ICP-AES在高纯稀土氧化物分析中应用的研究Ⅶ——ICAP9000多道光谱仪用于15个稀土杂质元素同时测定的评价

前言ICP光量计(多道光谱仪)在高纯稀土氧化物分析中的应用的报导还较少,本文将在以前摄谱分析法工作的基础上,对ICAP9000型多道光谱仪的稀土通道用于La_2O_3、CeO_2、Pr_6O_(11)、Nd_2O_3、Sm_2O_3、Y_2O_3等高纯稀土氧化物或它们的杂质富集物中15个稀土杂质元素同时测定的能力(主要是校正光谱干扰效应的能力及对各稀土杂质元素的检出能力)进行评价。     

小波多尺度正交校正在近红外牛奶成分测量中的应用

光谱分析中,干扰信号的存在直接影响所建分析模型的质量。基于信号和干扰的不同特性,提出了一种扣除背景和噪声干扰的新方法——小波多尺度正交校正(WMOSC)法。首先将原始光谱进行小波变换(DWT),消除噪声及背景信息,然后采用正交信号校正(OSC)滤除与待测组分浓度无关的全部信息。与单纯的小波变换及正交信号校正相比,WMOSC能有效地扣除背景和噪声干扰,使模型具有更强的抗干扰能力,提高了模型的预测精度。利用该方法对牛奶样品的近红外光谱进行处理,采用偏最小二乘法建立校正模型,其牛奶中脂肪、蛋白质和乳糖的预测均方根误差(RMSEP)分别为0.101 6%,0.087 1%和0.110 7%。实验结果表明该方法能有效地去除干扰,保留有用信息。     

Ce_(0.8)Pr_(0.2-x)Nd_xO_(2-δ)(x=0.02,0.05,0.1)固溶体的合成与性质研究

采用溶胶-凝胶法制备了双稀土掺杂氧化铈Ce_(0.8)Pr_(0.2-x)Nd_xO_(2-δ)(x=0.02,0.05,0.1)固溶体。X射线衍射分析阐明,经800℃烧结的全部固溶体都形成了单相立方萤石结构,平均晶粒尺寸在20~25 nm之间。拉曼光谱结果阐明,固溶体Ce_(0.8)Pr_(0.2-x)Nd_xO_(2-δ)是具有氧空位的立方萤石结构,适量的掺杂Nd有利于Ce_(0.8)Pr_(0.2-x)Nd_xO_(2-δ)氧空位浓度的增加。阻抗谱结果阐明,稀土双掺杂的Ce_(0.8)Pr_(0.2-x)Nd_xO_(2-δ)比稀土单掺杂的Ce_(0.83)Sm_(0.17)O_(2-y)的电导率高,Ce_(0.8)Pr_(0.18)Nd_(0.02)O_(2-δ)的电导率最大,600℃时电导率为1.85×10~(-2)S/cm。     

傅里叶变换红外光谱的水泥生料在线分析

及时获取水泥原料中的关键成分的含量,对水泥产品的品质控制至关重要。而当前的主流分析方法需要现场人工采样和样品制备,存在时效性问题。利用傅里叶变换红外光谱技术对水泥生料样品中的Fe_2O_3, SiO_2, CaO, Al_2O_3四种关键氧化物成分的漫反射光谱进行了快速定量分析。首先探讨了傅里叶变换红外光谱技术检测水泥原料成分的理论基础。水泥原料是一种复杂混合体系,主要由铁质原料(如褐铁矿),硅质原料(如石英),钙质原料(如方解石)及铝质原料(如绿柱石)等矿物岩石组成。而这些矿物岩石在可见近红外光谱波段的特征谱带较宽,强度较低,且存在重叠的部分。因此,使用了多元校正进行定量分析。其次,设计并搭建了对应的实验系统进行水泥生料样品的成分含量分析。样品选用水泥厂家提供的60种关键成分含量各异的磨匀的水泥生料样品,成分覆盖了Fe_2O_3, SiO_2, CaO, Al_2O_3四种关键氧化物。使用搭建的实验平台采集样品的漫反射光谱。并使用了X射线荧光分析法方法测定样品中各氧化物成分含量作为参考值。之后,结合了偏最小二乘法建立了Fe_2O_3, SiO_2, CaO, Al_2O_3四种成分的定量分析模型。使用了Kennard-Stone算法将样品集按7∶3的比例分为校正集和预测集。PLS建模波段选择了4 000～5 000 cm~(-1)波数范围,总计包含520个谱元。建立了校正集中42个样品光谱与其Fe_2O_3, SiO_2, CaO, Al_2O_3成分含量的回归模型。依据交叉有效性因子Q■≥0.009 75的条件,选择了7个因子来建立最终的定量分析模型。在建立的Fe_2O_3, SiO_2, CaO, Al_2O_3四种氧化物的FTIR定量分析模型中,其校正的4种氧化物含量与X射线荧光分析法测量的含量之间的相关系数分别为98.49%, 98.03%, 98.18%, 99.24%,均方根误差分别为0.04, 0.22, 0.26, 0.08。模型的校正准确度比较高。最后使用该定量分析模型对预测集样品中的Fe_2O_3, SiO_2, CaO, Al_2O_3的含量进行预测,并与X射线荧光分析法测量的参考值进行比较。最终模型预测的相关系数分别为91.35%, 91.50%, 91.57%, 94.67%,预测的均方根误差分别为0.08, 0.45, 0.54, 0.26,表明了模型预测准确度较高。所建基于傅里叶变换红外光谱的定量分析模型为实现水泥生产控制中水泥原料成分的快速定量分析建立了基础。     

