The effects of delayed annealing on the luminescent activity of heavy metal cadmium zinc phosphate glasses activated by: Er3+ and Tb3+ ions.

The luminescent spectra of the RE2O3-doped P2O5-CdO-ZnO glasses (RE = Er, and Tb) were investigated to separate the effects of two studied rare-earth elements and the annealing regime on the emission performance of the prepared glasses. The glasses undergo a series of collective measurements including UV-visible absorption, luminescence, thermal expansion, XRD, TEM, and FTIR. The optical UV-visible spectra of the two doped glasses reveal a UV band due to undoped glass beside and extra extended 11 peaks with the Er3+ ions with high distinct features while the Tb3+ ions samples exhibit peaks within the visible region. These peaks are correlated with transitions from the ground state in each case to specific energy transitions. The overall optical data indicate that the two rare earth ions are present in a stable trivalent state. Under UV excitation, both Er3+ and Tb3+ emit a characteristic green light corresponding to 4S3/2 → 4I15/2 and 5D4 → 7F5 transitions, respectively. The performance of the green light was identified to be enhanced by increasing the concentration of rare earth and the effect of annealing temperature. Moreover, the intensity of the infrared emission of Er3+ at 1532 nm corresponds to the (4I13/2 → 4I15/2) transition which is assumed to be developed with the effect of heating. The resultant IR spectra show distinct vibrational peaks due to phosphate groups that undergo only minor modifications when doped with rare earth elements or over-annealed.

Crystallization effects on the photoluminescence efficiency of SrO-B2O3 glass activated by W6+, Eu3+, Dy3+ or Pr3+ ions.

Binary strontium borate host glass together with samples doped with 0.25 %WO3 and one of the rare - earth ions (0.125% Eu3+, Dy3+ or Pr3+) were prepared by conventional melting - annealing technique. DTA analysis of the host base glass was carried out to derive the proper temperatures which are necessary to convert glasses into their corresponding glass -ceramic through controlled thermal heat -treatment regime. Measurements of optical, FTIR, and PL spectra were carried out with special analysis of the spectral properties. The identity of glass - ceramic derivatives were investigated through x-ray diffraction, and TEM & SEM tools to identify their crystalline morphological features. The absorption spectrum of WO3 - doped glass refers to the existence of dominant hexavalent tungsten ions. The RE- doped glass reveal characteristic visible - NIR absorption peaks due to the respective rare earth ions. FTIR spectra show absorption bands due to both triangular and tetravalent borate groups (BO3, BO4).PL spectra reveal excitation and emission characteristic peaks due to each specific rare earth ions. XRD indicate the preference of the host glass to form strontium pyroborate (SrB4O7) crystalline phase. This facilitates the clear knowledge of the crystallization behavior and hence can justify the effect of the crystallization on the studied properties.

Optical, structural and thermal properties of sodium metaphosphate glasses containing Bi2O3 with interactions of gamma rays.

Sodium metaphosphate glasses with successive increasing added Bi2O3 contents (5-40%) were prepared to improve their chemical stability and increase their optical and thermal properties through the additional building BiO6 and BiO3 units. The optical spectrum of the base metaphosphate glass reveals strong UV absorption due to the presence of trace iron (Fe3+) ions present as impurities. Glasses containing additional 5, 7.5 and 10% Bi2O3 show further band around 406nm which can be related to absorption of Bi3+ ions. With increasing the Bi2O3 content, this near visible band is observed to disappear indicating peculiar behavior needing further work. Gamma irradiation causes only minor changes in the position of the strong UV peaks but an obvious induced visible broad band centered at 452-460nm in the base and Bi2O3 containing glasses. This induced band is related to the generation of phosphorus oxygen hole center or non bridging oxygen hole center as revealed by various authors. FTIR results reveal characteristic vibrational bands due to phosphate groups and with the addition of Bi2O3, some interference of BiO vibrational units are expected. Gamma irradiation causes limited changes in the IR spectra due to suggested shielding effect of the heavy metal oxide Bi2O3.

Effect of 3d-transition metal doping on the shielding behavior of barium borate glasses: a spectroscopic study.

UV-visible and FT infrared spectra were measured for prepared samples before and after gamma irradiation. Base undoped barium borate glass of the basic composition (BaO 40%-B2O3 60mol.%) reveals strong charge transfer UV absorption bands which are related to unavoidable trace iron impurities (Fe(3+)) within the chemical raw materials. 3d transition metal (TM)-doped glasses exhibit extra characteristic absorption bands due to each TM in its specific valence or coordinate state. The optical spectra show that TM ions favor generally the presence in the high valence or tetrahedral coordination state in barium borate host glass. Infrared absorption bands of all prepared glasses reveal the appearance of both triangular BO3 units and tetrahedral BO4 units within their characteristic vibrational modes and the TM-ions cause minor effects because of the low doping level introduced (0.2%). Gamma irradiation of the undoped barium borate glass increases the intensity of the UV absorption together with the generation of an induced broad visible band at about 580nm. These changes are correlated with suggested photochemical reactions of trace iron impurities together with the generation of positive hole center (BHC or OHC) within the visible region through generated electrons and positive holes during the irradiation process.

