电子俘获材料Zn_4B_6O_(13)∶Dy~(3+)的热释光特性研究

通过高温固相扩散反应合成了稀土元素镝掺杂的 Zn4 - x B6 O1 3∶ x Dy3+ 磷光体 .测定了该化合物在高能6 0 Co伽玛射线辐照下的热释发光曲线和三维热释光谱 .三维热释光谱表明 ,位于大约 480 nm和 5 80 nm的发光谱带来自于 Dy3+ 离子的 f-f 跃迁 .基质中掺杂的 Dy3+ 离子浓度的变化能够改变陷阱的相对分布 ,随着Dy3+浓度的增加 ,发光峰温向高温方向移动 ,这可提高剂量器的热稳定性 .当辐照剂量增加时 ,发光峰温亦向高温方向移动 ,即陷阱加深 .确定了 Zn3.86 B6 O1 3∶ 0 .1 6Dy3+样品主峰的陷阱深度 E=0 .73 e V,频率因子S=2 .43× 1 0 9s- 1 .在 1～ 1 0 0 Gy治疗级范围内 ,Zn3.86 B6 O1 3∶ 0 .1 6Dy3+ 对 6 0 Co伽玛射线辐照的热释光剂量响应呈良好的线性关系 .实验结果表明 ,Zn3.86 B6 O1 3∶ 0 .1 6Dy3+是一个潜在的应用于临床医疗的伽玛射线电离辐射热释光剂量计材料 .     

稀土Dy~(3+),Tm~(3+)单掺杂的四硼酸锌磷光体的热释光

通过高温固相法合成了Dy3+,Tm3+单掺杂的四硼酸锌(ZnB4O7)磷光体,测定了室温下这2个磷光体经60Coγ-射线辐照后的三维热释光谱。从三维热释光谱可以观察到:这2个磷光体的主发光峰均位于218℃;ZnB4O7∶Tm3+磷光体的主热释光峰的发射波长为366、453、475、651和754 nm,ZnB4O7∶Dy3+磷光体的主热释光峰的发射波长为480、573、665和755 nm,分别为稀土离子Tm3+和Dy3+的特征跃迁发射。对于Tm3+掺杂的ZnB4O7磷光体,热释光发射强度较高,在辐射剂量学领域有潜在的应用。利用峰形法,评估了ZnB4O7∶Tm3+磷光体在218℃时发光峰的动力学参数,其陷阱深度E为1.64 eV,频率因子为3.42×1016s-1,遵循二级动力学。     

SrB_6O_(10)∶Tb的热释光性质研究

通过高温固相法合成了SrB6O10∶Tb热释光磷光体,并系统地研究了Ce3+,Li+共掺杂,Tb3+掺杂浓度以及60Coγ射线辐照剂量对其热释发光的影响,同时观察了其热释光发射。研究发现:Ce3+,Li+共掺杂对SrB6O10∶Tb磷光体的热释光灵敏度并没有提高。Tb3+掺杂浓度对SrB6O10热释光磷光体的灵敏度有一定影响:在从1%~10%(摩尔分数)的Tb3+掺杂浓度范围内,2%为最佳掺杂浓度。在此掺杂浓度条件下,用Chen的峰形法评估了此磷光体的动力学参数,发现其遵守二级动力学;增加辐照剂量,热释光发射也随之增强,并在所研究的剂量范围内呈线性变化;在其三维热释光发射谱中,观察到了Tb3+离子的特征发射。     

SrB6O10:Tb的热释光性质研究

通过高温固相法合成了SrB6O10：Tb热释光磷光体, 并系统地研究了Ce3＋, Li＋共掺杂, Tb3＋掺杂浓度以及60Co γ射线辐照剂量对其热释发光的影响, 同时观察了其热释光发射. 研究发现： Ce3＋, Li＋共掺杂对SrB6O10：Tb磷光体的热释光灵敏度并没有提高. Tb^3＋掺杂浓度对SrB6O10热释光磷光体的灵敏度有一定影响： 在从1%～10%（摩尔分数）的Tb3＋掺杂浓度范围内, 2%为最佳掺杂浓度. 在此掺杂浓度条件下, 用Chen的峰形法评估了此磷光体的动力学参数, 发现其遵守二级动力学;增加辐照剂量, 热释光发射也随之增强, 并在所研究的剂量范围内呈线性变化;在其三维热释光发射谱中, 观察到了Tb^3＋离子的特征发射.     

