微量样品制样时不灼烧、不称重量、不固定体积对XRF分析结果的影响

XRF法分析毫克量级的微量试样,采用不灼烧、不称重量、不固定体积的制样方法,并与灼烧、称重量、固定体积的制样方法比较,分析结果非常接近。文中还讨论了此法用于实际样品分析应注意的几个问题。

XRF聚酯薄膜-薄纸片法测定微量稀土元素

本方法是用贴在聚酯薄膜上的薄纸片来控制样品面积和富集被测元素,可用于绝对量的X射线荧光光谱分析,可测定比普通滤纸片法要求溶液浓度低50—100倍的样品溶液。该方法使用计算机进行谱线干扰校正、背景扣除,并使用最小二乘法进行线性回归。此方法具有快速、简便、灵敏、准确的特点。

The formation mechanism of low leaching glassy slag during plasma arc vitrification treatment of fly ash

In this paper, the glass formation theory is applied to study the formation mechanism of the low leaching glassy slag during the process of plasma waste treatment. The research shows that SiO2 acts as network former to form a 3-dimensional Si-O tetrahedral network in which heavy metals are bonded or encapsulated, so the Si-O tetrahedron protect heavy metals against leaching from the vitrified slag or acid corrosion. For given chemical compositions of waste, the formation ability of the vitrified slag can be represented by the ratio of the whole oxygen ions to the whole network former ions in glass (O/Si) which is appropriate in the range of 2~3. A plasma arc reactor is used to conduct the vitrification experiments of two kinds of fly ashes with additives in which effects of various parameters including arc power, cooling speed, treatment temperature are studied. The chemical compositions of fly ashes are analyzed by X-ray fluorescence (XRF) spectrometry. The experimental results show that both cooling speed and O/Si have important influence on the formation of the vitrified slag, which is qualitatively in accordance with the predictions of the glass formation theory.

THE FORMATION MECHANISM OF THE VITRIFIED SLAG IN A PLASMA ARC REACTOR FOR HAZARDOUS WASTE TREATMENT

Various hazardous wastes with additives have been vitrified to investigate the formation mechanism of the glassy slag by a 30 kW DC plasma-arc reactor developed by the Institute of Mechanics, Chinese Academy of Sciences. The average temperature in the reaction area is controlled at 1500°C. The chemical compositions of three sorts of fly ashes are analyzed by XRF (X-Ray Fluorescence). Fly ashes with vitrifying additives can be vitrified to form glassy slag, which show that the ratio of the whole oxygen ions to the whole network former ions in glass (R) is appropriate in the range of 2~3 to form durable vitrified slag. In this experiment, the arc power is controlled below 5 kW to inhibit waste evaporation. To enhance the effects of heat transfer to wastes, ferrous powder has been added into the graphite crucible, which aggregates as ingot below the molten silicate after vitrification. The slag fails to form glass if the quenching rate is less than 1 K/min. Therefore, the slag will break into small chips due to the sharp quenching rate, which is more than 100 K/sec.

