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1.
AG MP-1M阴离子分离Cu、Fe、Zn及其在Fe同位素测定上的应用 总被引：1，自引：0，他引：1
采用新型阴离子交换树脂AG MP-1M,分别以8.2 mol/L HCl+0.01%HF、4 mol/L HCl、2 mol/L HCI和0.5 mol/L HNO,可以有效分离地质样品中Cu、Co、Fe和Zn,克服了AG MP-1阴离子交换树脂分离Cu时Co随Cu同时淋洗下来,以及在分离Co含量较高的地质样品时Co和Cu需过二次柱分离的弊端.对花岗闪长岩等地质标样的研究结果表明,AG MP-1M阴离子交换树脂能有效分离Cu、Fe和Zn,并且它们的回收率均大于99%.标准样品经过离子交换分离后Fe同位素未发生分馏,可满足多接收器电感耦合等离子体质谱(MC-ICPMS)的同位素测定要求. 相似文献
2.
离子交换树脂法分离沉积物中锶和钕的影响因素研究 总被引：3，自引：3，他引：0
Sr和Nd同位素是地质学研究中经典的同位素定年和示踪体系。传统沉积物中Sr和Nd分离方法通常是利用AG50W-X8树脂分离Sr与稀土元素(REEs),再用Sr和Ln特效树脂分别对Sr和Nd纯化,但对于Fe元素含量较高的沉积物样品,该方法对REEs的洗脱率偏低,仅有50%。另外,AG50W-X8树脂高度、洗脱酸种类、Sr特效树脂淋洗酸体积以及Ln特效树脂过柱方式对Sr和Nd分离都有影响。为分析上述因素对Sr和Nd分离效果的影响,本文以水系沉积物标准物质GBW07309为例进行了研究,结果表明:(1)高含量的Fe会显著影响Sr和Nd的分离效果,而AG1-X8树脂可以有效去除Fe;(2)当AG50W-X8树脂高度为1 m L,硝酸作为洗脱酸时,Sr和REEs的分离效果较好;(3)Sr特效树脂淋洗酸中硝酸淋洗体积达到15 m L时可以有效分离Sr和Rb;(4)Ln特效树脂采用重力过柱方式时Sr和Nd分离效果较好,没有拖尾现象。本研究解决了Fe对分离Sr和Nd的干扰,K、Na、Ca、Mg、Fe、Rb、Sm去除率达到99%以上,完全满足Sr和Nd同位素分析的要求,为离子交换树脂法分离沉积物中Sr和Nd提供了较详细的前处理经验数据。 相似文献
3.
AG MP-1阴离子交换树脂元素分离方法再研究 总被引：2，自引：0，他引：2
目前不同实验室建立的用于MC-ICP-MS铜铁锌同位素测定的离子交换分离方法多适用于一般地质样品的Fe同位素高精度测定,而对于一些类似于白云鄂博Fe-Nb-REE矿床的特殊地质样品,这些分离方法的适用情况有待进一步研究。为研究REE、Nb、Ta、Co、Cu、W等元素是否能够和Fe有效分离,采用AG MP-1阴离子交换树脂,依次以6 mol/L HCl和2 mol/L HCl为介质对这些元素进行淋洗,并利用ICP-AES和ICP MS对淋洗液中的各元素含量进行测定。实验结果表明,在6 mol/L HCl介质条件下,运用AG MP-1树脂可以将REE、W与Fe有效地分离,能够将Nb、Ta的含量降低一个数量级;Fe、Co、Cu的淋洗行为和前人研究结果一致。 相似文献
4.