基于近红外光谱和化学计量学的驴肉鉴别方法研究

驴肉具有极高的食用价值,资源的缺乏使其价格持续走高,由此引发的欺骗和掺假亟待解决。选取了不同部位(脖子、肋板、后墩和腱子)的驴肉样品(n=167)及牛肉(n=47)、猪肉(n=51)和羊肉(n=32)样品在4 000~12 500cm-1光谱范围上建立了驴肉的近红外光谱鉴别模型。比较了马氏距离判别分析、簇类独立软模式分类法、最小二乘-支持向量机方法分别结合平滑(5点、15点及25点)、一阶和二阶微分、多元散射校正和标准归一化的光谱预处理方法对肉块样品及大中小三个不同粉碎粒径(7,5,3mm)肉糜样品的分类模型结果发现,原始光谱前11个主成分得分作为输入的马氏距离判别及前6个主成分作为输入的最小二乘-支持向量机肉块样品分类模型较优,校正集和预测集正确率分别为100%和98.96%;原始光谱前5个主成分作为输入的LS-SVM大粒径肉糜样品分类模型结果较优,校正集和预测集判别正确率为100%和97.53%;原始光谱前8个主成分得分作为输入的簇类独立软模式分类法中粒径肉糜样品分类模型结果较优,校正集和预测集的判别正确率均为100%;而对于小粒径肉糜样品,原始光谱前7主成分输入的马氏距离判别和前9主成分输入的簇类独立软模式分类法模型均得到了校正集和预测集100%的判别正确率。以上模型中的驴肉样品均得到了100%的判别正确率。研究结果表明,使用近红外光谱分析技术结合化学计量学方法鉴别驴肉是可行的。     

镨掺杂对无钴钙钛矿型氧化物BaFeO_(3-δ)电导率和透氧性能的影响（英文）

本文尝试通过镨部分取代铁来改善无钴型钙钛矿材料BaFeO_(3-δ)在室温下的结构稳定性,考察镨掺杂对材料导电及透氧性能的影响,获得新型的高性能无钴透氧膜材料.实验中通过固相反应法合成了BaFe_(3-y)Pr_yO_(3-δ)(y=0、0.025、0.05、0.075、0.1)复合粉末,并由此制得烧结体样品.XRD测试结果表明,BaFe_(3-y)Pr_y O_(3-δ)材料在镨掺杂量为(y=0.05、0.075、0.1)时仍然保持立方相,这表明掺杂Pr~(n+)有利于材料立方相结构的稳定.SEM观测表明,烧结样品中仅含有少量闭孔,说明Pr~(n+)的掺杂促进了烧结致密化.电导率和透氧率测试结果表明,900℃时,BaFe_(0.9)Pr_(0.1)O_(3-δ)的电导率和透氧率分别为6.5L/cm和1.112 mL/(cm~2.min),镨掺杂可以改善BaFe_(1-y)Pr—yO_(3-δ)材料的传导性能.高温XRD结果表明,BaFe_(0.975)Pr_(0.025)O_(3-δ)的晶体结构在700℃完全转变为立方相.BaFe0_3中Pr~(n+)对Fe~(m+)的部分取代可以稳定立方相结构,提高BaFe_(1-y)Pr_yO_(3-δ)的导电性和透氧率.     