X射线荧光光谱分析方法的研究

本工作研究了X荧光光谱进行痕量元素分析，谱线重迭干扰校正及基体效应的校正方法，共分六个部分。一．X荧光光谱滤纸片法分析痕量稀土元素。为了降低XRF滤纸片法的检出限，分析痕量稀土，我们对XRF的制样方法，标准工作曲线的制作，谱线干扰校正，背景扣除等进行研究，将滤纸片法应用到分析痕量稀土，方法准确可靠、快速、简便，测定精度优于1％，检出限为0.X-X微克，特别适合萃取分离流程中低含量稀土的测定。二．XRF中谱线重迭干扰的校正方法。在J. L. Brandle 假定合成峰的强度是各了成份的线性迭加的基础上，引入非零截距，提出了用线性规划法校正稀土元素谱线重迭的方法，其中R_i为第i个元素衍射角（20）处测量的谱线强度，C_i为浓度，K_(ij)为衍射角处的特性常数。通过实验求出K_(ij)，然后求出在[1]式约束条件下，使目标函数E = Σ from i=1 to n|Σ from j=1 to n of (k_(ij)(j+b_i)-R_i|(i,j=1,…n)为最小的C_i值。为了证明方法的有效性，实验中选用了干扰较大的分析线。本文对Eu Lβ, (56.96°)和Dy Lα_1 (56.58°)；Ho Lβ_1, (48.28°)，和Lu Lα, (47.40°)；Ho Lα, (54.52°)和Gd Lβ_1, (54.56°)的谱峰重迭进行校正，取得满意结果。三．XRF测定土壤中痕量铬钒时谱线干扰校正方法：在研究了薄样中稀土元素谱线重迭问题的同时，还研究了土壤直接压片时，Cr的K_α线(69.35°)和V的K_β线（69.12°）的谱线重迭问题。由于Cr的K_α线和V的K_β均处于铁的K系吸收限的长波侧，铁的基体效应是不可忽略的。同时，由于谱线的相互重迭，使得元素间不存在简单的线性关系，本文提出一种新的数模来校正Cr和V的谱线干扰及Fe的基体效应：C_i = K_0 + K_1R_1 + K_2R_2 + K_3R_3 + K_4R_1~2 + K_5R_1R_2 + K_6R_1R_3 + K_7R_2~2 + K_8R_1R_3 + K_9R_3~2 其中C_i(i = 1,2)分别为Cr, V 的浓度，单位为ppm；R_i(i = 1,2,3)分别为Cr、V和Fe的峰／背比值，K_i(i = 0,…,9)为参数。通过几种常用校正模型的比较表明，本文所提模型的剩余标准差最小。说明由于该模型同时考虑了基体的影响及谱线重迭而产生的非线性影响因素，用交叉项表示非线性项，对谱线重迭及基体效应的校正是有效的。四．土壤中常量元素的XRF测定：在XRF中，选择影响元素，解决元素间的基体效应是极其重要的问题。一般采用Plesch判据来选择影响元素，但该法需要知道主要基体和干扰元素对分析元素的质量吸收系数及干扰元素含量变化范围。本文采用逐步回归方法，对共存元素进行筛选，根据每个共存元素对分析元素的方差贡献大小选择影响元素，并以散射内标与经验系数相结合校正基体效应的影响。同时，对几种常用的经验校正模型进行比较。利用最小剩余标准作为判据。结果表明，几种常用的数模没有明显差别，当分析范围比较窄时，强度模型较好，当分析范围宽时，浓度模略优。同时用微型计算机，以基本参数法和若干标样，直接与X荧光谱仪进行联机分析，显示了基本参数法和经验系数法相结合解决实际问题的优越性。五．土壤中十三种痕量元素的XRF测定：用逐步回归方法选择基体元素，以散射内标和强度校正模型分析了土壤中十三种痕量元素。六．土壤中Cu、Zn、Rb、y的XRF测定：以相干／非相干散射之比为内标分析了Cu、Zn、Rb和y, 并考察了基体的影响，对参考标样的分析结果表明，结果满意。

Enhancement on the hydrothermal stability of ZSM-5 zeolites by the cooperation effect of exchanged lanthanum and phosphoric species

It was explored by density functional calculations that exchanged La or P species exert great influence on the local Al sites as well as on the adjacent exchanged species. In partially exchanged La- or P/H-ZSM-5 zeolite, some of the Al sites will fall off from the zeolite framework even more easily than in H-form ZSM-5, consistent with our XRF experiments. However, when exchanged by both La and P species, Al at either of the two exchanged sites shows better stability compared to H-from. zeolite. La and P species will interact strongly with each other, as evidenced by the charge donation process and the shortening of P-O-1 bond length. It was just the cooperation of La and P species that enabled RSCC catalysts worked normally under severe conditions. (C) 2004 Elsevier B.V. All rights reserved.

