Nd-Fe-B-Si合金的研究

为了探索提高Nd-Fe-B磁性材料的居里温度T_C,我们采用了与文献不同的组成和制 条件,研究了Si对合金的物相、T_C等的影响,得出Nd-Fe-B-Si是一种有希望的非钴高居里温度合金体系. 试样系以钕铁、硅铁、硼铁和还原铁粉为原料,按 Nd_(15)Fe_(77-x)Si_xB_8(x=4、8、16、18 at％)配比,在石墨电阻炉内于Ar气保护下熔炼而成.T-σ曲线在日本MB-2型磁天平上测得;微区分析和x-射线衍射分别用JXA-840扫描电镜和日本理学2028x-射线衍射仪进行.

甲醇氨氧化合成氢氰酸Fe-Mo氧化物催化剂的研究

利用固定床反应器,研究了 Fe-Mo 氧化物/载体催化剂对甲醇氨氧化制氢氰酸的催化性能,考察了催化剂组成和反应条件(如温度)对催化活性的影响。氢氰酸的单程收率可达94%。发现催化剂的活性与表面酸性有关。活性相的结构为 Fe_2(MoO_4)_3。

萃取-非水介质氢化物发生-ICP-AES中的干扰及Ni-Fe基合金的分析

本文结合溶剂萃取研究了非水介质中氢化物发生-ICP-AES的分析条件、干扰等因素的影响。利用KI~+H_2SO_4/MIBK萃取体系将As,Sb,Bi萃取到MIBK中而与基体元素分离,然后将该有机相与甲酸按等体积混合后,即可直接进行氢化物发生-ICP-AES分析。还对影响萃取和氢化物发生的一些因素及共存元素的干扰进行了讨论。该方法应用于Ni-Fe基合金中As和Sb的分析,取得了较满意的结果。

电活性质点Fe~(2+)离子在六氰亚铁钒薄膜中的传输

电活性质点Fe~(2+)可穿透六氰亚铁钒薄膜在玻璃碳基体电极表面于较负电位处直接氧化,也可经VHF膜中氧化还原点位的媒介在较正电位处于膜-溶液界面及膜内部发生催化氧化.两个过程分别在用VHF修饰过的旋转GC电极上的伏安曲线中产生,可明确分辨的第一波和第二波.第一波的极限电流受Fe~(2+)离子在溶液中和膜中的扩散速率控制.VHF薄膜对Fe~(2+)离子的透过能力,kD_m/d,为10~(-3)-10~(-2)cm·s~(-1)数量级,随膜厚度增大而减小,不随溶液中Fe~(2+)离子浓度改变.

He, Ne and Ar isotopic composition of Fe-Mn crusts from the western and central Pacific Ocean and implications for their genesis