Characterization by combined optical and FT infrared spectra of 3d-transition metal ions doped-bismuth silicate glasses and effects of gamma irradiation.

Optical and infrared absorption spectral measurements were carried out for binary bismuth silicate glass and other derived prepared samples with the same composition and containing additional 0.2% of one of 3d transition metal oxides. The same combined spectroscopic properties were also measured after subjecting the prepared glasses to a gamma dose of 8 Mrad. The experimental optical spectra reveal strong UV-near visible absorption bands from the base and extended to all TMs-doped samples and these specific extended and strong UV-near visible absorption bands are related to the contributions of absorption from both trace iron (Fe(3+)) ions present as contaminated impurities within the raw materials and from absorption of main constituent trivalent bismuth (Bi(3+)) ions. The strong UV-near visible absorption bands are observed to suppress any further UV bands from TM ions. The studied glasses show obvious resistant to gamma irradiation and only small changes are observed upon gamma irradiation. This observed shielding behavior is related to the presence of high Bi(3+) ions with heavy mass causing the observed stability of the optical absorption. Infrared absorption spectra of the studied glasses reveal characteristic vibrational bands due to both modes from silicate network and the sharing of Bi-O linkages and the presence of TMs in the doping level (0.2%) causes no distinct changes within the number or position of the vibrational modes. The presence of high Bi2O3 content (70 mol%) appears to cause stability of the structural building units towards gamma irradiation as revealed by FTIR measurements.

Ultraviolet and infrared absorption spectra of Cr2O3 doped-sodium metaphosphate, lead metaphosphate and zinc metaphosphate glasses and effects of gamma irradiation: a comparative study.

The effects of gamma irradiation on spectral properties of Cr2O3-doped phosphate glasses of three varieties, namely sodium metaphosphate, lead metaphosphate and zinc metaphosphate have been investigated. Optical spectra of the undoped samples reveal strong UV absorption bands which are attributed to the presence of trace iron impurities in both the sodium and zinc phosphate glasses while the lead phosphate glass exhibits broad UV near visible bands due to combined absorption of both trace iron impurities and divalent lead ions. The effect of chromium oxide content has been investigated. The three different Cr2O3-doped phosphate glasses reveal spectral visible bands varying in their position and intensity and splitting due to the different field strengths of the Na(+), Pb(2+), Zn(2+) cations, together with the way they are housed in the network and their effects on the polarisability of neighboring oxygens ligands. The effects of gamma irradiation on the optical spectral properties of the various glasses have been compared. The different effects for lead and zinc phosphate are related to the ability of Pb(2+), and Zn(2+) to form additional structural units causing stability of the network towards gamma irradiation. Also, the introduction of the transition metal chromium ions reveals some shielding behavior towards irradiation. Infrared absorption spectra of the three different base phosphate glasses show characteristic vibrations due to various phosphate groups depending on the type of glass and Cr2O3 is observed to slightly affect the IR spectra. Gamma irradiation causes minor variations in some of the intensities of the IR spectra but the main characteristic bands due to phosphate groups remain in their number and position.

Optical and infrared absorption spectra of 3d transition metal ions-doped sodium borophosphate glasses and effect of gamma irradiation.

Undoped and transition metals (3d TM) doped sodium borophosphate glasses were prepared. UV-visible absorption spectra were measured in the region 200-900nm before and after gamma irradiation. Experimental optical data indicate that the undoped sodium borophosphate glass reveals before irradiation strong and broad UV absorption and no visible bands could be identified. Such UV absorption is related to the presence of unavoidable trace iron impurities within the raw materials used for preparation of this base borophosphate glass. The TMs-doped glasses show absorption bands within the UV and/or visible regions which are characteristic to each respective TM ion in addition to the UV absorption observed from the host base glass. Infrared absorption spectra of the undoped and TMs-doped glasses reveal complex FTIR consisting of extended characteristic vibrational bands which are specific for phosphate groups as a main constituent but with the sharing of some vibrations due to the borate groups. This criterion was investigated and approved using DAT (deconvolution analysis technique). The effects of different TMs ions on the FTIR spectra are very limited due to the low doping level (0.2%) introduced in the glass composition. Gamma irradiation causes minor effect on the FTIR spectra specifically the decrease of intensities of some bands. Such behavior is related to the change of bond angles and/or bond lengths of some structural building units upon gamma irradiation.