ICP—AES法分析高纯氧化钪中十二种杂质元素

本文介绍用HCl(1 1)溶样,在基体匹配的标准曲线下测定。元素采用在适当波长处扣除背景的办法进行光谱校正,回收率达92-118%,可满足对氧化钪(Sc_2O_3)含量为99.95%的样品分析。     

电感耦合等离子体-串联质谱(ICP-MS/MS)法测定道路尘土中的铂族元素(PGEs)含量

建立了道路尘土中的铂族元素(platinum group elements,PGEs)含量测定的分析方法。道路尘土以王水(2mL HNO_3+6mL HCl)为混合消解试剂经微波消解后直接测定。在MS/MS模式下向碰撞反应池中通入氧气或氨气,分别利用氧气质量转移、氧气原位质量和氨气原位质量法消除多原子离子质谱干扰。在MS/MS模式下,分别向碰撞/反应池(CRC)中加入O_2和NH_3-He(1∶9,V/V),消除质谱干扰,采用O_2质量转移法对铑进行测定,O_2原位质量法和高氦(HeHe)法对钯进行测定,NH_3原位质量法对铑和铂进行测定。通过分析国际标准参考物质(BCR-723)验证方法的准确性和精密度,所测定结果与参考值基本一致,RSD≤7.8%,表明本方法具有良好的准确性和精密度。本方法具有前处理简单、高灵敏度、无干扰、稳定性好等优势,可用于道路尘土样品中超痕量铂、铑,钯含量的测定。     

ICP-MS法测钪的干扰研究及选冶尾矿中钪的直接测定

白云鄂博矿经选铁后,尾矿中钪含量可达0.05%,具有很高的开发利用价值。建立了一种操作简便、灵敏度高并能够准确测定尾矿及富铌渣中微量钪的电感耦合等离子体质谱(ICP-MS)测定方法。对仪器参数、试样处理方法、共存元素的干扰和消除方法进行了系统研究,选用铯、铊和铑作为内标元素,对非谱干扰加以校正。对质谱干扰研究表明,尾矿中的硼、硅、钙、锆和铝均可能对钪的测定造成质谱干扰,其中硼浓度较低(<100 μg·mL-1)时,对钪测定没有明显干扰,在测定条件下铝和钙的干扰较小,可以忽略。锆和硅的质谱干扰较严重,其中锆的干扰为双电荷(90Zr++)干扰,由于双电荷离子电离产率一般不高,锆含量低时干扰可忽略,锆的含量较高时,采用公式c′=0.021c_(Zr)-0.55对结果加以校正。硅的干扰为氧化物干扰,而硅氧键解离能大,硅的氧化物(28Si17O+,29Si16O+)稳定性高,且相关同位素丰度较大,在测定条件下干扰较严重,可以采用式c″=0.013c_(Si)+0.019扣除该影响。选择了四种不同的样品处理方式,结果表明采用HCl+HF+H₂SO₄混酸方法处理,标样测定结果与标准值一致,且能有效的克服硅和硼的质谱干扰,同时降低了测定液的含盐量,减小了非质谱干扰,标样回收率在97%~99%之间。标准样品及实际样品测定表明,采用ICP-MS法直接测定白云鄂博选冶尾矿中钪含量,结果准确,相对标准偏差小于5%,方法测定下限为0.000 1%。     

近红外光谱技术在小麦条锈病菌和叶锈病菌定性识别和定量测定中的应用

利用近红外光谱技术结合定性偏最小二乘法(DPLS)和定量偏最小二乘法(QPLS)分别实现了小麦条锈病菌和叶锈病菌的定性识别和定量测定。获取两种锈菌单一夏孢子样品各50个以及条锈病菌纯度为2.5%~100%的混合样品120个。采集样品光谱后,将两类样品均按2∶1的比例分为建模集和检验集,在4 000~10 000cm-1内采用内部交叉验证法建模。散射校正预处理方法下、主成分数为3时,定性识别模型的建模集和检验集识别准确率均为100.00%。"极差归一+散射校正"预处理方法下、主成分数为6时,定量测定模型建模集的决定系数(R2)、校正标准差(SEC)、平均相对误差(AARD)分别为99.36%,2.31%,8.94%,检验集的R2、预测标准差(SEP)、AARD分别为99.37%,2.29%,5.40%。结果表明,利用该方法对这两种锈菌定性和定量分析是可行的。本研究为植物病原菌的定性识别和定量分析提供了一种基于近红外光谱技术的新方法。     

Guided-Wave Two-Dimensional Acousto-Optic Scanner Using Proton-Exchanged Lithium Niobate Waveguide

Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs.     

Hybrid Wavelength and Code Division Multiple Access in Optical Networks

A review of schemes for multiple access in fiber optic networks shows that a hybrid of wavelength and code division multiple access (WCDMA) combines the best features of both. In particular, the hybrid scheme retains the large information carrying capacity of wavelength division multiple access (WDMA) and flexibility of code division multiple access (CDMA). In this paper WDMA, optical CDMA (OCDMA), and WCDMA networks are discussed. In OCDMA networks, concept of incoherent and coherent coding including inverse decoding and matched filter is introduced. The delay performance of both WDMA and WCDMA networks, under the simple suboptimum access protocols based on cyclic search, is computed. It has been shown quantitatively that tuning delay significantly affects the delay performance of both WDMA and WCDMA networks. Futhermore, delay performance of WCDMA networks is always better than the WDMA networks for the same tuning delay, load, and number of users.     