Difference of ZSM-5 zeolites synthesized with various templates

ZSM-5 zeolites with similar SUM ratio were synthesized successfully using various templates (n-butylamine (BTA), ethylamine (ETA), isopropylamine (IPA), ethylenediamine (EDA), ethanol (ETL), ethanol-ammonium (ETL-AM) and no template (NT)) under hydrothermal conditions. The samples were characterized by XRD, SEM, XRF, NH3-TPD and BET surface area measurements in order to understand the template effects and the differences of the ZSM-5 samples. The synthesis of ZSM-5 with organic templates was relatively easier than those with inorganic templates and without template. SEM results revealed that ZSM-5 synthesized with different templates had different morphology and particle size. The Si/Al ratio and BET specific surface area of the sample with ethanol as template was the lowest. NH3-TPD results showed that the sample synthesized without template had fewer strong acid sites than others. n-Hexane cracking reaction was carried out over the samples to evaluate the catalytic properties. All ZSM-5 zeolites were effective in n-hexane cracking reaction, especially for the sample synthesized without template. (C) 2004 Elsevier B.V. All rights reserved.

Characterization of metal-containing molecular sieves and their catalytic properties in the selective oxidation of cyclohexane

Three types of metal-containing molecular sieves with AFI, AEL and CHA structures (Me = Co, Mn, Cr and V) were synthesized hydrothermally and characterized by XRD, XRF, TG, TPR, NH3-TPD and FT-IR. It was revealed that metals were incorporated into the framework of molecular sieves and induced the presence of charge centers. Both cobalt and manganese in the framework of AIPO-5, AlPO-11 and SAPO-34 were not reducible before the structure collapse. The redox behaviours of these catalysts in cyclohexane oxidation at 403 K using O-2 as oxidant were examined. CoAPO-11 exhibited best activity and good selectivities for the monofunctional oxidation products (88.5%). Cyclohexanol was the major product over most catalysts, whereas for Cr-containing molecular sieves, high selectivity of cyclohexanone was observed. Investigation of reaction mechanism based on CoAPO-11 and CrAPO-5 catalysts indicated that the decomposition of cyclohexyl hydroperoxide (CHHP), the intermediate in cyclohexane oxidation, followed the pathway: cyclohexanone <-- CHHP --> cyclohexanol -->cyclohexanone. (C) 2004 Elsevier B.V. All rights reserved.

A facile and effective method for the distribution of Mo/HZSM-5 catalyst active centers

Post-steaming treatment of Mo/HZSM-5 catalysts results in more molybdenum species migrating into and residing in the HZSM-5 zeolite channels. This is confirmed by XRF and XPS measurements. H-1 MAS NMR and Si-29 MAS NMR also demonstrate that the number of free Bronsted acid sites decreases in the Mo/HZSM-5 catalysts that underwent post-steaming treatment, compared to untreated Mo/HZSM-5 catalysts. As a result, the deactivation rate constant (kd) on the Mo/HZSM-5 catalyst after post-steaming treatment for 0.5 h is much smaller, and the catalyst therefore shows remarkable stability in the probe reaction of methane dehydro-aromatization. The results suggest that a more beneficial bi-functional balance between active Mo species for methane activation and acid sites for the following aromatization is developed over those Mo/HZSM-5 catalysts that have experienced post-steaming treatment for 0.5 h, in comparison with the untreated Mo/HZSM-5 catalysts.