离子交换分离过程中铅同位素分馏评估及针对MC-ICPMS铅同位素测定的分离纯化方法的修正 总被引：1，自引：0，他引：1
本文对分离纯化样品过程中铅同位素的分馏进行了评估,并描述了适于MC-ICPMS同位素测定的分离纯化方法。利用AG1-X8阴离子交换树脂分离纯化样品中铅的过程确实导致了铅同位素的质量分馏。尽管分离纯化过程导致的铅同位素分馏程度较小(0.43‰amu-1),但明显超出了仪器的测试误差(0.23‰amu-1),如果样品中铅的回收率太低,会导致铅同位素测试值明显偏离真值。利用AG1-X8阴离子交换树脂,以0.2mL 1mol/L HBr溶液为上样介质,以5mL 1mol/L HBr和0.5mL 2mol/L HCl溶液为淋洗液,1.5mL 6mol/L HCl溶液为洗脱液,利用该分离流程可以保证获得样品中铅同位素的准确值。在本实验研究条件下,相对于过柱前样品,前期淋洗液富集铅的轻同位素(δ208Pb0),后期淋洗液富集铅的重同位素(δ208 Pb0),表明在该实验条件下,铅的重同位素组分比轻同位素更容易和树脂结合,AG1-X8阴离子交换树脂吸附铅的配分系数208 D/204 D大于1。解吸被树脂吸附铅的过程中,铅在不同络合形式间的交换反应可能导致了铅同位素的分馏效应,意味着无机络合物或者有机大分子参与反应的过程可能会导致铅同位素的分馏。 相似文献
5.
利用多接收器等离子体质谱仪(MC-ICP-MS)进行同位素组成的准确测定,必须首先对待测样品中元素进行分离纯化.目前,用于分离Mg的主要方法为阳离子树脂交换方法.然而,利用阳离子树脂不能有效除去Mg接收液中的Fe、Al,而溶液中Fe、Al会明显干扰样品中Mg同位素组成的测定.本研究结合离子交换法和共沉淀法,探讨了针对不同种类样品的Mg分离纯化方法,分离提取了实际样品中Mg并进行了同位素组成的测定.实验结果显示:①对于m(Fe)/m(Mg0.1、m(Al)/m(Mg)0.2、m(Na)/m(Mg)1的样品,经过AG50w-X12树脂一次交换分离,即可用于Mg同位素组成的测定;②对于m(Fe)/m(Mg)0.1、m(Al)/m(Mg)0.2、m(Na)/m(Mg)〉1的样品,利用AG50W-X12树脂二次交换分离,可以满足MG-ICP-MS对Mg同位素测定的要求;③对于含有m(Fe)/优(Mg)0.1、m(Al)/m(Mg)>0.2、m(Na)/m(Mg)1的样品,可先利用稀释50倍的稀氨水沉淀除去样品中的Fe、Al后,再经过AG50W-X12树脂一次交换分离,可以满足MC-ICP-MS对Mg同位素测定的要求;④对于含有m(Fe)/m(Mg)〉0.1、m(Al)/m(Mg)0.2、m(Na)/m(Mg)1的样品,可先利用稀释50倍的稀氨水滴定沉淀除去样品中的Fe、Al后,再经过AG50W-X12树脂二次交换分离,可以满足MC-ICP-MS对Mg同位素测定的要求;⑤运用所建立方法对海水和地幔样品进行了Mg的分离和同位素组成的测定,其中,青岛附近海水的同位素组成为:δ25MgDSM=-0.43‰.δ25MgDSD3=-0.84‰;葫芦岛附近海水的同位素组成为:δ25MgDSM3=-0.44‰,δ26MgDSM3=-0.85‰. 相似文献
6.
详细报道了在低分辨和高分辨模式下运用MC-ICP-MS进行Fe同位素比值高精度测试的方法,对Fe同位素测定过程中谱峰干扰、基质效应、浓度效应、仪器测试的长期重现性等问题进行了评估,并对两种运行模式的测试结果进行了对比.在95%的可信度范围内,所建方法的外部精度优于0.5ε/ainu,达到国际同类实验室的先进水平,并且低分辨和高分辨两种模式下获得的Fe同位素测试结果是一致的.在此基础上对国家地质标准物质GBW07105(玄武岩)和GBW 07111(花岗闪长岩)进行了Fe同位素测定.相对于Fe同位素国际标样IRMM-014,GBW07105的Fe同位素成分为:ε57Fe=1.9±0.3(20),ε56Fe=1.3±0.2(2σ),ε57/56Fe=0.6±0.1(2σ);GBW 07111的Fe同位素成分为:ε57Fe=1.8±0.4(2σ),ε56Fe=1.2±0.2(2σ),ε57/56Fe=0.6±0.1(2σ). 相似文献
7.
