Mechanoluminescence, thermoluminescence, optically stimulated luminescence and photoluminescence in SrAl2O4:Eu micro- and nanophosphors: effect of particle size and annealing in different atmospheres.

SrAl2O4:Eu in microcrystalline form was prepared by a combustion method. The formation of the material in a single phase was confirmed by XRD analysis. The material was crushed and sieved to get particles with different particle size ranges. It was further ball milled for 1-7 days to get particles in the nanosize ranges. The broadening of the XRD peaks of the phosphor material in nanocrystalline form was used to determine average particle sizes. The shapes and sizes of these particles could also be seen in FESEM images. The materials thus obtained were annealed in reducing (10% H2 in Ar) and oxidizing (in air) atmospheres at different temperatures for 1.0 h. The increase in the mechanoluminescence (ML) intensity on annealing in a reducing atmosphere at different temperatures and decrease on annealing in an oxidizing atmosphere could be attributed to redox reactions. This was further confirmed by PL measurements. Mechanoluminescence (ML), thermoluminescence (TL), and optically stimulated luminescence (OSL) of the materials were studied. In all three cases (i.e., ML, TL, and OSL), the intensities are found to decrease with the particle size. A large shift of approximately 20 °C in the main peak of TL glow curves of micro- and nanocrystalline materials shows a widening of the band gap due to the particle size effect. A decrease in piezoelectric constant (d33) and field (F V m-1) with particle size was also observed. The present systematic study of particle size effect (over a wide range of particle sizes) on ML has great importance from a technological and application point of view for developing stress sensors.

Effect of redox reactions on the thermoluminescence characteristics of Cu-doped NaLi2PO4 phosphors.

A Cu-doped NaLi2PO4 phosphor material was successfully synthesized through the high-temperature solid state diffusion method. It was mainly doped with Cu2Cl2 and CuCl2 salts for impurities in the form of Cu+ and Cu2+, respectively. Formation of the material in the single phase of the phosphor material was confirmed by powder XRD. Morphological and compositional characterization was done using XPS, SEM and EDS techniques. The materials were annealed in reducing, (10% H2 in Ar) and CO/CO2 (by burning charcoal in a closed system), as well as in oxidizing (air) atmospheres at different temperatures. ESR and PL studies were conducted for studying redox reactions due to annealing and its effect on TL characteristics. It is known that the impurity Cu could exist in Cu2+, Cu+ and Cu0 forms. The material was doped with two different salts (Cu2Cl2 and CuCl2) as sources of the impurities in two different forms i.e., Cu+ and Cu2+, however, it was found that it gets incorporated in both the forms inside the material. Also, annealing in different atmospheres not only changed their ionic states but also affected the sensitivity of these phosphors. It was observed that at ∼10 Gy, NaLi2PO4:Cu(ii) is around 3.3 times, 3.0 times and almost equally sensitive than commercially available TLD-900 phosphor on annealing in air, 10% H2 in Ar and CO/CO2 at 400, 400 and 800 °C, respectively. However, NaLi2PO4:Cu(i) becomes 1.8 times sensitive after annealing in CO/CO2 at 800 °C as compared to TLD-900. With high sensitivity, both the materials NaLi2PO4:Cu(ii) and NaLi2PO4:Cu(i) are good candidates for radiation dosimetry with a wide dose response (mGy-5.0 kGy).

Spectroscopic analysis of Muga silk nanoparticles synthesized by microwave method.

Muga silk nanoparticles (MSNP) were synthesized using a microwave-assisted radiolysis method. The effect of microwave on the Muga protein secondary structures was analyzed. The evolution of the secondary structure from random coils to the ß-sheets was determined by using FTIR, circular dichroism and X-ray diffraction techniques. The results showed that Muga silk fibroin protein contained the primary structure in silk-I state. When the protein was irradiated with microwave, nanoparticle synthesis was possible having silk-II state imparting crystallinity. The silk nanoparticles were characterized by a particle size analyzer and found to be of ~240 nm in size. The optical properties of these nanoparticles were studied by UV-vis. spectroscopy and photoluminescence. For studying thermal properties, differential scanning calorimetry was performed that revealed early glass transition, which could be attributed to the presence of water and proteins. It also revealed that nanoparticles are thermally stable. Such studies are important for understanding more about the MSNP and would be beneficial for their further wide applications.

