Thermoluminescence of irradiated polystyrene

Thermoluminescence of irradiated polystyrene has been studied in the temperature range 100 to 440°K. Three glow peaks with maximum at 160, 221, and 378°K have been observed. These peaks are analyzed by different methods and the activation energies which were obtained are compared. The activation energies are found to be 0.22, 0.48, and 1.45 eV for the peaks with maxima at 160, 221, and 378°K, respectively. Second-order kinetics is appropriate to all these cases. The glow peaks are attributed to the decay of the free radicals formed on irradiation and subsequent thermal stimulation. The peak with the maximum at 160°K is attributed to electron trapping by the carbonyl groups or peroxy radicals formed on irradiation. The curve with the peak at 221°K is attributed to the cyclohexadienyl radical, and the curve with the peak at 378°K is attributed to the chain radical ? CH₂? C (C₆H₅)? CH₂? . The centers responsible for the observed thermoluminescence are identified by correlation with electron spin resonance (ESR) data obtained on the same samples.     

Ion recombination luminescence in polymer glasses induced by electron irradiation. I. High-vinyl polybutadiene

The luminescence of 1,2-polybutadiene was measured during and following irradiation with 1.4-MeV electrons at 90 °K. Measured under isothermal conditions, the light intensity at first increases sharply on start-up of irradiation, and then reaches a plateau after several seconds. The equilibrium value was found to be linearly dependent on the dose rate employed. The postirradiation luminescence decay measured at 90°K follows second-order kinetics. The light emitted by the irradiated sample during warm-up to room temperature is characterized by the appearance of four intensity maxima at 118, 168, 223, and 261 °K. The first three peaks are attributable to the onset of local motion, whereas the peak at 223 °K is caused by the long-range motion occurring at the glass-to-rubber transition. A preirradiation of the polymer in vacuo causes an increase in these four peaks as well as the formation of a new maximum at 143 °K. Intermittent exposure of the irradiated sample to light of wavelengths λ > 450 nm causes the isothermal luminescence decay to be interrupted by a burst of light emitted by the sample during and shortly following the light exposure. This treatment also results in considerably reduced intensity maxima during warm-up to room temperature. An interpretation of the findings reported is given on the basis of reactions involving primary and secondary transient species produced during irradiation and on the molecular parameters of the polybutadiene.     

Radiation-induced emission from golden hamster embryo cells

Emission from high-energy-electron-irradiated golden hamster embryo (GHE) cells has been studied over the temperature range 12–300 K both by a one-shot-single-photon-counting method and by photocurrent measurements with an oscilloscope. Emission from the irradiated phosphate buffered saline (PBS) also has been studied. The emission spectra from PBS at 12 and 77 K show a maximum around 330 and 380 nm, respectively, which are the same spectra as those from irradiated pure H₂O. The emission from irradiated GHE consists of the new band at 480 nm in addition to the emission from H₂O. The 480 nm emission is observed at the temperature range of 12–300 K, though the emission at 300 K is much lower than that at low temperature. The 480 nm emission is ascribed to the transition from excited organic substances in GHE cells. The intensity of 480 nm emission at 300 K increases linearly with increasing irradiation-dose in the range of 11–600 Gy.     

Origin of Porous Silicon Photoluminescence Peaks in the Wavelength Range 460–700 nm

The change in the photoluminescence peaks of porous silicon at λ = 640–670 and 540–560 nm at 300 and 77 K, as well as their behavior after low-temperature annealing of the samples at 500°С, has been studied. The change in these peaks correlated with that in the IR spectra. The peak at 640–670 nm has been explained by the existence Si–OH groups on the porous silicon layers and the peak at 540–560 nm, by the photoluminescence of the silicon matrix per se.     

