基于EDXRF的土壤中痕量镉的快速检测方法研究

对于土壤中重金属元素的检测,传统的化学分析方法测试周期长,前处理复杂,使用的强酸还会对环境造成二次污染,能量色散X射线荧光光谱法具有无损、快速、前处理简单、仪器轻便等优点,特别适合现场快速检测,但用该方法对镉元素进行检测时,通常用到的K系特征线能量较大,普通能谱的检出限较高。基于能量色散X射线荧光光谱技术,研究了土壤中痕量重金属镉的快速检测方法,通过选择合适的仪器部件,搭建仪器测试系统,综合考虑待测元素的谱峰强度和相对强度,对仪器结构和测试条件进行优化。研究表明,峰强度随着管电流的升高基本上是线性增加的,而相对强度则没有明显的变化,对于镉的测试,在光管条件允许的情况下选择尽可能大的管电流进行测试,之后,综合考虑镉的峰强度和相对强度随滤光片厚度以及管电压的变化情况,使用理论标准偏差确定测试最优条件为：管电压为55 kV,管电流为48 μA,滤光片为1.25 mm钼片;测试时间会影响测试结果的相对标准偏差,在测试时间小于500 s时,峰强度的相对标准偏差随着测试时间的增加是降低的,在测试时间大于500 s时,峰强度的相对标准偏不再有明显的变化趋势,由于测试结果的相对标准偏差越小,测试结果的短期精密度越好,仪器的重现性就越好,因此测试时间最终选择为500 s;样品测试条件也会对测试结果产生影响：随着测试薄膜厚度的增加,镉的峰强度和相对强度均是降低的,根据实验结果,最终选择厚度为12.5 μm的聚酯膜进行测试;镉的峰强度和相对强度随着样品质量的增加而增加,在样品质量大于3 g时,镉的峰强度随样品质量的增加变化比较缓慢,相对强度则没有明显的变化,选择样品的质量大于3 g进行测试;随着含水量的增加,镉的峰强度和相对强度均会略有降低,因此水分会对测试结果产生影响,对土壤样品的测试应该风干或烘干。使用以上经过优化的测试条件,用国家标准样品和电感耦合等离子体质谱法定值的样品绘制工作曲线,线性相关系数可达0.993;使用镉含量为1.12 mg·kg-1的国家标准样品GSD-10测试11次,测试的结果的标准偏差为0.09,相对标准偏差为8.22%;用高纯二氧化硅测试方法检出限,可达0.16 mg·kg-1,小于国标一级土壤的限值;测试实际样品,并与电感耦合等离子体质谱法测试的结果进行对比,测试结果的一致性较好。通过对仪器结构和样品测试条件进行优化,基于能量色散X射线荧光光谱法对土壤中痕量重金属镉的检出限有了很大的降低,对污染地区土壤镉的快速筛查及大面积测定意义重大。     

Objective Voice Quality Analysis Before and After Onset of Unilateral Vocal Fold Paralysis

This study was designed to investigate objective voice quality measurements in unilateral vocal fold paralysis (UVFP) by eliminating intersubject variability. To our knowledge this is the first report objectively analyzing paralytic dysphonia as compared to the same voice before onset of UVFP. The voices of two male subjects were prospectively recorded before and after the onset of iatrogenic UVFP (thoracic surgery).The following acoustic measurements of the vowel /a/ were performed using the CSL and MDVP (Kay Elemetrics): jitter, shimmer, harmonics-to-noise ratio, cepstral peak prominence, the relative energy levels of the first harmonic, the first formant and the third formant, the spectral slope in the low-frequency zone (0-1 kHz and 0-2 kHz), and the relative level of energy above 6 kHz. Distribution of spectral energy was analyzed from a long-term average spectrum of 40 seconds of text. Laryngeal aerodynamic measurements were obtained for one patient before and after onset of paralysis using the Aerophone II (Kay Elemetrics). Pitch and amplitude perturbation increased secondary to UVFP, while the harmonics-to-noise ratio and the cepstral peak prominence decreased. A relative increase in the mid-frequency and high-frequency ranges and a decrease in the low-frequency spectral slope were observed. Mean airflow rate and intraoral pressure increased, and glottal resistance and vocal efficiency decreased secondary to UVFP. The findings of this self-paired study confirm some but not all the results of previous studies. Measures involving the fundamental and the formants did not corroborate previous findings. Further investigation with vocal tract modeling is warranted.     

