , if the overstretching of the chain is avoided. We also investigate the effects of a finite polymer length and of an additional excluded-volume interaction, which modify the resultant scaling behavior. Applications to experiments and computer simulations are discussed. Received 24 December 1997     

Luminescence of silicon Dioxide — silica glass, α-quartz and stishovite

This paper compares the luminescence of different modifications of silicon dioxide — silica glass, α-quartz crystal and dense octahedron structured stishovite crystal. Under x-ray irradiation of pure silica glass and pure α-quartz crystal, only the luminescence of self-trapped exciton (STE) is detected, excitable only in the range of intrinsic absorption. No STE luminescence was detected in stishovite since, even though its luminescence is excitable below the optical gap, it could not be ascribed to a self-trapped exciton. Under ArF laser excitation of pure α-quartz crystal, luminescence of a self-trapped exciton was detected under two-photon excitation. In silica glass and stishovite mono crystal, we spectrally detected mutually similar luminescences under single-photon excitation of ArF laser. In silica glass, the luminescence of an oxygen deficient center is presented by the so-called twofold coordinated silicon center (L.N. Skuja et al., Solid State Commun. 50, 1069 (1984)). This center is modified with an unknown surrounding or localized states of silica glass (A.N. Trukhin et al., J. Non-Cryst. Solids 248, 40 (1999)). In stishovite, that same luminescence was ascribed to some defect existing after crystal growth. For α-quartz crystal, similar to silica and stishovite, luminescence could be obtained only by irradiation with a lattice damaging source such as a dense electron beam at a temperature below 80 K, as well as by neutron or -irradiation at 290 K.     

Characterization of structural modifications in poly-tetra-fluoroethylene induced by electron beam irradiation

The effects of electron beam irradiation doses on the poly-tetra-fluoroethylene (PTFE) have been studied. Several techniques, such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical properties and Fourier transform infrared spectroscopy (FTIR) were applied to characterize the PTFE samples and to study the radiation effects on the crystal structure of the polymer.The irradiation dose up to 150 kGy showed an increase in the crystallinity degree of PTFE, which has been observed and confirmed during the DSC and XRD measurements. The increase in crystallinity was attributed to the scissions of the chain in the amorphous region. Moreover, the number-average molecular weights were estimated from the heat of crystallization measured by DSC technique. The results indicated that the molecular weights were decreased by increasing the heat of crystallization due to irradiation with doses up to 150 kGy. Radiation resistance of the irradiated and non-irradiated PTFE was investigated during its mechanical properties at room temperature. The dose at half value of the elongation at break is about 3.10 kGy while the dose at half value of the tensile strength is about 1.70 kGy.