Dielectric relaxations in polymers with pendent phenyl or pyridine groups at temperatures from 4°K to 80°K

Isochronal measurements of dielectric loss are made for polystyrene (PS), poly(4-vinyl pyridine) (P4VP), poly(2-vinyl pyridine) (P2VP), poly(L-phenylalanine) (PLPA), and poly(γ-benzyl-L-glutamate) (PBLG) at temperatures ranging from 4°K to 80°K and at frequencies from 10 Hz to 100 kHz. PS, P4VP, and PLPA show loss peaks around 50°K (10 kHz) while P2VP exhibits a loss peak around 20°K (10 kHz). PBLG has no detectable peak in this temperature range. The 50°K and 20°K peaks are ascribed to wagging and rotation, respectively, of phenyl or pyridine groups between two energy minima. The barrier height and energy difference between the minima evaluated from the experimental data are reasonably explained by assuming that the double minima are caused by interaction between a pair of phenyl or pyridine groups, each belonging to adjacent chains which pack irregularly.     

Dielectric study of low-temperature relaxations in poly(isobutyl methacrylate), poly(n-butyl methacrylate), poly(isopropyl methacrylate), and poly(4-methylpentene-1)

Isochronal measurements of dielectric constant and loss are made for poly(isobutyl methacrylate) (PiBMA), poly(n-butyl methacrylate) (PnBMA), poly(isopropyl methacrylate) (PiBMA), and poly(4-methylpentene-1) (P4MP1) at temperatures ranging from 4°K to 250°K. Loss peaks are found around 120°K (10–100 Hz) for PiBMA, PnBMA, and P4MP1. By comparing the activation energy with the calculated potential barrier for the internal rotation of alkyl group in the side chain, the motion responsible for the 120°K peak is concluded to be essentially the rotation of the isopropyl group as a whole for PiBMA and P4MP1 but, for PnBMA, the rotation of n-propyl group accompanied by the rotation of the end ethyl group. Multiple paths of internal rotation are involved with the 120°K peaks of PiBMA and, in particular, PnBMA, which explain differences between PiBMA and PnBMA in the broadness and the temperature location of the 120°K peak. The 120°K peak is in general assigned to a side chain including a sequence? O? C? C? C or ? C? C? C? C. PiPMA without this sequence in the side chain does not show the 120°K peak, but it exhibits the 50°K peak (1 kHz) like poly(ethyl methacrylate). The 50°K peak is assigned to the rotation of ethyl or isopropyl group attached to COO group. Poly-L-valine in which the isopropyl group is directly attached to carbon does not have the 50°K peak. An additional loss peak at 20°K (1 kHz) for P4MP1 is also discussed on the basis of the calculated potential.     

Effect of solvents on the cryogenic dynamic mechanical properties of polystyrene

Young's modulus and mechanical damping of 15 organic liquids in polystyrene have been measured from 4°K to 250°K. The concentration was generally in the range from 10 to 15%, but the polystyrene–toluene system was investigated over the range from 0 to 16%. Some liquids cause the 40°K damping peak of polystyrene to disappear, other liquids do not. Seven of the liquids which cause the disappearance of the 40°K peak give rise to new large damping peaks at the temperature expected for the secondary glass transition temperatures of the liquids, that is, at 0.77 T_g of the liquids. Some of the liquids produced large unexplained damping peaks at temperatures above the expected glass transition temperatures T_g of the liquids. It is suggested that the γ peak in polystyrene is caused by styrene monomer.     

ESR studies of some γ-irradiated organic crystals

Acrylamide, N-tert-butylacrylamide, and propionamide crystals were irradiated at ?196°C and the structures of radicals studied by ESR spectroscopy at various temperatures. The γ-irradiated acrylamide crystals show a five-line spectrum which is similar in shape to the signal obtained from the γ-irradiated propionamide crystals. Two types of radicals are produced in irradiated acrylamide and propionamide crystals at ?196°C. When the irradiated samples are kept at ?78°C the spectrum of propionamide remains the same, except in intensity. In contrast to this, the acrylamide spectrum changes to a triplet because of dimerization. Upon warming the irradiated acrylamide sample to between ?50 and ?30°C, some small new peaks become apparent on either side of the triplet. These new peaks disappear above ?20°C and the spectrum changes to a triplet because of polymerization. To observe the changes in the ESR spectra of γ-irradiated N-tert-butylacrylamide we kept the sample at various temperatures from ?196 to 100°C. From ?196°C to about room temperature the spectrum is a quintet. At and above 35°C, the spectrum changes to a triplet with shoulders on either side of the main peaks. With further warming above 80°C the spectrum changes to a broad triplet.     