The noble gas nuclide abundances and isotopic ratios of the upmost layer of Fe-Mn crusts from the western and central Pacific Ocean have been determined. The results indicate that the He and Ar nuclide abundances and isotopic ratios can be classified into two types: low He-3/He-4 type and high He-3/He-4 type. The low He-3/He-4 type is characterized by high He-4 abundances of 191x10(-9) cm(3.)STP(.)g(-1) on average, with variable He-4, Ne-20 and Ar-40 abundances in the range (42.8-421)x10(-9) cm(3.)STP(.)g(-1), (5.40-141)x10(-9)cm(3.)STP(.)g(-1), and (773-10976)x10(-9) cm(3.)STP(.)g(-1), respectively. The high He-3/He-4 samples are characterized by low He-4 abundances of 11.7x10(-9) cm(3.)STP(.)g(-1) on average, with He-4, Ne-20 and Ar-40 abundances in the range of (7.57-17.4)x10(-9) cm(3.)STP(.)g(-1), (110.4-25.5)x10(-9) cm(3.)STP(.)g(-1) and (5354-9050)x10(-9) cm(3.)STP(.)g(-1), respectively. The low He-3/He-4 samples have He-3/He-4 ratios (with RIRA ratios of 2.04-2.92) which are lower than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (447-543) which are higher than those of air (295.5). The high He-3/He-4 samples have He-3/He-4 ratios (with R/R-A ratios of 10.4-12.0) slightly higher than those of MORB (R/R-A=8 +/- 1) and Ar-40/Ar-36 ratios (293-299) very similar to those of air (295.5). The Ne isotopic ratios (Ne-20/Ne-22 and Ne-21/Ne-22 ratios of 10.3-10.9 and 0.02774-0.03039, respectively) and the Ar-38/Ar-36 ratios (0.1886-0.1963) have narrow ranges which are very similar to those of air (the Ne-20/Ne-22, Ne-21/Ne-22, Ar-38/Ar-36 ratios of 9.80, 0.029 and 0.187, respectively), and cannot be differentiated into different groups. The noble gas nuclide abundances and isotopic ratios, together with their regional variability, suggest that the noble gases in the Fe-Mn crusts originate primarily from the lower mantle. The low He-3/He-4 type and high He-3/He-4 type samples have noble gas characteristics similar to those of HIMU (High U/Pb Mantle)- and EM (Enriched Mantle)-type mantle material, respectively. The low He-3/He-4 type samples with HIMU-type noble gas isotopic ratios occur in the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain and the Mid-Pacific Seamounts whereas the high He-3/He-4 type samples with EM-type noble gas isotopic ratios occur in the Line Island Chain. This difference in noble gas characteristics of these crust types implies that the Magellan Seamounts, Marcus-Wake Seamounts, Marshall Island Chain, and the Mid-Pacific Seamounts originated from HIMU-type lower mantle material whereas the Line Island Chain originated from EM-type lower mantle material. This finding is consistent with variations in the Pb-isotope and trace element signatures in the seamount lavas. Differences in the mantle surce may therefore be responsible for variations in the noble gas abundances and isotopic ratios in the Fe-Mn crusts. Mantle degassing appears to be the principal factor controlling noble gas isotopic abundances in Fe-Mn crusts. Decay of radioactive isotopes has a negligible influence on the nuclide abundances and isotopic ratios of noble gases in these crusts on the timescale of their formation.

Formation of Fe-oxyhydroxides from the East Pacific Rise near latitude 13 degrees N: Evidence from mineralogical and geochemical data

The mineralogical and geochemical characteristics of Fe-oxyhydroxide samples from one dredge station (long. 103 degrees 54.48'W, lat. 12 degrees 42.30'N, water depth 2655 m) on the East Pacific Rise near lat 13 degrees N were analyzed by XRD, ICP-AES, and ICP-MS. Most Fe-oxyhydroxides are amorphous, with a few sphalerite microlites. In comparison with Fe-oxyhydroxides from other fields, the variable ranges in the chemical composition of Fe-oxyhydroxide samples are very narrow; their Fe, Si, and Mn contents were 39.90%, 8.92%, and 1.59%, respectively; they have high Cu (0.88%-1.85%) and Co (65x10(-6)-704x10(-6)) contents, and contain Co+Cu+Zn+Ni > 1.01%. The trace-element (As, Co, Ni, Cu, Zn, Ba, Sr) and major-element (Fe, Ca, Al, Mg) contents of these samples are in the range of hydrothermal sulfide from the East Pacific Rise near 13 degrees N, reflecting that this type of Fe-oxyhydroxide constitutes a secondary oxidation product of hydrothermal sulfide. The Fe-oxyhydroxide samples from one dredge station on the East Pacific Rise near 13 degrees N are lower in Sigma REE (5.44x10(-6)-17.01x10(-6)), with a distinct negative Ce anomaly (0.12-0.28). The Fe-oxyhydroxide samples have similar chondrite-normalized rare-earth-element (REE) patterns to that of seawater, and they are very different from the REE composition characteristics of hydrothermal plume particles and hydrothermal fluids, showing that the REEs of Fe-oxyhydroxide are a major constituent of seawater and that the Fe-oxyhydroxides can become a sink of REE from seawater. The quick settling of hydrothermal plume particles resulted in the lower REE content and higher Mn content of these Fe-oxyhydroxides, which are captured in part of the V and P from seawater by adsorption. The Fe-oxyhydroxides from one dredge station on the East Pacific Rise near 13 degrees N were formed by secondary oxidation in a low temperature, oxygenated environment. In comparison with the elemental (Zn, Cd, Pb, Fe, Co, Cu) average content of hydrothermal sulfide samples from the East Pacific Rise near 13 degrees N, the Zn, Cd, and Pb contents of the Fe-oxyhydroxides are lower, and their Fe, Co, and Cu contents are higher.