Crystallization and Si incorporation mechanisms of SAPO-34

In this study of the synthesis of SAPO-34 molecular sieves, XRD, SEM, XRF, IR and NMR techniques were applied to monitor the crystalloid, structure and composition changes of the samples in the whole crystallization process in order to get evidence for the crystallization as well as Si incorporation mechanism of SATO-34. XRD results revealed that the crystallization contained two stages. In the first 2.5 h (the earlier stage), high up to similar to80% of relative crystallinity could be achieved and the crystal size of SAPO-34 was almost the same as that of any longer time, indicating a fast crystallization feature of the synthesis. In this stage, IR revealed that the formation of SAPO-34 framework structure was accompanied by the diminution of hydroxyls, suggesting that crystal nuclei of SAPO-34 may arise from the structure rearrangement of the initial gel and the condensation of the hydroxyls. NMR results reveal that the template and the ageing period are crucial for the later crystallization of SAPO-34. Preliminary structure units similar to the framework of SAPO-34 have already formed before the crystallization began (0 h and low temperature). Evidence from IR, NMR, and XRF shows that the formation of the SAPO-34 may be a type of gel conversion mechanism, the solution support and the appropriate solution circumstance are two important parameters of the crystallization of SAPO-34. Meanwhile, NMR measurements demonstrated that about 80% of total Si atoms directly take part in the formation of the crystal nuclei as well as in the growth of the crystal grains in the earlier stage (<2.5 h). Evidence tends to support that Si incorporation is by direct participation mechanism rather than by the Si substitution mechanism for P in this stage (<2.5 h). In the later stage (>2.5 h), the relative content of Si increased slightly with a little decrease of Al and P. The increase of Si(4Al) and the appearance of the Si(3Al), Si(2Al), Si(1Al) and Si(OAl) in this stage suggest that substitution of the Si atoms for the phosphorus and for the phosphorus and aluminum pair takes place in the crystallization. The relationship among structure, acidity and crystallization process is established, which suggests a possibility to improve the acidity and catalytic properties by choosing a optimum crystallization time, thus controlling the number and distribution of Si in the framework of SAPO-34. (C) 2002 Elsevier Science Inc. All rights reserved.

稀土元素的X射线荧光光谱分析

近十年来,国内外的稀土元素X射线荧光光谱分析工作有了很大进展。随着稀土应用的日益广泛,XRF不仅是常量稀土分析手段,也已用于微量和痕量稀土分析。本文着重在样品的预富集,制样技术,仪器条件,校正谱线干扰以及消除基体效应的数学校正法等方面做了阐述。

渤海近代沉积物的古地磁与古环境研究

本论文的主要实验测量工作可分为古地磁学与地球化学二大部分。在古地磁学方面。对JX91-2A（168），JX91-2B（80），JX91-3A（66）和JX91-3B（137）共451个样品进行了天然剩磁（NRM）及交变退磁测量，还进行了磁化率及磁化率各向异性的测量。对JX91-2A，JX91-2B和JX91-3A开展了岩石磁学研究，测量了非粘滞性剩磁（ARM），等温剩磁（ARM），饱和等温剩磁（FIRM）以及个别样品的FIRM衰减曲线，对JX91-3B求出了中间破坏强度（MDF）。在地球化学方面，对JX91-2A（79），JX91-3B（67），JX91-3m(50)和JX91-4G（27）共223个样品进行了X光萤光（XRF）分析。包括10种主要元素及21种向量元素，以及X光衍射（XRD）分析。还对JX91-2A进行了有机碳、微体古生物学及稳定碳氧同位素分析；对JX-91-3B进行了~（210）Pb 测量。另外还对此四岩芯测定了含水量及粒度分布等。所有实验数据都用计算机进行了分析处理，并做了广泛的多学科综合对比研究。在充分借鉴前人成果的基础上，本论文就以下四个方面的问题得到了一点新的认识。一、渤海黄河口外的浊流系统及浅水浊流沉积。这一浊流系统的存在具有多方面的证据。二、渤海沉积物的高精度年代学。对于渤海中央盆地沉积物主要采用了全新世以来的海平面变化曲线及古地磁场强度曲线确定年代，定出JX91-2A底部年代为距今8，500年。三、古地磁记录改正方法及渤海地区古地磁长期变样本曲线的建立。四、渤海古环境综合分析及黄河全新世以来的河道变迁。