N,N′-二-(2-吡啶基)苝四羧酸二酰亚胺的合成及性能研究

合成了N,N′ 二 (2 吡啶基)四羧酸二酰亚胺,并纯化、调晶.对产物进行了元素分析和IR光谱研究(环状二酰亚胺的CO以双峰1708.8cm-1、1664 5cm-1).α晶型产物溶液的紫外可见光谱(最大吸收波长为526.00nm)和荧光光谱(最大发射波长为538.0nm)存在很好的镜像对称关系.薄膜紫外可见光谱图在450—570nm范围内,α晶型比β晶型有较强的吸收峰.X粉末衍射也反映出α晶型在2θ为25.5°、26.3°上的衍射峰强度分别为1954、2603.α、β晶型分别作为电荷产生材料制得的功能分离型有机光导体,在光源波长λ=532nm曝光下,测得含α的感光体达到饱和电位的时间45s、半衰曝光量5.7μJ/cm2、残余电位22V等数据.测得含β的感光体达到饱和电位的时间49s、半衰曝光量9.9μJ/cm2、残余电位22V等性能数值.     

QUANTUM YIELD RATIO OF THE FORWARD and BACK LIGHT REACTIONS OF BACTERIORHODOPSIN T LOW TEMPERATURE and PHOTOSTEADY-STATE CONCENTRATION OF THE BATHOPRODUCT K*

The maximum photosteady state fraction of K, x_K^max, and the ratio of the quantum yields of the forward and back light reactions, trans-bacteriorhodopsin (bR) hArr; K, φ_bR/φ_K, were obtained by measuring the absorption changes produced by illumination of frozen water-glycerol (1:2) suspensions of light-adapted purple membrane at different wavelengths at -165°C. An independent method based on the second derivative of the absorption spectrum in the region of the β-bands was also used. It was found that The quantum yield ratio (0.66 ± 0.06) was found to be independent of excitation wavelength within experimental error in the range510–610 nm. The calculated absorption spectrum of K has its maximum at603–606 nm and an extinction 0.85 ± 0.03 that of bR. At shorter wavelengths there are P-bands at 410, 354 and 336 rim. Using the data of Hurley et al. (Nature 270,540–542, 1977) on relative rates of rhodopsin bleaching and K formation, the quantum yield of K formation was determined to be 0.66 ± 0.04 at low temperature. The quantum efficiency of the back reaction was estimated to be 0.93 ± 0.07. These values of quantum efficiencies of the forward and back light reactions of bR at - 165°C coincide with those recently obtained at room temperature. This indicates that the quantum efficiencies of both forward and back light reactions of bacteriorhodopsin are temperature independent down to -165°C.     

Thermoluminescence and chemical characterization of natural calcite collected from Kodwa mines

This paper reports the thermoluminescence (TL) and chemical characterization of natural calcite collected from Kodwa mines of the C.G. Basin. The sample was irradiated with a 10-Gy dose from an Sr-90 beta source. The heating rate used for TL measurements was 6.7 °/s. The sample had a good TL peak at approximately 127 °C and the corresponding kinetic parameter were calculated. The effect of annealing temperature is also described for natural calcite. The photoluminescence excitation spectrum at ~254 nm and the corresponding emission spectrum peak at 395 nm are reported. Inductively coupled plasma–activated emission spectroscopy (ICP–AES) was conducted to determine the percentages of elements in the calcite mineral.     

