运用ESR方法测定一些地质样品年龄的尝试

本文介绍了用ESR测地质年代方法的发展、现状及基本原理。给出了用ESR方法测定四川鲜水河地震活动断裂带的泉华样品、泥河湾的丽蚌化石样品、北京周口店洞穴中石笋样品的天然辐射总剂量AD的初步结果。测定周口店洞穴中石笋样品的年龄为(6×10⁴)年。并对结果进行了讨论。最后,还就有关ESR测年代方法的一些有关问题进行了探讨。     

碳酸盐沉积物的ESR断代

本文用ESR断代法测定某些碳酸盐沉积物的年代,其结果与¹⁴法符合得很好。对影响ESR断代法测定精度的一些因素进行了详细的讨论,如样品的处理、ESR测量、数据处理,年剂量和总累积剂量的测定。     

X-波段电子自旋成象

报道了自行设计研制的X-波段ESR成象装置并用之对典型样品作了ESR成象测定;用解卷积和分析图象重建中卷积滤波法对自旋样品体系进行了二维的图象重建,获取了能反映真实自旋分布的二维自旋密度图象.     

ESR研究非晶Ag+导体的晶化

用电子自旋共振(ESR)方法对非晶Ag⁺离子导体0.85AgI~0.15Ag₄P₂O₇的热处理晶化过程进行研究,在样品中掺入微量(约1×10^-3 g/g)的Mn²⁺或V⁴⁺离子作为自旋探针离子,它们的ESR谱强度随升温线性减弱,当样品完全晶化时ESR谱消失。这样测定的样品完全晶化的温度分别为98℃(掺Mn的)和108℃(掺V的).本文还对Mn²⁺和V⁴⁺的ESR谱进行了分析。     

纳米FeAl合金的磁共振谱分析

在与晶粒组元相当的包裹纳米FeAl晶粒的无序界面或/和表面组元中,存在Fe-Al-Fe电子的超交换作用或/和Fe-Fe交换作用,使多晶FeAl合金因晶粒纳米化出现非磁性—磁性转变.X波段(频率为9.48GHz)的电子自旋共振(ESR)实验表明多晶FeAl合金没有磁共振信号.纳米晶样品的铁磁共振(FMR)信号是一个线宽ΔH_pp为8×10⁴A/m以上的宽峰.还观测到纳米晶体样品中Fe²⁺离子的ESR精细结构双峰,两峰间隔为1.316×10关键词：     

纳米NiAl的电子自旋共振研究

对纳米NiAl样品进行电子自旋共振(ESR)研究时发现晶粒尺寸效应产生的非磁-磁性转变.大块多晶NiAl合金的没有ESR信号,只有很弱的Pauli顺磁性.而粒径为8.6nm的纳米NiAl样品的ESR信号,随温度的增高而显著下降,其居里温度T_C为124K,在室温下ESR信号很弱.8.6nm的纳米NiAl样品经550℃和707℃退火处理后得到粒径分别为12nm和21nm的两个样品,它们在室温下都有较强的ESR信号,并能够被永磁体吸起。多晶NiAl合金与纳米NiAl之间存在非磁-磁性转变,     

五种氨基酸钆络合物的ESR波谱

迄今未见任何稀土氨基酸络合物的ESR波谱报道,本文在合成Gd³⁺分别与甘氨酸、β-丙氨酸、谷氨酸、天冬氨酸和天冬酰胺五种氨基酸络合物的基础上,测定了不同温度下,水溶液、粉末及分子筛吸附样品的ESR谱,讨论了络合物中晶体场强,对称性及成键特性。     

Yb~(3+)/Tm~(3+)掺杂BaMoO_4上转换发光晶体的热稳定性能

采用水热法制备了BaMoO_4∶Yb~(3+)/Tm~(3+)纳米晶体。通过改变样品的合成温度及测试温度研究材料的热稳定性能和发光性能。结果显示,当C_(Yb~(3+))=6%、C_(Tm~(3+))=1.5%时,经过743 K高温再结晶的样品晶粒尺寸变大,发光性能及热稳定性能明显提升。对形貌和结构分析发现样品具有标准的四方晶格结构及较高的结晶度。上转换发射光谱及荧光衰减曲线的测定结果说明样品热稳定性能优异。量子产率达到1.5%,发射光颜色均匀。证明了BaMoO_4∶Yb~(3+)/Tm~(3+)纳米晶体实际应用价值高,热稳定性能及发光性能好。     

