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Shielding Behavior of Gamma-Irradiated MoO3 or WO3-Doped Lead Phosphate Glasses Assessed by Optical and FT Infrared Absorption Spectral Measurements

机译:通过光学和FT红外吸收光谱测量评估的γ辐照的MOO3或WO3掺杂铅磷酸盐玻璃的屏蔽行为

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Undoped and MoO3- or WO3- doped lead phosphate glasses were prepared by the melting-annealing technique. The glasses were characterized through UV-visible and infrared measurements which were repeated after gamma irradiation. Optical spectrum of binary lead phosphate glass shows distinct ultraviolet bands correlated with unavoidable trace iron impurities within the chemicals used for the preparation of the glasses. UV-visible absorption spectra of MoO3- orWO(3)- doped glasses exhibit additional UV-visible bands which are related to the presence of four oxidation states of the two transition metal (molybdenum or tungsten) ions (Mo3+, Mo4+, Mo5+, Mo6+, W3+, W4+, W5+, W6+). The extra UV band is related to hexavalent (5d(0)) state while the rest of the visible bands are related to (350-440 nm - trivalent state), (450, 550, 650 nm - tetravalent state) while the broad band centered at about 770 nm (pentavalent state). The intensities of the absorption bands are observed to change with the transition metal content and their valencies. Infrared absorption spectra reveal distinct vibrational bands which are assigned to phosphate groups with sharing of Pb-O vibrations within both the range 460620 cm(-1) and the range 900-1100 cm(-1) revealing a compact network structure. Gamma irradiation causes a minor increase in intensity of one of the UV band due to suggested photo-oxidation of some trace ferrous ions to additional ferric ions but the remaining spectral curve remains unaffected which is obviously related to some shielding effects of heavy atomic weight of PbO. This heavy metal oxide (PbO) is assumed to retard or prohibit the free passage of free electrons or positive holes generated during the irradiation process.
机译:通过熔化退火技术制备未掺杂的和MOO3-或WO3-掺杂的磷酸盐玻璃。通过UV可见和红外测量来表征玻璃的特征在于γ辐射后重复。二元铅磷酸盐玻璃的光谱显示出与用于制备玻璃的化学物质内的不可避免的痕量铁杂质相关的不同的紫外线带。 MOO3-或WO(3)掺杂眼镜的UV可见吸收光谱表现出额外的UV可见带,其与两个过渡金属(钼或钨)离子的四种氧化态有关(MO3 +,MO4 +,MO5 +,MO6 + ,W3 +,W4 +,W5 +,W6 +)。额外的UV频段与六价值(5D(0))状态有关,而宽带的可见频带的其余部分与(450,550,650nm - 四价状态)有关,而宽带以大约770nm(五价州)为中心。观察吸收带的强度以随过渡金属含量及其单位改变。红外吸收光谱揭示了分配给磷酸盐基团的明显振动带,其在460620cm(-1)范围内的Pb-o振动和900-1100cm(-1)范围内显示紧凑的网络结构。由于一些痕量铁离子的建议的光氧化,γ辐射导致紫外线带的强度小于uV频段的强度,但剩余的光谱曲线仍未受到影响,这显然是与PbO重原子重量的一些屏蔽效应有关。假设该重金属氧化物(PBO)延迟或禁止在照射过程中产生的自由电子或正孔的自由通道。

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