Thermo-X-ray-diffraction analysis of dimethylsulfoxide-kaolinite intercalation complexes

DMSO-kaolinite complexes of low- and high-defect Georgia kaolinite (KGa-1 and KGa-2, respectively) were investigated by thermo-XRD-analysis. X-ray patterns showed that DMSO was intercalated in both kaolinites with a d(001)-value of 1.11 nm (type I complex). The samples were gradually heated up to 170°C and diffracted by X-ray at room-temperature. With the rise in temperature, due to the thermal evolution of the guest molecules, the relative intensity of the 1.11 nm peak decreased and that of the 0.72 nm peak (neat kaolinite) increased indicating that the fraction of the non-intercalated tactoids increased. The 1.11 peak disappeared at 130–140°C. During the thermal treatment of both complexes two additional peaks appeared at 110 and 120°C, respectively, with d-values of 0.79–0.94 and 0.61–0.67 nm in DMSO-KGa-1 and 0.81–0.86 and 0.62–0.66 nm in DMSO-KGa-2, indicating the formation of a new phase (type II complex). The new complex was obtained by the dehydration of type I complex and was composed of intercalated DMSO molecules which did not escape. The new peaks disappeared at 150–160°C indicating the complete escape of DMSO.     

LASER FLASH PHOTOLYSIS OF RHODOPSIN AT ROOM TEMPERATURE

Abstract. Nanosecond flash photolysis of rhodopsin with 530 or 353 nm light produces an initial transient absorption spectrum with peaks at ˜57O and ˜420nm, and a subsequent transient species with a maximum absorption at 480 nm. These results are interpreted as the initial formation of prelumi-rhodopsin (570 nm) followed by its conversion to lumirhodopsin (470 nm). The peak at 420 nm in the first transient may be due to either hypsorhodopsin or isorhodopsin.     

Preparation and properties of novel low dielectric constant benzoxazole‐based polybenzoxazine

A novel benzoxazine monomer containing a benzoxazole group was synthesized using a nonsolvent method and then named DAROH‐a. The structure of DAROH‐a was confirmed by FTIR, ¹H NMR, elemental analysis, and mass spectrometry. The curing reaction activation energy was calculated at 140 kJ/mol. Its corresponding crosslinked polybenzoxazines, poly(DAROH‐a), displayed a higher glass transition temperature at 402 °C, a 9% weight loss at the said temperature, and a high char yield of 42 wt % (800 °C, in nitrogen). Moreover, the dielectric constants of poly(DAROH‐a) were low and changed only slightly at different temperatures. Furthermore, the dielectric constants and dielectric loss of poly(DAROH‐a) at the same frequency barely changed from room temperature to 150 °C. The photophysical properties of poly(DAROH‐a) film were also investigated. Poly(DAROH‐a) showed an absorption peak at 280 nm. The photoluminescent emission spectrum of poly(DAROH‐a) film displayed predominant emission peaks at 521 nm. It might have potential application as high‐performance materials because of its excellent dielectric constants stability and thermal stability under high temperature. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A NEW GLOW PEAK, IN RHODOPSEUDOMONAS SPHAEROIDES

Abstract— A new glow peak at 120 K has been observed in Rhodopseudomanas sphaeroides and in its carotenoidless green mutant. This peak (labelled Z_n ), which is composed of two peaks at 120 and 150 K, appears when the bacteria are illuminated with white light while being cooled to 77 K and then warmed in darkness at a heating rate of 10 K per min. Delayed light emission and prompt fluorescence spectra show peaks around 530, 610 and 660 nm. The action spectra of light emission show a major peak at 410 nm and a smaller peak around 545 nm. The pigment responsible for the light emission is also leached out in the suspension medium. The chromophore responsible for the light emission appears to be magnesium protoporphyrin IX, not bacteriochlorophyll.     