Microstructure and wear properties of laser clad Fe based amorphous composite coatings

A FeNiSiBV amorphous composite coating was developed by laser cladding of metallic powders on AISI 1020 low carbon steel substrate. The coatings were studied using X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The coating reveals different microstructures along the depth of the coating. The transition zone exhibits good metallurgical bonding between the substrate and the coating. The layer consists of amorphous phase in majority and nanocrystalline phase/crystalline phase in minority. Accompanied with the nanocrystalline phase, the amorphous phase is concentrated in the middle of the coating. The crystalline phase in the coating is identified as Fe2B. A gradient distribution of the microhardness ranges from 1208 HV0.2 to 891 HV0.2 in the coating along the depth. The coating shows higher microhardness and better wear property than the substrate.

华北克拉通新生代玄武岩携带的地幔橄榄岩Fe同位素地球化学及含金云母地幔岩岩石学研究

In recent years, thanks to the improvement of analytical methods and the use of MC-ICP-MS, Fe isotope can be measured precisely. Fe isotope shows considerable variation both in biological and inorganic processes (from low T to high T) in nature, Therefore, Fe isotope has become one of the exciting frontier sciences and has favorable prospects of the application to the geosciences and life sciences. Based on a comprehensive review of available references in the related field, this study focuses on the development of techniques for high-precision measurement of iron isotope using MC-ICP-MS, and application of the techniques developed to study the Fe isotopes as well as major and trace element compositions of minerals (Ol, Opx, Cpx and Sp) from spinel peridotitic xenoliths from Cenozoic alkaline basalts to investigate Fe isotopic features of the lithospheric mantle beneath the North China Craton. The minerals from these xenoliths are similar to those off-cratonic peridotites world-wide, but are remarkably different from those on-cratonic peridotites and clinopyroxenes from these spinel lherzolites exhibit two types of chondrite-normalized REE patterns i.e. LREE-depleted and flat or spoon-shaped. It is noted that total abundances of REE in clinopyroxenes from these peridotites show a broad negative correlation with Cr# numbers of Cpx and Sp. The Fe isotope results show that the spinel peridotitic xenoliths have small but distinguishable Fe isotopic variations in minerals (generally Ol < Opx < Cpx) and samples, and the isotopic range in spinel is relatively large. Positive linear relationship with the ε57Fecpx/ε57Feopx ratio close to one unit has been observed between Fe isotopes of coexistent Opx and Cpx, indicating that the Cpx and Opx have generally reached Fe isotopic equilibrium. However, Fe isotopes between the Ol and Sp show apparent disequilibrium. The broadly negative correlation between mineral Fe isotopes and oxygen fugacity (fo2), metasomatic indexes such as spinel Cr#, (La/Yb) N and (La/Sm) N ratios of clinopyroxenes suggest that Fe isotopic variations in different minerals and peridotites were probably produced by melt-peridotite interaction. This study further confirms the previous observation that the lithospheric mantle has distinguishable and heterogeneous Fe isotopic variations at a scale of xenoliths. Mantle metasomatism that induces the interaction of the lithospheric mantle peridotite with metasomatic agent is a most potential mechanism for the Fe isotope fractionation in mantle peridotites. Therefore, Fe isotope could be a new and powerful tool to probe the evolution of the lithospheric mantle. We also report mineral compositions, clinopyroxene trace element concentrations and Sr-Nd isotopes for newly-discovered phlogopite-bearing spinel lherzolite and olivine clinopyroxenite xenoliths from three different localities （Hannuoba, Hebei Province; Jining Sangyitang, Inner Mongolia; Hebi, Henan Province）of the North China Craton. Systematic comparisons with phlogopite-free spinel lherzolite xenolith from the same locality reveals that the phlogopite-bearing peridotitic xenoliths have relatively higher Al2O3, CaO, Na2O, K2O, TiO2 contents and lower MgO contents than those phogopite-free counterparts. The former also has higher LREE concentrations, but relatively less radiogenic Sr-Nd isotopic ratios. This demonstrates that mantle metasomatism can not only enrich the basaltic components and trace element concentrations, but also make a decrease in Mg# of the peridotites and olivines and a relative depletion in Sr-Nd isotopes. 87Rb/86Sr-87Sr/86Sr isochrons of the phlogopite-bearing xenoliths indicate that mantle metasomatism happened in the Mesozoic and/or Cenozoic time. The metasomatic agent was derived from the asthenosphere. The result also manifests that the widespread similarity of the geochemical features such as major and trace elements and isotopic compositions in the Cenozoic lithospheric mantle beneath the North China Craton to those “oceanic” lithospheric mantle could be as a result of the ubiquitous presence of the interaction between the old refractory peridotites and the infiltrated asthenospheric melt, rather than the actually newly-accreted lithospheric mantle.