Mo同位素的研究在地学领域应用广泛,它可以示踪Mo的全球循环、古海洋氧化还原条件、成矿过程、天体演化过程等。应用多接收电感耦合等离子体质谱法(MC-ICP-MS)分析Mo同位素比值前需对样品进行分离纯化,以富集Mo和去除Zr、Ru、Fe、Mn等干扰元素。处理某些Fe含量特别高且Ca含量也高的特殊地质样品(如含大量黄铁矿的钙质泥岩、钙质页岩等),若根据传统的阴阳离子交换树脂双柱法,需多次使用阳离子交换树脂分离Fe,步骤较繁琐且Mo回收率也会降低,而根据传统的阴离子交换树脂单柱法,使用1mol/L氢氟酸-0.5mol/L盐酸介质会产生较多CaF_2沉淀影响分离纯化效果。针对此类特殊地质样品,本实验使用同一阴离子树脂柱(AG1-X8,100～200目)对样品进行两次淋洗,第一次使用6mol/L盐酸,第二次使用1mol/L氢氟酸-0.1mol/L盐酸和6mol/L盐酸。结果表明Mo的回收率96%,干扰元素的去除效果好,尤其是Ru的去除率接近100%,比原方法提高了约12%。对实际样品进行实验的结果也显示,Mo的回收率和干扰元素的去除都符合要求,δ~(98/95)Mo测定值与文献报道值一致。改进后的阴离子交换树脂单柱-二次淋洗法适用于Fe、Ca含量较高的特殊样品,降低了分析成本,也适用于绝大多数地质样品。 相似文献
8.
多接收器等离子体质谱仪(MC-ICP-MS)高精度同位素组成的准确测定,依赖于对样品中待测元素的分离纯化.本研究比较了两种溶样方法对有机样品积累植物海州香薷的消解效果,检测了AG MP-1阴离子交换树脂对样品中Cu、Zn的分离效果,并测定了样品中的Cu、Zn同位素组成.结果表明:①两种不同溶样方法均能有效地破坏累植物海州香薷样品中的有机质;②AG MP-1树脂能有效分离纯化植物中的Cu、Zn,经过AG MP-1树脂一次交换分离和二次交换分离的植物根样品的Cu接收液基体元素的去除基本没有差别,经过一次交换分离的Zn溶液,基体元素也基本除去,可以用于MC-ICP-MS对Cu、Zn同位素组成高精度的测定;③Cu、Zn同位素组成测定误差不大于仪器的长期重现性,表明样品的化学处理过程、各离子交换树脂柱分离交换过程和仪器测试过程均有很好的重现性,符合样品测定的要求. 相似文献
9.
同一岩石试样的Lu-Hf和Sm-Nd快速分离及国家岩石标准物质的Hf-Nd同位素比值精确测定 总被引：1，自引：2，他引：1
本文报道基于Li_2B_4O_7熔融样品、采用AG50W-X8和HDEHP组合或RE和HDEHP组合色谱交换柱,对同一岩石试样快速分离Sm-Nd-Lu-Hf的方法。用这两种方法对国际岩石标准BHVO-2、GSP-2和JB-1进行了Lu-Hf、Sm-Nd分离和~(143) Nd/~(144)Nd、~(176)Hf/~(177)Hf测定,并测定了BHVO-2、JB-1和JB-3的Lu/Hf和Sm/Nd比值,获得的结果在误差范围内与这些样品的参考值一致。同时,我们对国家岩石标准物质GBW07109、GBW07110和GBW07113进行了多次平行分析,首次获得了这些岩石标准的Nd-Hf同位素结果。 相似文献
10.
《矿物岩石地球化学通报》2016,(3)
使用AGMP-1M阴离子交换树脂提纯样品中的Fe同位素,利用Nu1700大型多接收等离子体质谱在高分辨率模式下测定铁同位素比值,采用标样-样品交叉法校正仪器的质量歧视效应,对回收率、化学流程本底、酸度效应、浓度效应进行了检验,建立了可靠的高精度铁同位素分析技术。本文测定了常用地质标准样品(BCR-2,BHVO-2,AGV-2,GSR-2,GSR-3)的Fe同位素组成,测定结果与文献报道值在误差范围内一致,其测试精度优于(BCR-2,BHVO-2,AGV-2,GSR-3)0.03‰(2SD)。GSR-2可能受Fe含量较低(TFe_2O_3=4.95%)和均一性的影响,获得的δ~(56)Fe和δ~(57)Fe的测试精度分别为0.05‰和0.07‰(2SD)。 相似文献
11.