共掺La3+对Sr2SnO4∶Sm3+的余辉增强

研究了以La3+离子为辅助激活剂,对Sm3+掺杂的发光材料Sr2SnO4:Sm3+余辉性能的影响。采用传统的高温固相法合成Sr2SnO4∶Sm3+,La3+红色长余辉发光材料。利用X射线粉末衍射仪、荧光光谱仪、热释光剂量仪等手段对粉末样品进行了表征。分析结果表明,在1400℃得到了单相Sr2SnO4,Sr2SnO4∶Sm3+,La3+发光粉末有563、599和646 nm 3个发射峰,与Sm3+单掺杂的Sr2SnO4∶Sm3+相比,其光谱发射峰位没有明显变化。余辉亮度衰减曲线表明适量的La3+掺杂可以延长Sr2SnO4∶Sm3+的余辉时间。通过对热释光谱的分析,解释了双掺杂发光粉余辉性能增强的原因,La3+掺杂增加了更多适宜深度的陷阱(VSr″),可以有效存储光能,增强余辉的时间和强度。     

Yb3+共掺杂对Zn2GeO4∶Mn2+绿色长余辉发光性能增强研究

利用高温固相法合成了Zn2GeO4∶Mn2+以及Zn2GeO4∶Mn2+,Yb3+绿色发射长余辉发光材料,对样品进行了X射线衍射分析、荧光光谱分析、色坐标、热释发光以及发光寿命测量。分析结果表明,在1 050℃下烧结3 h的Zn2GeO4为单相产物,所得Zn2GeO4∶Mn2+发光材料具有良好的发光性能,在紫外灯激发下发出最强发射位于528 nm的宽带发射并具有优良的长余辉发光特性,其色坐标值分别为x=0.145,y=0.773。Yb3+共掺杂对其长余辉发光性能提高明显。余辉发光在暗场环境下肉眼可观察的持续时间超过2 h。通过热释光谱对陷阱进行了分析。对Yb3+共掺杂的长余辉发光增强机理进行了讨论。     

Ce和Dy在Cd0.5Zn0.5B4O7中的发光特性及能量双向传递

采用高温固相法制备了白蓝光双发射为一体的Cd0.5Zn0.5B4O7∶Ce/Dy系列发光材料. 由XRD测得Cd0.41Zn0.5B4O7∶Ce0.04/Dy0.02的晶胞参数: a=1.3885 nm, b=0.8020 nm, c=0.8670 nm, 属于正交晶系, Pbca空间群. 在Ce/Dy双掺的体系中存在Ce3+和Dy3+两种发光中心, 254~350 nm激发主要是Dy3+的 4F9/2→6H15/2和4F9/2→6H13/2跃迁发射, 而355—390 nm激发主要为Ce3+的5d→4f跃迁发射. 340 nm激发Ce/Dy双掺发光体的发射强度是同浓度Dy3+单掺的31倍, Ce3+是Dy3+的高效敏化剂, 而355—390 nm激发Dy3+是Ce3+的敏化剂. 体系中存在少见的Ce3+→Dy3+与Dy3+→Ce3+的能量双向传递.     

Yb3+共掺杂对Zn2GeO4:Mn2+绿色长余辉发光性能增强研究

利用高温固相法合成了Zn2GeO4:Mn2+以及Zn2GeO4:Mn2+,Yb3+绿色发射长余辉发光材料,对样品进行了X射线衍射分析、荧光光谱分析、色坐标、热释发光以及发光寿命测量.分析结果表明,在1050℃下烧结3h的Zn2CeO4为单相产物,所得Zn2GeO4:Mn2+发光材料具有良好的发光性能,在紫外灯激发下发出最强发射位于528 nm的宽带发射并具有优良的长余辉发光特性,其色坐标值分别为x=0.145,y=0.773.Yb3+共掺杂对其长余辉发光性能提高明显.余辉发光在暗场环境下肉眼可观察的持续时间超过2h.通过热释光谱对陷阱进行了分析.对Yb3+共掺杂的长余辉发光增强机理进行了讨论.     

ZnO-B2O3∶Tb3+长余辉玻璃的发光性质

通过还原方法制备了Tb³⁺离子掺杂的硼酸锌玻璃，并观察到在254 nm紫外光激发后有明亮的绿色长余辉发光现象，余辉时间达6 h。通过激发与发射光谱、余辉光谱、余辉衰减曲线、热释光谱、热释光释出速率衰减曲线等得到的信息，研究了Tb³⁺离子掺杂的硼酸锌玻璃的发光性质。     

Dy3+单掺及Dy3+,Er3+共掺GdVO4纳米粒子的制备及发光性能的研究

用水热法制备了Dy3+单掺及Dy3+,Er3+双掺GdVO4纳米荧光粉,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱仪(FTIR)和荧光(FL)光谱对合成样品的结构、形貌和发光性能进行表征;探讨了Dy3+掺杂浓度、络合剂对GdVO4:Dy3+纳米晶的结构、形貌和发光性能的影响;考察了不同波长的近红外光和紫外光激发的GdVO4:Dy3+,Er3+,得到不同颜色的上转换和下转换荧光光谱。以760~830 nm近红外光和210~380 nm紫外光激发GdVO4:Dy3+纳米晶,可获得Dy3+蓝绿色双模发光;其中蓝光来自于Dy3+离子的4F9/2→6H15/2跃迁,绿光由Dy3+离子4F9/2→6H13/2跃迁产生。     

Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ～343°C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.     