Effect ofγ-radiation on the spectral luminescence characteristics of impure cadmium tungstate crystals

Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·10⁴ Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.     

Femtosecond Transform-Limited Pulse Generation by Compensating for the Linear Chirp of SPM Spectra in Dispersion Shifted Fibers

A simple technique of pulse compression, based on the linear chirp compensation of self-phase modulation (SPM) spectra in dispersion shifted fibers, is demonstrated. The optimization procedure is carried out, for a short span of a single-mode fiber, using a parabolic law, which describes the behavior of the squared output pulse width versus the pump peak power in the case of Gaussian pulses. The experimental results give a minimum pulse duration of 233 fs, which is in good agreement with the model. Shorter and coherent pulses, down to 90 fs, have been obtained by inserting an interference filter at the optical output.     

Sorting of bending magnets for the SSRF booster

The Shanghai Synchrotron Radiation Facility(SSRF)booster ring,a full energy injector for the storage ring,is deigned to accelerate the electron beam energy from 150MeV to 3.5GeV that demands high extraction efficiency at the extraction energy with low beam loss rate when electrons are ramping.Closed orbit distortion(COD)caused by bending magnet field uniformity errors which affects the machine performance harmfully could be effectively reduced by bending magnet location sorting.Considering the affections of random errors in measurement,both ideal sorting and realistic sorting are studied based on measured bending magnet field uniformity errors and one reasonable combination of bending magnets which can reduce the horizontal COD by a factor of 5is given as the final installation sequence of the booster bending magnets in this paper.     

Measurement of nonlinear coefficient of optical fiber based on small chirped soliton transmission

We measure the waveform and phase curves of short optical pulses before and after transmission over different lengths of fibers by use of the pulse analyzer with the frequency-resolved optical gating (FROG),and numerically simulate pulse evolution under the experimental conditions.The nonlinear coefficient of the fiber is given by comparing the experimental results with the numerical ones.Difference between the experiment and numerical simulation is analyzed.     

Resonance scattering of canonical elastic shells in absorbing fluid medium

Resonance scattering of elastic spherical shell and cylindrical shell while the surrounding fluid medium has absorption is studied. The normal mode solution derived using exact elastic theory and the separation of variables is still applicable. However, the scattering form function has to be modified for the absorbing medium, otherwise the unreasonable result would be obtained. The backscattering form function in the absorbing medium is redefined, and the form function of elastic spherical and cylindrical shell with vacuum or solid matter filled is calculated in various absorption conditions. The results show that the absorption of surrounding fluid leads to notable attenuation of the coincidence resonances in the mid-frequency, but it has a little influence on the low-frequency resonance scattering induced by the filler inside the shell.     

Single-beam self-referenced phase-sensitive surface plasmon resonance sensor with high detection resolution

A versatile and low-cost single-beam self-referenced phase-sensitive surface plasmon resonance(SPR)sensing system with ultra-high resolution performance is presented.The system exhibits a root-mean-square phase fluctuation of ±0.0028.over a period of 45 min.i.e.a resolution of±5.2×10-9 refractive index units.The enhanced performance has been achieved through the incorporation of three design elements:a true single-beam configuration enabling complete self-referencing so that only the phase change associated with SPR gets detected,a differential measurement scheme to eliminate spurious signals not related to the sensor response,and the elimination of retardation drifts by incorporating temperature stabilization in the liquid crystal phase modulato .Our design should bring the detection sensitivity of non-labeling SPR biosensing closer to that achievable by conventional fluorescence-based techniques.     

Influences of SiO2 protective layers and annealing on the laser-induced damage threshold of Ta2O5 films

Ta2O5 films are prepared on BK7 substrates with conventional electron beam evaporation deposition.The effects of SiO2 protective layers and annealing on the laser-induced damage threshold (LIDT) of the films are investigated.The results show that SiO2 protective layers exert little influence on the electric field intensity(EFI)distribution,microstructure and microdefect density but increase the absorption slightly.Annealing iS effective on decreasing the microdefect density and the absorption of the films.Both SiO2 protective layers and annealing are beneficial to the damage resistance of the films and the latter is more effective to improve the LIDT.Moreover,the maximal LIDT of Ta2O5 films is achieved by the combination of SiO2 protective layers and annealing.