The sediments atop the sequence of ophiolite usually contain Fe(-Mn-Si)exhalites,chemical sediments that aremainlycomposedofamorphousFe-Mn oxy-hydroxides and chert/jasper.They were precipitated from hydrothermal fluids produced by deep leaching of basalt particularly during volcano activity or seafloor spreading.These hydrothermal Fe exhalites provide a good record for the depositional environment and the ocean environment as well.A well-preserved Phanerozoic Fe deposit,Motuosala Fe-Mn deposit,resulted from hydrothermal exhalation,was investigated for its trace element and Fe isotope geochemistry.The deposit is located in Xinjiang province,China and is hosted in a suit of Carboniferous volcano-sedimentary clastic rocks.The Fe deposit is mainly composed of massive hematite Fe oreand banded hematite-jasper ore.The hematite ore/band and jasper band were subjected to be analyzed.They are both composed mainly of Fe2O3 and Si O2,with very low contents of Al2O3 and Ti O2(1%),indicating they werechemical precipitates with little detrital contamination.They both show slightly LREE depleted or near flat PAAS-normalised REE patterns,with positive Eu anomalies and Y anomolies,indicating that they were sourced from a mixture of high-temperature fluids and seawater.Compared to the hematite Fe ore/band,the jasper band shows higher EuSN/EuSN*but lower Y/Ho values.δ56Fe values for the hematite Fe ores are clustered around-0.3‰,similar to those for high-temperature fluids.The jasper samples show heavier Fe isotope compositions varying from-0.1‰to0.5‰,indicating that they were resulted from partial Fe precipitation.For all samples,δ56Fe values are related to Y/Ho and EuSN/EuSN*values.The results indicate that the hematite Fe ore and jasper were deposited in different environments.The jasper was deposited in a more anoxic condition with higher hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was more intense;while the hematite Fe ore was deposited in a more oxic condition with lower hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was weaker. 相似文献
12.
Ravi K. Kukkadapu John M. Zachara James P. McKinley Steven C. Smith 《Geochimica et cosmochimica acta》2006,70(14):3662-3676
A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe2+, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)2, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products. 相似文献
13.
A pyralspite garnet from an anomalously magnetic concentrate of a pegmatitic cassiterite ore has been investigated using 57Fe nuclear gamma-ray resonance spectroscopy. The quadrupole splitting and isomer shift values of 3.6 mm/s and 1.4 mm/s, respectively, are among the largest observed for Fe2+ ions and indicate a very low covalency of the dodecahedral Fe2+ — O2-bonds. These data support the more recent and lower value (10.2–10.1 kcal/ mole) of White and Moore (1972) for the CFSE of the dodecahedral Fe2+ ion and suggest that the CFSE should be a useful approximation to the site preference energy of Fe2+ for this site. 相似文献
14.
Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl−) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using 57Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60-80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl− (∼10 mM HNO3) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl− solutions.The average measured equilibrium isotope fractionations, ΔFe(III)-Fe(II), in 0, 11, and 111 mM Cl− solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured ΔFe(III)-Fe(II) fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl− solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: where the isotopic fractionation is independent of Cl− contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl− contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation. 相似文献
15.
Synthetic Fe3+-melilites containing NaCaFe3+-Si2O7-, Ca2Fe3+AlSiO7- or Sr2Fe3+AlSiO7-components have been studied by 57Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe3+Si2O7-component consists of one doublet identified to belong to Fe3+ in T1 sites. The spectra of åkermanite and gehlenite containing Ca2Fe3+ AlSiO7- or Sr2Fe3+ AlSiO7-component consist of two doublets. The inner and outer doublets are identified to belong to Fe3+ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe3+ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe3+ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic. 相似文献
16.