坦桑石的矿物学及谱学特征研究

对来自坦桑尼亚Merelani地区的坦桑石样品,分别采用电子探针、EMXPLUS型ESR谱仪、同步热分析仪、紫外可见光谱仪以及傅里叶变换红外光谱仪进行了测试与分析。结果表明：坦桑石样品的主要成分为SiO₂,Al₂O₃和CaO,微量成分中V₂O₅含量相对最多,平均含量为0.36%;坦桑石样品本身不含吸附水,结晶水, 加热至780 ℃附近时,脱失结构水,样品中结构水大约占总质量的2%;ESR实验结果中显示出明显Fe3+和Mn2+的电子顺磁信号;紫外-可见光谱显示,样品在385 nm处出现吸收窄带,575和750 nm处分别出现较为宽缓的吸收;红外光谱测试表明,样品在6 500~9 000 cm-1波段的倍频振动区,基本没有吸收。在4 000~6 500 cm-1波段主要为和频振动,5 956 cm-1附近呈较宽缓的吸收峰,5 413,5 184,4 336和4 046 cm-1处出现较尖锐的吸收峰,主要可能由O-H,矿物内的Si-O,以及空气里面的H₂O分子和CO₂振动所引起。综合EPMA以及ESR分析结果,蓝-紫色坦桑石颜色可能主要由V3+和V5+共同引起,Fe3+晶体场的d-d电子跃迁、Fe2+→Ti4+的电荷转移辅助致色。     

红外光谱中挥发性液体的气态样品取样技术

采用设计的真空装置 ,将挥发性液体的气态样品吸入气体样池中进行红外光谱测定。用此装置测得的液体的红外光谱图不出现常规液体样品测定时的平头峰 ,峰位易辨认 ,且可定量。并探讨了挥发性液体的取样范围、浓度范围和压力条件。     

A method for identification of interfering signals in EPR dating of tooth enamel

In this paper, a method for identifying interfering EPR signals in fossil tooth enamel is presented. This method consists of optimizing EPR parameters to enhance spectral resolution of the fossil signals followed by a g-factor and intensity normalized subtraction of a high-dosed, modern tooth enamel sample spectrum. By scanning the modern tooth enamel sample with the same parameters as the fossil sample, the difference spectrum of the fossil and modern irradiated tooth enamel samples can resolve numerous hyperfine and other interfering signals. This method was successfully applied to a fossil sample studied elsewhere (Grün, R., 1998a. Ancient TL 16, 51–55; Grün, R., Clapp, R., 1996. Ancient TL 14, 1–5; Martin Jonas, 1997. Ph.D. Thesis, Cambridge University; Jonas, M., Grün, R., 1997. Radiat. Meas. 27, 49–58; Vanhaelewyn et al., 2000. Appl. Radiat. Isot. 52, 1317–1326). This sample has shown discrepancies in dose estimations obtained from the power absorption curve versus those obtained from the first derivative spectra (Grün, R., 1998b. Radiat. Meas. 29, 177–193). The reason for this, and other discrepancies, are accounted for by the signals resolved using the method presented here.     

Dose response of ESR signals in tooth enamel

Radiation-induced growth in the g = 2.0018 signal in fossil tooth enamel can be used to determine the age of fossil teeth. Porat and Schwarcz (1994) [Integrative Paths to the Past: Paleoanthropological Advances in Honor of F.C. Howell (eds Corrucini R. and Ciochon R.), pp. 521–530. Prentice- Hall, Englewood Cliffs] suggested that the radiation sensitivity of all tooth enamel is quite similar, and have constructed a Universal Growth Curve (UGC) to estimate equivalent dose (D_E). To further test this concept, we use a saturating exponential of the form I = I_max (1 - exp[- D/D₀]) to fit normalized ESR intensity (I) data for teeth from various sites. We show that the ranges of fitting parameters I_max and D₀ overlap for modern and fossil enamels. This suggests that no significant diagenetic changes in the enamel have occured to affect the ESR signal in most samples. Sensitivity, as measured by normalized intensity at D = 32 Gy, varies by 22% (n = 24); modern samples have the same mean sensitivity, but show less variation (8%). The normalized dose-response curve (natural intensity vs D_E) is a good predictor of D_E, although there are some outliers. I_max is strongly correlated with D₀, suggesting a relationship between trap concentration and capture cross-section for migrating charges.     

Evaluating the accuracy of ESR dose determination of pseudo-Early Pleistocene fossil tooth enamel samples using dose recovery tests

In ESR dating of Early Pleistocene fossil tooth enamel samples, the fitting function used for the evaluation of the D_E value is undoubtedly among the major sources of uncertainty. Dose recovery tests performed on fossil tooth enamel showing D_E values >1,000 Gy demonstrate: (i) that high precision ESR measurements (<0.5%) and high D_E reproducibility (<5%) may be achieved; (ii) the appropriateness of the Double Saturating Exponential (DSE) fitting function for ESR dose reconstruction. In contrast, the SSE function, which has been almost exclusively used so far, does simply not correctly describe the behavior of the radiation induced ESR signal of tooth enamel with the dose.Several fitting functions and data weighting options were tested and the combination of a DSE with data weighted by the inverse of the squared intensities is the procedure providing the most accurate D_E results. However, the SSE may nevertheless sometimes produce consistent results if D_max does not exceed 6*D_E. Further work is required in that direction in order to determine more precisely in which conditions the SSE could be used as a fair approximation of the DSE function for these samples.     