The thermoluminescence response of Ge-doped optical fibre subjected to photon irradiation

A radiation dosimeter based on Ge-doped silica fibre is described. Parameters concerning thermoluminescence (TL) induced by ⁶⁰Co irradiation are investigated, including activation energies, frequency factors, and reproducibility with dose and fading. It is concluded that Ge-doped silica fibres provide a good basis for medical radiation dosimetry at therapy levels. In particular, doses are reproducible to within 3%, the fibres are reusable and show linearity of dose versus TL output over the approximate range of dose 1 Gy to in excess of 100 Gy. At room temperatures, fading within the first 30 d following irradiation has been found to be of the order of 7%.     

Thermoluminescence characteristics of neodymium-doped silicon dioxide optical fibers subjected to X-ray

In this article, we investigate thermoluminescence properties of Nd³⁺ doped silicon dioxide optical fiber. The samples were exposed to 10 MV X-ray using a linear accelerator. The optical fiber was read out using Harshaw 3500 TLD reader. Nd-doped optical fiber displays a linear TL response for the absorbed dose. The sensitivity of Nd-doped optical fiber is 82.87 nC. mg^–1 Gy^–1, which is more sensitive to the other types of optical fiber. Nd⁺³-doped optical fiber displays clear single glow peak around 180°C. The peak shape method analysis reveals that the peaks obey general order kinetics. The activation energy of Nd-doped optical fiber is found to be nearly 0.5 eV less than TLD-100 (1.6 eV). Z_eff of neodymium-doped silicon dioxide optical fiber is 13.48 that is near to the human bone. All of these TL characteristics indicate that Nd107-doped optical fiber as a potential TL dosimeter, for measuring photon irradiation.     

单掺杂与共掺杂离子对Sr2Mg(BO3)2磷光体热释发光的影响

通过高温固相法合成了Sr2Mg(BO3)2磷光体, 并研究了Li＋, Bi3＋, Gd3＋, Ti4＋共掺杂对Sr2Mg(BO3)2∶Dy磷光体热释发光的影响. 研究发现: Li＋的共掺杂使Sr2Mg(BO3)2∶Dy磷光体的热释光主峰强度增加, 而 Bi3＋, Gd3＋或Ti4＋的掺入使样品的热释光强度降低. 在Li＋, Bi3＋, Gd3＋或Ti4＋共掺杂的Sr2Mg(BO3)2∶Dy磷光体高温热释光发射谱中, 我们观察到了480, 579, 662和755 nm的发射峰, 为特征Dy3＋离子的4F9/2→6H15/2, 4F9/2→6H13/2, 4F9/2→6H11/2和4F9/2→6H9/2跃迁, 与Sr2Mg(BO3)2∶Dy磷光体的发射一致. 利用峰形法, 我们评估了Sr2Mg(BO3)2∶ , ( )热释光磷光体234 ℃发光峰的动力学参数, 陷阱深度E＝1.1 eV, 频率因子s＝6.3×109 s－1, 遵循二级动力学.     

Phase diagram, crystal chemistry and thermoelectric properties of compounds in the Ca-Co-Zn-O system

In the Ca-Co-Zn-O system, we have determined the tie-line relationships and the thermoelectric properties, solid solution limits, and structures of two low-dimensional cobaltite series, Ca₃(Co, Zn)₄O_9−z and Ca₃(Co,Zn)₂O_6−z at 885 °C in air. In Ca₃(Co,Zn)₄O_9−z, which has a misfit layered structure, Zn was found to substitute in the Co site to a limit of Ca₃(Co_3.8Zn_0.2)O_9−z. The compound Ca₃(Co,Zn)₂O_6−z (n=1 member of the homologous series, Ca_n+2(Co,Z_n)_n(Co,Zn)′O_3n+3−z) consists of one-dimensional parallel (Co,Zn)₂O₆⁶⁻ chains that are built from successive alternating face-sharing (Co,Zn)O₆ trigonal prisms and ‘n’ units of (Co,Zn)O₆ octahedra along the hexagonal c-axis. Zn substitutes in the Co site of Ca₃Co₂O₆ to a small amount of approximately Ca₃(Co_1.95Zn_0.05)O_6−z. In the ZnO-CoO_z system, Zn substitutes in the tetrahedral Co site of Co₃O₄ to the maximum amount of (Co_2.49Zn_0.51)O_4−z and Co substitutes in the Zn site of ZnO to (Zn_0.94Co_0.06)O. The crystal structures of (Co_2.7Zn_0.3)O_4−z, (Zn_0.94Co_0.06)O, and Ca₃(Co_1.95 Zn_0.05)O_6−z are described. Despite the Ca₃(Co, Zn)₂O_6−z series having reasonably high Seebeck coefficients and relatively low thermal conductivity, the electrical resistivity values of its members are too high to achieve high figure of merit, ZT.     