K. Kaplun 《Geochimica et cosmochimica acta》2011,75(20):5865-5878
The leaching kinetics of chalcopyrite (CuFeS2) concentrate in sulfuric acid leach media with and without the initial addition of Fe3+ under carefully controlled solution conditions (Eh 750 mV SHE, pH 1) at various temperatures from 55 to 85 °C were measured. Kinetic analyses by (i) apparent rate (not surface area normalised), and rate dependence using (ii) a shrinking core model and (iii) a shrinking core model in conjunction with Fe3+ activity, were performed to estimate the activation energies (Ea) for Cu and Fe dissolution.The Ea values determined for Cu and Fe leaching in the absence of added Fe3+ are within experimental error, 80 ± 10 kJ mol−1 and 84 ± 10 kJ mol−1, respectively (type iii analyses Ea are quoted unless stated otherwise), and are indicative of a chemical reaction controlled process. On addition of Fe3+ the initial Cu leach rate (up to 10 h) was increased and Cu was released to solution preferentially over Fe, with the Ea value of 21 ± 5 kJ mol−1 (type ii analysis) suggestive of a transport controlled rate determining process. However, the rate of leaching rapidly decreased until it was consistently slower than for the equivalent leaches where Fe3+ was not added. The resulting Ea value for this leach regime of 83 ± 10 kJ mol−1 is within experimental error of that determined in the absence of added Fe3+. In contrast to Cu release, Fe release to solution was consistent with a chemical reaction controlled leach rate throughout. The Fe release Ea of 76 ± 10 kJ mol−1 is also within experimental error of that determined in the absence of added Fe3+. Where type (ii) and (iii) analyses were both successfully carried out (in all cases except for Cu leaching with added Fe3+, <10 h) the Ea derived are within experimental error. However, the type (iii) analyses of the leaches in the presence of added Fe3+ (>10 h), as compared to in the absence of added Fe3+, returned a considerably smaller pre-exponential factors for both Cu and Fe leach analyses commensurate with the considerably slower leach rate, suggestive of a more applicable kinetic analysis.XPS examination of leached chalcopyrite showed that the surface concentration of polysulfide and sulfate was significantly increased when Fe3+ was added to the leach liquor. Complementary SEM analysis revealed the surface features of chalcopyrite, most likely due to the nature of the polysulfide formed, are subtly different with greater surface roughness upon leaching in the absence of added Fe3+ as compared to a continuous smooth surface layer formed in the presence of added Fe3+. These observations suggest that the effect of Fe3+ addition on the rate of leaching is not due to the change in the chemical reaction controlled mechanism but due to a change in the available surface area for reaction. 相似文献
17.
Summary Tetrahedrites with the composition between Cu12Sb4S13 and Cu10Fe2Sb4S13 were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of57Fe. Between Cu12Sb4S13 and Cu11Fe1Sb4S13 iron is predominantly ferric. Between Cu11Fe1Sb4S13 and Cu10Fe2Sb4S13 iron is predominantly ferrous and occupies the tetrahedral M1-sites.
Zusammenfassung Die Rolle von Fe2+ und Fe3+ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu12Sb4S13 and Cu10Fe2Sb4S13 wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von57Fe untersucht. Zwischen Cu12Sb4S13 and Cu11Fe1Sb4S13 ist Eisen überwiegend dreiwertig. Zwischen Cu11Fe1Sb4S13 and Cu11Fe2Sb4S13 ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.相似文献
18.
Mossbauer measurements have been carried out on three natural chromite minerals from different locations in China over the temperature range 50 to 750 K. The experiments showed these samples to be magnesioferrochromites. The Mossbauer spectra measured could be decomposed into three doublets: two attributed to the tetrahedral T-site Fe2+ ions and the third to the octahedral M-site Fe3+ ions. Thus for the chromite spinels the results strongly supported the ordered distribution with Fe2+ in the T-site and Fe3+ in M-site. 相似文献
19.
Mössbauer spectra of biotite at 4 K are reported. The biotite crystals were oriented with the c-axis parallel to the γ-ray direction and some spectra were recorded with external magnetic fields of 40 kOe applied at right angles to the c-axis. Decrease of the magnetic-hyperfine field of both Fe2+ and Fe3+ ions on application of the external field shows that both Fe3+-Fe3+ pairs and Fe2+-Fe2+ pairs are coupled ferromagnetically. 相似文献
20.
The spinel solid solution was found to exist in the whole range between Fe3O4 and γ-Fe2SiO4 at over 10 GPa. The resistivity of Fe3−
x
Si
x
O4 (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe3+ and Fe2+ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy
of the electron hopping becomes larger with increasing γ-Fe2SiO4 component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe3+–Fe2+ electron hopping with increasing the total Si content. This is probably because a large number of Si4+ ions occupies the octahedral site and the adjacent Fe2+ keeping the local electric neutrality around Si4+ makes a cluster, which generates a local deformation by Si substitution.
The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases
from 124(±2) K at x=0 (Fe3O4) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si4+ substitution.
Received: 15 March 2000 / Accepted: 4 September 2000 相似文献