新疆东昆仑蛇绿岩岩石学、地球化学特征及其大地构造意义

The East Kunlun area of Xinjiang (briefly EKAX) is the western part of broadly speaking East Kunlun orogenic zone. The absence of geological data (especially ophiolites) on this area has constrained our recognition to its geology since many years. Fund by National 305 Item (96-915-06-03), this paper, by choosing the two ophiolite zones (Muztag and Southwestern Margin of Aqikekule Lake ophiolite zones) exposed at EKAX as the studied objects and by the analysis of thin section, electron probe, XRF, ICP-MS, SEM and Sm-Nd isotope, totally and sys ematically dealt with the field geological, petrological, minerological, petrochemical and geochemical characteristics (including trace, rare earth element and Sm-Nd isotope) and the tectonic setting indicated by them for each ophilite zone. Especially, this paper discussed the trace and rare earth element patterns for metamorphic peridotites, their implications and related them to the other components of ophiolite in order to totally disclose ophiolite origins. Besides, this paper also studied the petrological, geochemical and paleobiological characteristics for the cherts coexsisted with the Muztag ophiolite and the tectonic setting indicated by them. Based on these, the author discussed the tectonic evolution from Proterozoic to Permian for this area. For Muztag ophiolite, their field geological, petrological, minerological, petrochemical and geochemical characteristics show that: ① outcropped along the Muztag-Jingyuhu fault with west-to-east strike, the ophiolite is composed of such three components as metamorphic peridotites, cumulates and volcanic rocks; ② metamophic peridotites consist of such types as lherzolites, serpentinized lherzolites and serpentinites, only pyroxenites is seen of cumulates and volcanic rocks include basalts, basaltic andesites and andesites; ③ mineralogical data on this ophiolite suggest it formed in supra-subduction zone (SSZ)environment, and its mantle wedge is heterogeneous; ④ whole-rock TiO_2 and Al_2O_3 of metamorphic peridotites indicate their original environment with the MORB and SSZ characteristics; ⑤ metamorphic peridotites have depleted LREE and flat REE patterns and volcanic rocks have enriched LREE patterns; ⑥ trace element characteristics of metamorphic peridotites imply that they had undergone Nb and Ta enrichment event after partial melting; ⑦ trace element characteristics of volcanic rocks and their tectonic diagrams show they are formed in the spreading and developed island arc environment with back-arc basin, such as rifted island arc, which is supported by the ε_(Nd)(t) -2.11～+3.44. In summary, the above evidence implies that Muztag ophiolite is formed in SSZ environment, where heterogeneous mantle wedge was metasomatised by the silica-enriched melt from subducted sediments and/or oceanic crust, which makes the mantle wedge enriched again, and this enriched mantle wedge later partially melted to form the volcanic rocks. For Southwestern Margin of Aqikekule Lake ophiolite, their field geological, petrological, minerological, petrochemical and geochemical characteristics show that: ① it outcropped as tectonic slices along the near west-to-east strike Kunzhong fault and is composed of metamorphic perodotties, cumulates and volcanic rocks, in which, chromites are distributed in the upper part of metamorphic peridotites as pods, or in the lower part of cumulates as near-strata; ② metamorphic peridotites include serpentinites, chromite-bearing serpentinites, thlorite-epidote schists and chromitites, of which, chromitites have nodular and orbicular structure, and cumulates include pyroxenits, serpentinites, chromite-bearing serpentinites, chromites and metamorphically mafic rocks and only basalts are seen in volcanic rocks; ③ Cr# of chromites suggest that they formed in the SSZ and Al_2O_3 and TiO_2 of metamorphic peridotites also suggest SSZ environment; ④metamorphic peridotites have V type and enriched LREE patterns, cumulates have from strongly depleted LREE, flat REE to enriched LREE patterns with universally striking positive Eu anomalies and basalts show flat REE or slight enriched LREE patterns with no Eu anomalies; ⑤ trace element and Sm-Nd isotope characteristics of metamorphic peridotites imply their strikingly heterogeneous mantle character(ε_(Nd)(t)+4.39～+26.20) and later Nb, Ta fertilization; ⑥ trace element characteristics of basalts and their tectonic diagrams show they probably formed in the rifted island arc or back-arc basin enviromnent. In summary, the above evidence shows that this ophiolite formed in the SSZ environment and melts from subudcted plate are joined during its formation. Rare earth element, whole-rock and sedimentary characteristics of cherts with the Muztag ophiolite show that they formed in the continental margin environment with developed back-arc basin, and radiolarias in the cherts indicate that the upper age of Muztag ophiolite is early carboniferous. Based on the accreted wedge models of Professor Li Jiliang for Kunlunshan Mountain and combined with study on the two typical ophiolite profiles of EKAX, the author discussed the tectonic evolution of EKAX from Proterzoic to Permian.