内蒙古白云鄂博地区元古宙构造-岩浆演化史与超大型REE-Nb-Fe矿床成因

Bayan Obo giant REE-Nb-Fe deposit in the northen margin of the North China Craton (NCC) is well known in the world for its abundant rare earth element resources. There is nearly one hundred year of studying history in substance component, chronology and geochemistry of the ore deposit, since the main ore body was found in 1927. However, there still exist remarkable divergences in genesis, mineralized age and material origin. Especially the REE enrichment mechanism leaves us a secret. Recent research shows that the Bayan Obo ore deposit likely resulted from the carbonatite magma activity, which is a favorable factor for REE accumulation. Based on the analysis of tectonic evolution history of north margin of NCC this thesis mainly discussed the formation background of cratonic margined rifts in Bayan Obo, and presented the analytical results of formation environment, intrusion age and deep origin of Proterozoic carbonatite magma. These research results can provide evidence for ore genesis. LA ICP-MS U-Pb dating on zircon shows that the Neoarchean basement was mainly composed of calc-alkaline TTG gneisses (2588±16Ma). The collision orogeny movement of the northen margin of the NCC between 2.0 Ga to 1.9 Ga brought the swarm of diorite-granodiotite magma (2023±16Ma) and intense regional metamorphism event (1906.3±7.7 Ma to 1892.7±6.7 Ma). In the sequent super continent break up background, intense metamorphic and deformed basement complex was uplifted to the surface suffered denudation, forming Mesoproterozoic Bayan Obo group in the contemporary continental margin rifts. The uplift of basement complex and formation of continental rifts were likely related with mantle plume activity. Evidence from petrological and geochemical data suggests that abundant alkaline-basic magma resulted from enhancement of continental breakup activity, that separated into carbonatite veins and mafic dykes by melt immiscibility mechanism, intruded in Bayan Obo margin rifts at the late stage of extension movement. Carbonatite veins can be divided into three main types by mineral composition: dolomite carbonatite, dolomite-calcite coexistent carbonatite and calcite carbonatite. Intrusion relationship between different types of carbonatite veins show that the calcite carbonatite veins were formed latter than the dolomite type as well as the coexistent type. Moreover, geochemical data also reveals successive and evolutive character between them. The content of REE increases together with the calcite minerals component. That is to say that REE gradually accumulated as the evolution of carbonatite magma. High precision Sm-Nd isochron data shows that the intrusion age of carbonatite veins was at 1319±48Ma. Moreover, the REE mineralization age in calcite carbonatite veins was around 1275±87Ma that is consistent with the intrusion age in error range. According to these data the abundant REE already existed in the carbonatite magma before intrusion and result in the earlier ore mineralization. The average age of mineralized dolomite was at 1353±100Ma, and the mineralization age of apatite in coarse grain dolomite was around 1329±150Ma. These data is consistent with carbonatite. Considering the coincident rare, trace element and isochron composition between them, it is presumed that mineralized dolomite was also the carbonatite intrusion and was the mainly factor for huge REE enrichment.