X‐ray studies on the double melting behavior of poly(butylene terephthalate)

The double melting behavior of poly(butylene terephthalate) (PBT) was studied with differential scanning calorimetry (DSC) and wide‐angle X‐ray analysis. DSC melting curves of melt‐crystallized PBT samples, which we prepared by cooling from the melt (250 °C) at various cooling rates, showed two endothermic peaks and an exothermic peak located between these melting peaks. The cooling rate effect on these peaks was investigated. The melt‐crystallized PBT sample cooled at 24 K min^?1 was heated at a rate of 1 K min^?1, and its diffraction patterns were obtained successively at a rate of one pattern per minute with an X‐ray measurement system equipped with a position‐sensitive proportional counter. The diffraction pattern did not change in the melting process, except for the change in its peak height. This suggests that the double melting behavior does not originate from a change in the crystal structure. The temperature dependence of the diffraction intensity was obtained from the diffraction patterns. With increasing temperature, the intensity decreased gradually in the low‐temperature region and then increased distinctly before a steep decrease due to the final melting. In other words, the temperature‐dependence curve of the diffraction intensity showed a peak that is interpreted as proof of the recrystallization in the melting process. The peak temperature was 216 °C. The temperature‐dependence curve of the enthalpy change obtained by the integration of the DSC curve almost coincided with that of the diffraction intensity. The double melting behavior in the heating process of PBT is concluded to originate from the increase of crystallinity, that is, recrystallization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2005–2015, 2001     

Thermally Stimulated Luminescence in ZnSe:Ag and ZnSe:(Ag,Gd) Phosphors

With a view to understanding the luminescence mechanism in ZnSe, a systematic study of thermally stimulated luminescence (TSL) of UV ray (3650 Å) irradiated ZnSe:Ag and ZnSe:(Ag, Gd) phosphors has been undertaken. TSL glow curves of these phosphors are recorded in the temperature range 110–340 K. The TSL parameters like trap depth, frequency factor, order of kinetics, and capture cross-section of the glow peaks are evaluated employing Cutie's method, various heating method, and peak shape method.     

γ-radiolysis of acetylated cotton cellulose: An ESR study

The nature and behavior of free radicals induced in acetylated cotton celluloses irradiated with γ-rays have been studied by electron spin resonance (ESR) spectroscopy. Dehydrogenation and deacetylation appear to be responsible for the free radicals observed from samples irradiated at 77°K. The degree of substitution enhanced the yield of acetyl radicals when the samples were irradiated at 77°K and adversely affected the overall radical concentration when irradiation was done at 300°K. In addition, the ESR spectra of samples irradiated under vacuum at 300°K were more intense than those obtained from samples irradiated in air. The nature, yield, and post-irradiation behavior of the primary radicals are discussed in the light of the ultimate chemical effects observed.     

Luminescence characteristics of minerals separated from irradiated onions during storage under different light conditions

The aim of this study was to determine the effects of light conditions during 2 years of storage on the luminescence characteristics of contaminating minerals, isolated from irradiated onions of 2 different origins. The potential use of photostimulated luminescence (PSL) as a screening and thermoluminescence (TL) as a confirmatory identification method was investigated during post-irradiation periods. Nonirradiated onions had 1,612 photon counts (PCs), However, the irradiated onions had much higher PCs (45,672–469,696, positive). The PCs of the irradiated onions decreased with storage time. However, all the irradiated onions had PCs with positive values (>5,000) even after 2 years of storage except onions stored under natural light. The decline in PCs because of light conditions during storage was in the order of sunlight, artificial light, and a darkroom, respectively. Minerals extracted from the nonirradiated samples exhibited TL glow curves of low intensities with maximum peak after 300 ^°C. However, all irradiated samples had TL glow peaks in the temperature ranges of 185–225 ^°C. The TL intensity and TL ratio of the irradiated samples decreased during storage with a slight shift in the TL peak temperature towards higher temperatures. The TL characteristics were most promising for samples stored under natural light conditions, however all the irradiated onions could be identified even after 2 years of storage.