内蒙古乌拉特中旗北部宝音图群研究

The Baoyintu Group, lies in Wulate-zhongqi, Inner Mongolia, is a set of medium-grade metamorphic rock series which undergoes complex deformations. It consists of pelite schist, greenschist, plagioclase amphibolite quartzite and marble. The pelite schist is the main rock type and contains the classic medium pressure metamorphic minerals. The author divided Baoyintu group into five assemblages, investigated the rock association and plotted geological section of each assemblage in this area. Based on the systemically study of structural geology, petrology, geochemistry and mineralogy, the author reconstructs the protolith, sedimentary environment and tectonic evolution, discusses the mesoscopic and microscopic structure, metamorphism, geochemistry characters and the correlation between porphyroblast growth and deformation-metamorphism. There are three phase deformations in the research area: the earliest one occurred as the Baoyintu group deformed and metamorphosed and the main structure pattern is tight fold within layers during the Dl, large scale reversed fold and two phase faults (Fl fault and F2 fault) during the D2, and superimposed fold and F3 fault during D3. The F3 trancate the Wenduermian group of Silurian. The second and third phase deformation are relate to the orogenic event of late period of early Paleozoic. According to the rock association ,characteristics of the rocks and research of geochemistry, we get some information of the sedimentary environment and tectonic evolution of Baoyintu group. The source rocks are a set of terrigenous deposits-volcanic formation which reflect the history of the tectonic setting: stable- active-restable. And there are two sedimentary cycle from first assemblage to fifth assemblage: from first assemblage to fourth assemblage is a course of progression and the fifth assemblage is a start of regression. We also get the information of the P-T-t path by studying petrographies and calculating temperature and pressure. The path is not similiat to any classic type. And the interpretation is different from the traditional opinion. The P-T-t path reflects the dynamic course of convergence and uplift, magma underplating, back-arc extension and convergence of continental margin. Applying the theory of deformation partitioning to this area, the author discuss the relationship between deformation and porphyroblast growth, and get the conclusion of the sequence of deformation and metamorphism. At the first time we measure the distribution of chemical composition within the porphyroblast by XRF, confirm the theory of deformation partitioning quantitative and get new understanding about growth phase of porphyroblast and growth mode of porphyroblast: porphyroblast grow in the manner as "rose flower", the growth is controlled by the deformation. The elements distribution in porphyroblast reflects the growth manner and indicate history of metamorphism and deformation. So, we can deduce the metmorphism and deformation from the elements distribution in porphyroblast.

个旧岩浆杂岩地质地球化学及成因研究

燕山中晚期，个旧岩浆活动强烈，并形成基性、中性、酸性及碱性杂岩体。对此前人已做过很多工作，但对其成因机制并未做详细探讨。本文以神仙水花岗岩、卡房花岗岩及贾沙辉长-二长岩为研究对象采用XRF、ICP-MS、EMPA-1600等分析测试方法，对个旧岩浆杂岩体的元素地球化学特征做了详细的分析和总结，并初步得出以下结论： 1、贾沙辉长-二长岩富集LILE、LREE，相对亏损HREE，并具有富碱特征和Eu的弱负异常，说明其为富集地幔来源；但与OIB相比，具有Nb、Ta、Ti等元素的亏损，说明其受到地壳混染作用。 2、个旧花岗岩普遍具有高硅、高铝、富碱（尤其富钾）等特征。随着SiO2含量的增加，Al2O3、Fe2O3T、MgO、CaO、TiO2、P2O5的含量呈线性降低；当SiO2含量大于70%时，Na2O和K2O含量变化不大。 3、岩石类型上，个旧各花岗岩体的铝质系数A/CNK值为0.92～1.08，属于I型花岗岩；构造环境上，个旧花岗岩形成于大陆碰撞环境，为碰撞晚期或后碰撞构造环境；其主要成分来源于地壳，并有基性成分和酸性成分的混合特征。 4、初步研究表明，个旧花岗岩形成于与玄武质岩浆底侵有关的下部大陆壳重熔作用。