Study of optically stimulated luminescence and calculation of trapping parameters of K2Ca2(SO4)3:Eu nanophosphor.

K2Ca2(SO4)3:Eu nanophosphor was synthesized by chemical coprecipitation method and annealed at different temperatures from 400 to 900 °C. The nanophosphor annealed at 600 °C showed cubic structure with crystallite size ~25 nm. TEM shows morphology of K2Ca2(SO4)3:Eu nanophosphor was in the form of nanorods having diameter ~20 nm and length of ~100-200 nm. These samples were irradiated with gamma radiation for the doses varying from 10 mGy to 10 kGy and their Thermoluminescence (TL) and continuous-wave optically stimulated luminescence (CW-OSL) have been studied. CW-OSL response was found to be maximal for the sample annealed at 600 °C. The TL glow curve of the nanophosphor apparently showed a major peak at around 160 °C accompanied by three low intensity peaks at ~75, 215 and 285 °C. The traps responsible for all the TL peaks in K2Ca2(SO4)3:Eu were also found to be OSL sensitive. The qualitative correlation between TL peaks and CW-OSL response suggested that the traps associated with low temperature peaks are responsible for fast decay and the traps associated with the higher temperature peaks are responsible for slow decay of the OSL signal. OSL response showed linear behavior up to 1 kGy and saturated with further increase in the gamma dose. The wide OSL response makes studied K2Ca2(SO4)3:Eu nanophosphor a good candidate for high dose measurement.

Effect of size variation and gamma irradiation on thermoluminescence and photoluminescence characteristics of CaSO4:Eu micro- and nanophosphors.

Microcrystalline CaSO4:Eu phosphor particles prepared by the acid re-crystallization method were grinded by ball-milling method and reduced to small particles of sizes ~50 nm, 200 nm, 400 nm and 5 µm. For comparison, nanocrystalline CaSO4:Eu phosphor of size ~20 nm was also prepared by chemical coprecipitation method. The recorded photoluminescence emission and excitation spectra revealed that Eu is doped in CaSO4:Eu in the form of Eu2+ and Eu3+ in all the samples of microcrystalline and nanocrystalline powders. The samples of CaSO4:Eu, with different particle sizes, were irradiated with gamma rays over a range of doses ranging from 1 Gy to 100 kGy. The results of characterization by thermoluminescence method show that the intensity of the thermoluminescence peak for a given dose of gamma-rays decreases with the decrease in the particle size of CaSO4:Eu. A comparison shows that CaSO4:Eu of size 50 nm exhibited linear response between the thermoluminescence peak and the gamma-ray dose in the range of 1 Gy-10 kGy. This phosphor can, therefore, be used for the measurement of gamma ray dose in medical and industrial applications. A comparative study also showed that the sensitivity of thermoluminescence to gamma ray dose for the nanophosphor prepared by the ball milling technique is better than that of the nanophosphor prepared by chemical co-precipitation method.

Thermoluminescence studies of CaSO4:Dy nanophosphor for application in high dose measurements.

Nanorods of CaSO4:Dy (having diameter ∼20 nm and length ∼200 nm) were prepared by chemical coprecipitation method and their thermoluminescence (TL) characteristics were studied after annealing at different temperatures in the range 400-1000 °C. Microcrystalline material was also prepared through acid recrystallization method. TL glow curves of the nanocrystalline material annealed at 700 °C showed a major peak at around 283 °C. The effect of annealing temperature on the phase structure/morphology of particles was studied. Phase change was observed when CaSO4:Dy was annealed at different temperatures as confirmed by XRD and TG-DTA. It was observed from the TEM images that the nanomaterial originally in the nanorods form broke into nanoparticles due to strain developed by phase change on annealing at higher temperatures. The combined effect resulted in changes in TL glow curve structure. For better clarity the TL glow curves were further deconvoluted by Computerized Glow Curve Deconvolution (CGCD) method and kinetic trapping parameters were determined. It was found that the values of kinetic parameters also changed for the nanocrystalline material annealed at different temperatures. These were also compared with the corresponding values of the microcrystalline material. It was also observed that the TL intensity saturates at about 100 Gy in case of microcrystalline phosphor, while that in case of nanocrystalline phosphor did not do saturate even up to 5 kGy.

Optically stimulated luminescence (OSL) response of Al2O3:C, BaFCl:Eu and K2Ca2(SO4)3:Eu phosphors.