Caller sex and orientation influence spectral characteristics of "two-voice" stereotyped calls produced by free-ranging killer whales

This study investigates how particular received spectral characteristics of stereotyped calls of sexually dimorphic adult killer whales may be influenced by caller sex, orientation, and range. Calls were ascribed to individuals during natural behavior using a towed beamforming array. The fundamental frequency of both high-frequency and low-frequency components did not differ consistently by sex. The ratio of peak energy within the fundamental of the high-frequency component relative to summed peak energy in the first two low-frequency component harmonics, and the number of modulation bands off the high-frequency component, were significantly greater when whales were oriented towards the array, while range and adult sex had little effect. In contrast, the ratio of peak energy in the first versus second harmonics of the low-frequency component was greater in calls produced by adult females than adult males, while orientation and range had little effect. The dispersion of energy across harmonics has been shown to relate to body size or sex in terrestrial species, but pressure effects during diving are thought to make such a signal unreliable in diving animals. The observed spectral differences by signaler sex and orientation suggest that these types of information may be transmitted acoustically by freely diving killer whales.     

Absolute triple differential cross sections for electron impact ionization of helium: Comparison between experimental and theoretical results at 256 eV collision energy

Triple differential cross sections have been measured for electron impact ionization of helium at 256 eV collision energy, 3 eV energy of the slow outgoing electrons and scattering angles of the fast outgoing electrons of 4°, 6°, 8°, and 10°. The data have been put on absolute scale by extrapolating the generalized oscillator strength to zero momentum transfer. In this optical limit the triple differential cross sections can be normalized by using the well-known cross sections for photoionization. The experimental data are compared with results of different theoretical approaches. For nearly all calculated curves rather good agreement with the measurements is obtained for the relative shape of the binary peak, while often its absolute cross section is overestimated. Concerning the recoil peak, larger discrepancies are found with respect to both, relative shapes and cross sections. A perceptible improvement can be stated for calculations which have been performed in a distorted wave approximation and in second Born approximation.     

Quantitative XPS: I. Analysis of X-ray photoelectron intensities from elemental data in a digital photoelectron database

An analysis of the correlation of theoretical predictions for photoelectron intensities is made with experimental data from an XPS digital database for 46 solid elements measured using a spectrometer with calibrated intensity and energy scales. This analysis covers single element samples measured for Al and Mg K X-rays. The spectral data are for widescans at 1 eV energy intervals with kinetic energies from 200 to 1506 eV using Al X-rays and to 1273 eV using Mg X-rays. In addition are narrow scans around the photoelectron peaks at 0.1 eV energy intervals. All spectra have the instrument intensity/energy response function removed so that the peak areas are proportional to the number of electrons emitted per steradian per incident K photon. Correlations are made for the ionisation cross sections of Scofield and the inelastic mean free paths given by the TPP-2M formula. The correlations are excellent, apart from a factor which may be associated with the background removal arising from the use of the Tougaard Universal cross section. These correlations lead directly to pure element relative sensitivity factors suitable for quantitative analysis. General equations are also provided to extract values for a new form of relative sensitivity factor for an average matrix. These average matrix relative sensitivity factors lead to simpler equations involving matrix factors that are effectively unity instead of the traditional values in the range 0.3 to 3.0.     

Response function of the CdZnTe SPEAR detector

The response function of the SPEAR CdZnTe detector developed by eV Microelectronics was studied in detail. This compact detector includes a CdZnTe crystal and a preamplifier. It is operational at room temperature. The energy range of the detector is between 10 keV and 1 MeV, and its relative resolution is less than 4% at 122 keV. The goal of our study was to establish an empirical analytical approximation of the response function to be used in Monte Carlo simulations (e.g. for spectrum unfolding). Various radionuclides were used for the study. The energy spectrum obtained from the detector not only showed smooth peaks but also had a tail on the low‐energy side of the peak. This tail part was more prominent at higher energies. By using the experimental spectrum for various nuclides such as ²⁴¹Am, ¹⁰⁹Cd, ⁵⁷Co and ¹³⁷Cs, the parameters required to replicate the experimental response with a peak plus exponential model were evaluated. Copyright © 2011 John Wiley & Sons, Ltd.     