内蒙古白云鄂博超大型REE-Nb-Fe矿床脉状矿化时代与成矿流体特征

Bayan Obo REE-Nb-Fe ore deposit is the largest REE deposit in the world. Owing to its unique type and tremendous economic value, this deposit has widely attracted interests from geological researchers and vast amount of scientific data have been accumulated. However, its genesis, especially ore-forming age and REE sources, have been under dispute for a long time. On the basis of previous research works, this paper mainly conducts studies on the Early Paleozoic ore-forming event in the Bayan Obo deposit. The following results and conclusions can be suggested: Sm-Nd isotopic analytical results of bastnaesite, beloeilite, albite and fluorite samples from a coarse-crystalline ore lode present an isochron age of 436±35Ma. Besides, Rb-Sr isotope dating of the coarse-crystalline biotite lode that intruded into banded ores gives an isochron age of 459±39Ma. The two ages verify the exist of Early Paleozoic ore-forming event at Bayan Obo, which characterized by extensive netted mineralization of REE fluorocarbonates, aeschynite and monazite, accompanied by widely fluorite-riebeckite-aegirine-apatite alteration. Sr-Nd isotope composition of vein minerals is located between EMI and ancient lower crust component in the ISr(t)-εNd(t) correlation diagram, indicating that there is a crustal contamination during veined mineralization. A large area late Paleozoic granitoids are distributed in the southeast region of east open pit of the mine. The granitoids intruded directly into the ore-bearing dolomite, and produced intense skarnization. Moreover, at 650-660m of the drill core on 22 line and 1598m level flat in the south of East Open Pit, we firstly found skarnization rocks. Single grain and low background Rb-Sr isochrone dating on phlogopite in skarn gives 309±12Ma. Considering the intruded contacting relationship, the late Paleozoic granitoids, already extended to the under part of REE ore bodies, must be posterior to the latest intense REE mineralization, and is only a destructive tectonic and magmatic activity. Fluid inclusion types of fluorite in the Bayan Obo deposit consist of multiphase daughter mineral-bearing inclusion, two or three phase CO2-bearing inclusion and two phase aqueous inclusion. Petrography, laser Raman analysis and microthermometry study indicate that the fluids involving in REE-Nb-Fe mineralization at Bayan Obo might be mainly of H2O-CO2-NaCl-(F-REE) system. The presence of REE-carbonate as a daughter mineral in fluid inclusions shows that the original ore-forming fluids are rich in REE elements.

溶液介质条件对Fe^3＋共沉淀去除Cu^2＋的影响

采用室内试验方法，研究了溶液介质条件对Fe^3+共沉淀去除Cu^2+的影响。试验结果表明，pH是影响Fe^3+共沉淀去除Cu^2+的主要因素之一，其去除率随pH的增加而增加，并且其固液分配系数Kd的对数值与pH之间显示出较好的线性关系；天然水体中溶解的电解质离子及无机和有机配位体对Cu^2+的去除均产生很大影响，Cu^2+的去除率随加入的NaCl和NaClO4浓度的增加而降低，而随Ca(NO3)2和Mg(NO3)2浓度的增加而增加，除磷酸盐的增强作用外，硫酸钠、碳酸氢钠、甘氨酸、草酸钠、柠檬酸钠以及十二烷基苯磺酸钠的加入则不同程度地减弱了Cu^2+的去除；与Cu^2+共存的等量竞争阳离子Pb^2+、Zn^2+和Cd^2+也同样减弱了Fe^3+对Cu^2+的去除。