EPR-dosimetry with carious teeth

The effect of caries in EPR dosimetry of tooth enamel (in the dose range of 0–1 Gy) was investigated. The enamel of each tooth was divided into carious, non-carious and intermediate portions. The EPR signals of enamel at g = 2.0018 (dosimetric) and g = 2.0045 (native) were examined. The intensity of the dosimetric signal was the same for all three portions, while that of the native signal was higher for carious portions than for non-carious and intermediate portions. Reconstruction of the laboratory applied doses was done using all portions. Reasonable correlation between nominal and reconstructed doses was found in most cases. The effect of alkali treatment on the native and dosimetric signals of enamel was also tested. Reduction of the native signal intensity, particularly in the carious portions, was found to be the only significant effect. This resulted in a slight improvement in the accuracy of the reconstructed doses.     

Analysis of EPR tooth enamel spectra exposed to combined radiation and mechanical effects

In the EPR spectra of tooth enamel samples exposed to sequential radiation and mechanical effect, the intensity of the signal in the spectra of tooth enamel samples exposed to sequential mechanical and radiation effects exceeded the amplitude of a signal in enamel samples that were only exposed to radiation. The increased dosimetric signal can be explained by superposition of mechanically and radiation-induced signals. The contribution of the mechanically induced component to the individual dose load reconstructed by EPR-spectra of tooth enamel has been evaluated.     

Dose response of hydrazine – Deproteinated tooth enamel under blue light stimulation

The beta dose response and Optically Stimulated Luminescence (OSL) signal stability characteristics of human tooth enamel deproteinated by hydrazine reagent under blue photon stimulation are reported. Removal of the protein organic component of tooth enamel resulted in a higher OSL sensitivity and slower fading of OSL signals. The effect of chemical sample preparation on the enamel sample sensitivity is discussed and further steps to make this deproteinization treatment suitable for in vitro dose reconstruction studies are suggested.     

Comparative EPR study CO2− radicals in modern and fossil tooth enamel

Comparative EPR investigation of CO₂⁻ radicals in modern (γ-irradiated) and fossil samples of tooth enamel was performed. The samples studied were the enamel powders and plates, the latter demonstrating an orientation dependence of EPR spectra in an external magnetic field. It was found that the ratio between the axial and orthorhombic CO₂⁻ centers amounts appears to be different for modern and fossil enamels. This ratio can be estimated by modeling of EPR spectra lineshape of powders or, in the case of plates, from the orientation dependence of EPR spectra in an external magnetic field. It was assumed that the difference between modern and fossil enamels is caused by the transformation, in the course of time, of orthorhombic CO₂⁻ centers into axial ones. The equations that describe this process were deduced. Their solutions show that the ratio between the amounts of the axial and orthorhombic centers does not depend on the dose rate. This finding can be used for the development of the method to determine the fossil enamel age avoiding the determination of the annual dose.     

Decomposition of the angular ESR spectra of fossil tooth enamel fragments

The ESR spectra of a fragment of fossil tooth enamel were measured by rotating it in 10° increments over 360° around its three major axes. We used an automated simulated annealing (SA) procedure for the mathematical decomposition of the spectra. The SA approach is particularly robust in finding global solutions rather than getting stuck in local minima. All angular measurements could be fitted with four Gaussian lines, all of which could be attributed to components of CO₂^? radicals. The results imply that the tooth enamel fragment contains at least two different types of oriented CO₂^? radicals, plus about 9% of non-oriented CO₂^? radicals. The oriented components were tentatively attributed to axial and orthorhombic CO₂^? radicals. Their explicit locations in the crystal domains of the tooth enamel remain unresolved.     

ISS protocol for EPR tooth dosimetry

The accuracy in Electron Paramagneetic Resonance (EPR) dose reconstruction with tooth enamel is affected by sample preparation, dosimetric signal amplitude evaluation and unknown dose estimate. Worldwide efforts in the field of EPR dose reconstruction with tooth enamel are focused on the optimization of the three mentioned steps in dose assessment. In the present work, the protocol implemented at ISS in the framework of the European Community Nuclear Fission Safety project “Dose Reconstruction” is presented. A combined mechanical–chemical procedure for ground enamel sample preparation is used. The signal intensity evaluation is carried out with powder spectra simulation program. Finally, the unknown dose is evaluated individually for each sample with the additive dose method. The unknown dose is obtained by subtracting a mean native dose from the back-extrapolated dose. As an example of the capability of the ISS protocol in unknown dose evaluation, the results obtained in the framework of the 2nd International Intercomparison on EPR tooth enamel dosimetry are reported.     

牙齿组织光热动态特性仿真与试验研究

调制激光作用牙齿组织发生散射形成光子密度波, 而由于光热效应产生热波, 基于一维介质辐射传输漫射近似方程与一维热传导方程建立了调制激光作用牙齿组织半透明混合介质的一维热波数学模型. 利用该模型仿真分析了牙齿龋损特性参数(牙釉质龋损层光吸收系数、散射系数、热扩散系数及龋损深度)对光热辐射动态响应特性的影响与规律. 利用红外探测器(HgCdTe, 2–12 μm)记录808 nm半导体激光激发牙齿组织产生的热波信号, 由锁相放大器计算热波信号的幅值与相位. 通过频率扫描试验获得了牙齿组织的光热动态响应, 利用多参数最佳统计拟合方法得到了牙齿组织特性参数. 结果表明光热辐射测量对牙齿组织不均匀性和龋损特性均具有较高敏感性与特异性.