强激光场中氢负离子双光子电离能量谱的研究

利用强场近似(Strong field approximation,SFA)方法研究氢负离子(H-)在强激光场中双光子电离的能量谱,所得到的电离谱随角度的变化规律与实验结果符合得很好.进一步的研究表明,H-离子在强激光场中双光子电离的能量谱与有质动力能有关.激光场强度越大,光电子的有质动力能也越大,能量谱向左移动越明显...     

强激光场中氢负离子双光子电离能量谱的研究

利用强场近似（Strong field approximation,SFA）方法研究氢负离子（H ）在强激光场中双光子电离的能量谱,所得到的电离谱随角度的变化规律与实验结果符合得很好.进一步的研究表明, H 离子在强激光场中双光子电离的能量谱与有质动力能有关.激光场强度越大,光电子的有质动力能也越大,能量谱向左移动越明显.我们的结果表明,使用强场近似是一种研究负离子在强激光场中电离过程的有效方法.     

Photoemission from Co on Pt(111) using synchrotron radiation in the range 40 eV ω 150 eV

Photoelectron spectra for CO adsorbed on the (111)-face of Pt have been measured using synchrotron radiation of energy 40 eV ω 150 eV. A dramatic increase of the molecular orbital (MO) intensity relative to the intensity of the Pt 5d valence band (VB) is observed for ω > 100 eV, to a ratio at that is a factor of three higher than at . The energy variation of the Pt 5d VB photoemission peak intensity has been derived independently in the 40–200 eV range from measurements on clean Pt. The 5d peak intensity is found to decrease steeply (by more than an order of magnitude) between 100 and 150 eV. The observed increase of the MO peak intensity relative to that of the 5d VB is attributed to this cross-section effect. The Pt VB peak nearest the Fermi energy which is mainly t_2g in character, is found to decrease in intensity on adsorption of CO. In the present case synchrotron radiation in the ω > 100 eV range appears to be especially valuable for studies of adsorbates.     

A conical piezoelectric transducer with integral sensor as a self-calibrating acoustic emission energy source

The experimental results of a conical piezoelectric transducer with integral backing sensor as a self-calibrating simulated acoustic emission (SAE) energy source are presented. It has been shown that there is a negative linear relationship between the energy of SAE signal detected by the backing sensor and the relative strength (signal energy) of SAE source in the structure detected by a reference sensor under different transducer-to-structure coupling efficiencies, with AC drives of the same wave packet, frequency and peak amplitude to excite the conical transducer as a SAE source at all the investigated frequencies over the frequency range of interest in AE measurements (nominally from 50 kHz to around 1 MHz). This should enable the relative strength of the SAE source in a structure to be determined using the SAE measurement from the backing sensor for the selected electrical inputs to the conical transducer, and hence to remove the concerns about inconsistent transducer-to-structure coupling affecting the relative strength of the SAE source for calibration.     

基于高斯锐化法的重叠峰分解方法研究

在放射性能谱测量中,由于探测器分辨率较低、待测样品中原子能级相近,往往会出现全能峰的重叠现象,对放射性核素的定性或定量检测带来较大的困难;常规的分离算法一般需要复杂的谱变换或大量的标准谱样本,不适用于现场测量中重叠峰的实时分解。因此,提出一种基于高斯锐化法的能谱重叠峰解析方法(GSM),结合峰锐化法的分辨率增强能力和褶积滑动变换法的平滑特性,可快速地识别、定位和解析γ能谱中的重叠峰。该方法首先对高斯函数进行锐化并做归一化处理,并以此作为变换算子,选择合适的高斯参数及窗宽度,通过对原始γ能谱数据进行褶积滑动变换,达到滤波和提高重叠峰分离度的目的;然后求解GSM成形处理后的谱线近似函数作为目标函数,并选取峰位中心附近若干点作为初始参数,最后以非线性拟合的方法进行重叠峰特征峰参数的解析。实验中,首先验证了该方法变换前后峰位、峰面积特征值的不变性,其次分别对重叠峰能谱段以及MCNP模拟的131I,137Cs,214Bi,206Bi和26Al混合放射源γ能谱进行方法验证。实验结果表明,该方法对于分离度大于0.375、信噪比大于40 dB的重叠峰具有较好分解效果,分解前后的峰位和峰面积的相对误差分别在1%和4.5%以内;对于γ能谱进行全谱解析后,重叠峰的峰位分离相对误差在1%以内,单峰的分离相对误差约为0.1%以内,且当变换算子的半宽度接近探测器能量分辨率时,重叠峰的分解结果更准确。该方法具备较好的噪声抑制性能,在全谱解析中无需进行能谱光滑及本底扣除等谱线预处理操作,且计算资源耗费少,分解精确度较高,便于能谱测量系统的嵌入式实时解谱应用,对放射性测量中能谱的现场快速解析具有实用性。     