Accidental and retrospective dosimetry using TL method

Retrospective dosimetry is one of the most important tools of accidental dosimetry for dose estimation when dose measurement was not planned. In the affected area many objects can be applied as natural dosimeters. The paper discusses our recent investigations on various electronic components and common salt (NaCl) having useful thermoluminescence (TL) properties. Among materials investigated the electronic components of cell phones seem promising for retrospective dosimetry purposes, having high TL responses, proper glow curve peaks and the intensity of TL peaks vs. gamma dose received provided nearly linear response in the dose range of 10 mGy–1.5 Gy.     

Methods for routine control of irradiated food: Determination of the irradiation status of shellfish by thermoluminescence analysis

In some countries, clearance has been given for treating certain types of shellfish by ionizing radiation in order to increase the shelf-life and to reduce health hazards which might be caused by contaminating microorganisms. In the present study, thermoluminescence (TL) analysis was used to examine the irradiation status of shellfish products purchased from local suppliers. For analysis minerals were isolated from the guts of the animals. Although on none of the examined products an irradiation treatment prior to analysis could be shown, the results obtained on non-irradiated and irradiated products have revealed that irradiation within the commercially used dose range can clearly be detected. Already first glow TL intensities of minerald indicated irradiation treatments. Normalized TL signals of non-irradiated and irradiated samples were clearly separated. By calculation of differences of TL intensities and TL signals between non-irradiated and irradiated samples in dependency of integration temperature an optimized integration area for glow curves was determined. The result of this study agree well with results obtained by two large-scale intercomparisons between food control laboratories to detect irradiation treatment of spices and herbal products as well as of fruit and vegetables by TL analysis of contaminating minerals.     

Intrinsic dosimetry of glass containers: a potential interrogation tool for nuclear forensics and waste management

Intrinsic dosimetry is the method of measuring total absorbed dose received by the walls of a container holding radioactive material. By considering the total absorbed dose received by a container in tandem with the physical characteristics of the radioactive material housed within that container, this method has the potential to provide enhanced pathway information regarding the history of the container and its radioactive contents. We report the latest in a series of experiments designed to validate and demonstrate this newly developed tool. Thermoluminescence (TL) dosimetry was used to measure dose effects on raw stock borosilicate container glass up to 70 days after gamma ray, X-ray, beta particle or ultraviolet irradiations at doses from 0.15 to 20 Gy. Two main peaks were identified in the TL glow curve when irradiated with ⁶⁰Co, a relatively unstable peak around 120 °C and a more stable peak around 225 °C. Signal strength of both peaks decayed with time. The minimum measurable dose using this technique is 0.15 Gy, which is roughly equivalent to a 24 h irradiation at 1 cm from a 50 ng ⁶⁰Co source. As a result of fading, this dose would be detectable for approximately 1 year post-irradiation. In a more detailed analysis, the TL glow curves were separated into five peaks centered near 120, 160, 225, 300, and 340 °C. Differences in TL glow curve shape and intensity were observed for the glasses from different geographical origins. These differences can be explained by changes in the intensities of the five peaks. This suggests that mechanisms controlling radiation induced defect formation from gamma, beta, X-ray, and UV sources may be similar.     

柱撑阴离子粘土的合成、表征及催化性能研究(V)

Organic-anion-pillared layered double hydrotalcites such as Zn2AlTA(TA=terephthalate) are easily synthesized by using coprecipitation reaction of Zn2+ and Al3+ ions with terephthalic acid in NaOH solution. Exchange of this material under mild acidic conditions with the heteropolyanions proceeds smoothly to yield Zn2AlSiW11Co and Zn2Al-BW11Cu. Characterization has been carried out by elemental chemical analysis, powder X-ray diffraction and IR spectra. The results indicated that these materials possess exceptionally well-ordered gallery height of 0.98nm. It was found that this kind of pillared layered catalyst has high activity and selectivity for the oxidation of benzaldehyde to benzoic acid using H2O2 as oxidant in liquid-solid phase system.