This paper investigates the optically stimulated luminescence (OSL) response of BaFCl:Eu and K2Ca2(SO4)3:Eu phosphors for different doses and bleaching durations. The results have also been compared with the commercially available Landauer Al2O3:C (Luxel®) dosemeter. Nanocrystalline K2Ca2(SO4)3:Eu is known to be a sensitive thermoluminescent phosphor, but its OSL response is hardly reported. At first, pellets of nanocrystalline K2Ca2(SO4)3:Eu powder were prepared by adding Teflon as a binder. Their OSL signal was compared with that of the material in pure form, i.e. without adding the binder (in 100:1 ratio). It was observed that adding the binder does not appreciably affect the OSL intensity. On comparison with the commercially available Al2O3:C from Landauer, it was found that K2Ca2(SO4)3:Eu is around 15 times less sensitive than Al2O3:C. 'Homemade' BaFCl:Eu phosphor has also been studied. The intensity of BaFCl:Eu was ∼20 times more than the standard Al2O3:C dosemeter and ∼200 times more sensitive than K2Ca2(SO4)3:Eu in the dose range of 13-200 cGy. OSL dosemeters are believed to give luminescence signal even if they are read before, i.e. multiple reading may be possible under suitable conditions after single exposure. This was also checked for all the prepared dosemeters and it was found that Al2O3:C showed the least decrease of <2 %, followed by BaFCl:Eu of 15 % and K2Ca2(SO4)3:Eu with 20 %. Finally, Al2O3:C and BaFCl:Eu phosphors were also studied for their optical bleaching durations to which the respective signals get completely removed so that the phosphor can be re-used. It was observed that BaFCl:Eu is bleached faster and more easily than Al2O3:C.

Energy transfer studies in binary dye solution mixtures: Acriflavine+Rhodamine 6G and Acriflavine+Rhodamine B.

The effect of acceptor concentration on the energy transfer in Acriflavine (donar) plus Rhodamine 6G (Rh 6G) and Acriflavine plus Rhodamine B (Rh B) binary solution mixtures has been studied. The theoretical calculations are done to determine their lifetimes. Effect of these values on the total transfer efficiency at various acceptor concentrations have been studied to identify the appropriate energy transfer mechanism responsible for photon emissions, enhancement in lasing efficiency and dreading of the tenability of such mixed solutions. The energy transfer rate constants and critical transfer radius (R(0)) are calculated using Stern-Volmer plots and concentration dependence of radiative and non-radiative transfer efficiencies have also been determined. The experimental results indicate that dominant mechanism responsible for the efficient energy transfer in the binary mixtures is of non-radiative kind and is due to long-range dipole-dipole interaction.

Fluorescence quenching of 3-methyl 7-hydroxyl Coumarin in presence of acetone.

Fluorescence quenching of 3-methyl 7-hydroxyl Coumarin in prescence of the acetone is reported here. It was found that the quenching observed was of dynamic nature. It is also observed that quenching of the fluorescence of the indicator had a full reversiblity. As it has a full reversiblity, a novel optical sensor for acetone can be constructed on this quenching.

Excited state characteristics of acridine dyes: acriflavine and acridine orange.

The magnitude of the Stokes shift (frequency shifts in absorption and fluorescence spectra) is observed on changing the solvents and further has been used to calculate experimentally the dipole moments (ground state and excited state) of acriflavine and acridine orange dye molecules. Theoretically, dipole moments are calculated using PM 3 Model. The dipole moments of excited states, for both molecules investigated here, are higher than the corresponding values in the ground states. The increase in the dipole moment has been explained in terms of the nature of the excited state. Acriflavine dye overcomes the non-lasing behaviour of acridine orange due to quaternization of the central nitrogen atom.

Optical gain characteristics of C 460 and C 450.

Dye concentration dependent gain spectra for Coumarin 460 (C 460) and Coumarin 450 (C 450) in ethanol have been studied using Amplified Spontaneous Emission (ASE) technique under Nitrogen laser (337.1 nm) excitation in the concentration range 10(-2)-10(-5) m/l. The dependence of lasing wavelength and peak gain on concentration have been understood in terms of variation of fluorescence lifetime, which is due to photo-physical processes such as radiation trapping and concentration-quenching. Pump intensity dependence of efficiency is also explained in terms of fluorescence lifetime. A comparison of the stability of the two dyes has also been made on the basis of the functional groups at different positions of the basic coumarin.