拓扑缺陷对单壁碳纳米管电子结构及其光学光谱的影响

应用密度泛函理论计算了半导体型单壁碳纳米管(7,0)和(8,0)以及其发生镜像对称和非镜像对称Stone-Wales形变、形成异质结(7,0)—(8,0)情况下的能带结构、吸收光谱、反射光谱,并对计算结果进行了比较。研究发现： 引入拓扑缺陷态后,碳纳米管的能带结构发生了明显的变化,费米能级在不同缺陷情况下移动方向不一致;碳管的吸收和反射明显减弱且吸收峰和反射峰在低能区发生红移现象;在光子能量约为E=13 eV处各碳管的吸收谱和反射谱中均出现一特征峰,并且在引入缺陷以后该特征峰向高能区移动。文章对计算结果进行了分析和探讨,可望利用这种拓扑缺陷的引入而产生的光电特性来设计碳管光电器件。     

Surface structure determination by quasidynamical LEED intensity evaluation

The quasidynamical method for LEED intensity calculations is applied to Ir(100)1 × 1 over a broad energy range, 100–500 eV. The comparison with experiment and full dynamical calculations shows that peak positions and peak widths are well reproduced, but relative peak heights and therefore also shapes of peak groups can be considerably modified. This behaviour is discussed and explained in terms of the forward and backward diffraction properties of single layers. Finally, a structure determination is tried using the Pendry r-factor for the quantitative comparison of the experimental and quasidynamical data. The resulting value for the surface relaxation agrees with that determined from the full dynamical evaluation within the usual error of structure determination by LEED.     

Polarization and angular dependencies in the photoemission from gold

An elementary calculation of the polarization and angular dependencies of photoemission from the valence band of gold is presented. The results are applied to experiments using synchrotron radiation as a light source. We show that use of a cylindrical energy analyzer could result in modulations of the relative peak heights in the d-bands. Simple experimental tests of our conclusions are suggested.     

槽道流POD重构及湍流动能耗散率分析

采用二维粒子图像测速仪（2DPIV）对槽道内涡波流场进行实验研究,用POD技术对2DPIV瞬态速度矢量场进行主导模态重构,得到槽道内的平均流速和湍流动能分布;采用大涡PIV方法对湍流动能耗散率分布进行计算.结果表明：重构流场表征了原始流场的主导结构,剔除了噪声等干扰信息;大涡PIV方法能有效地估算动能耗散率的分布;湍流动能在壁面附近较小,在接近槽道中心区域湍流动能越来越大,呈现出射流的特征;动能耗散率的峰值出现在壁面附近和槽道中心区域,动能耗散率随着远离壁面程度的增加先降低后逐渐增加直至达到峰值.     

种群算法在能量色散X荧光重叠谱拟合中的应用

在能量色散X荧光光谱分析中,常用的闪烁探测器如NaⅠ(Tl)探测器的能量分辨率都不高,均在8%左右。能量分辨率低下往往对谱数据分析带来较大的难题,特别是在高本底低计数的情况下剥离仪器谱重叠峰会受到很大限制,越是重叠严重的峰越是无法剥离,进而无法分辨峰值和峰面积,更无法进一步对元素进行定性定量分析。为此,结合遗传算法和免疫算法的优势建立新的种群算法应用在重叠谱分析上,该算法以欧式距离为进化的判断依据,以最大相对相似误差值为迭代准则进行迭代。利用高斯函数模拟不同重叠程度的仪器谱图,将种群算法应用在重叠峰分离和全谱模拟中,峰道址偏差在±3道以内,峰面积偏差不超过5%,证明该方法在能量色散X荧光重叠谱分析中有较好的效果。     

Feasibility of the Precise Energy Calibration for Fast Neutron Spectrometers

Computational studies aimed at improving the accuracy of measurements performed using neutron generators with a tritium target were performed. A measurement design yielding an extremely narrow peak in the energy spectrum of DT neutrons was found. The presence of such a peak establishes the conditions for precise energy calibration of fast-neutron spectrometers.     

泡沫Al压缩形变及能量吸收特征

通过考察两种基体泡沫Al(分别为脆性和塑性)单向压缩应力-应变曲线，探讨了其形变和能量吸收特征及机理，得到了一些与以往不同的研究结果.研究发现，与其他多孔固体材料一样，泡沫Al的压缩形变过程也经历三个区域，即线性弹性区、平台区和致密化区；泡沫Al的吸能本领随屈服强度的提高而增强；在屈服强度相近的情况下，脆性泡沫Al的吸能本领高于塑性泡沫Al；泡沫Al吸能效率峰值对应于较低的应变值(约为0.15—0.25)；吸能效率峰值对基体成分和状态不敏感，随密度增加，吸能效率峰值呈下降趋势. 关键词：     

退火处理对YMnO3薄膜的结构和荧光性能的影响

室温下,采用脉冲激光沉积方法在Si(100)衬底上制备了YMnO3薄膜,并对其进行了不同温度的退火处理。采用X射线衍射和荧光光谱分析方法对薄膜的结构和荧光特性进行了研究。结果表明:通过退火处理,可以得到正交相和六方相共存的多晶态YMnO3薄膜,并且随着退火温度的升高,两相的比例发生变化,由正交相为主转变为六方相为主。YMnO3薄膜样品的荧光发射峰集中在波长430～620nm范围内,可能是由Mn3 离子从5T2到5E之间的能级跃迁所引起的。其荧光强度随着退火温度的升高逐渐增强,但峰位基本保持不变,说明薄膜结构的改变对Mn3 离子的能级跃迁几率有明显的影响,对能级位置的影响不大;而且荧光光谱还显示在同一薄膜中各个荧光峰的相对强度随着退火温度的变化不大。     

大气压氩气/空气针-环式介质阻挡放电发射光谱诊断

为了更加深入地了解氩气/空气等离子体射流内的电子输运过程及化学反应过程,通过针-环式介质阻挡等离子体发生器在放电频率10 kHz,一个大气压条件下对氩气/空气混合气进行电离并产生了稳定的等离子体射流。通过发射光谱法对不同峰值电压下氩气/空气等离子体射流的活性粒子种类、电子激发温度及振动温度进行了诊断。结果表明,射流中的主要活性粒子为N₂的第二正带系、Ar Ⅰ原子以及少量的氧原子,其中N₂的第二正带系的相对光谱强度最强、最清晰,在本试验的发射光谱中没有发现N+₂的第一负带系谱线,这说明在氩气/空气等离子体射流中几乎没有电子能量高于18.76 eV的自由电子。利用Ar Ⅰ原子激发能差较大的5条谱线做最小二乘线性拟合对等离子体射流的电子激发温度进行了计算,得到大气压氩气/空气等离子体射流的电子激发温度在7 000~11 000 K之间。随峰值电压的增大,电子激发温度表现出先增大后减小的变化趋势,这说明电子激发温度并不总是随峰值电压的增长单调变化的。通过N₂的第二正带系对等离子体振动温度进行了诊断,发现大气压氩气/空气等离子体射流振动温度在3 000~4 500 K之间,其随峰值电压的增大而减小,这意味着虽然峰值电压的提高可有效提高自由电子的动能,但当电子动能较大时自由电子与氮分子之间的相互作用时间将会缩短,进而二者之间的碰撞能量转移截面将会减小,从而导致等离子体振动温度的降低。