Iron-metal multilayers studied by Mössbauer spectroscopy,RBS and X-ray diffraction

Fe/M (M = Ag, Zn and Sn) multilayers prepared by a vacuum evaporation method are studied by Mössbauer spectroscopy (MS), Rutherford backscattering spectroscopy (RBS) and X-ray diffraction (XRD). For the case of an M = Ag multilayer, MS reveals that Fe in the multilayer remains as an-phase down to the layer thickness of 10 nm. This result is in agreement with the RBS result that Fe and Ag form a completely discrete layer structure without any mutual mixing. For the case of M = Zn and Sn, RBS reveals that a considerable mixing has taken place between Fe and Sn during the specimen preparation. MS on Fe/Sn specimens with different layer thickness shows that an alloy phase of about 5 nm thickness is formed at the interface. Structural as well as magnetic properties of the alloy phase are discussed based on MS at different temperatures and on reported results of the intermetallic compound FeSn.     

Study of archaeological iron objects by PGAA,Mössbauer spectroscopy and X-ray diffraction

Archaeological iron objects often corrode rapidly after their excavation, even though they have survived long times of burial in the ground. Chlorine that accumulates during burial is thought to play a major role in this destructive post-excavation corrosion. It is therefore important for the conservation of such objects to determine the chlorine content in a non-destructive manner and, if necessary, to remove the chlorine from the artefacts by appropriate methods. Such methods are leaching in alkaline solutions or heating in a reducing atmosphere at temperatures up to 800 ^°C. We have studied the efficiency of the heating method using prompt gamma activation analysis (PGAA) for monitoring the Cl content and Mössbauer spectroscopy at room temperature (RT) and 4.2 K as well as X-ray diffraction to study the mineralogical transformations of the rust layers. The heat treatments were performed a N₂/H₂ (90/10) mixture at temperatures up to 750 ^°C. As test specimens sections of iron rods from the Celtic oppidum of Manching (Bavaria) were used. The initial Cl contents of the pieces varied in the range of several hundred ppm, referring to the iron mass. Annealing for 24 h at 350, 550 and 750 ^°C was found to reduce the Cl contents of the specimens, to about 70, 30 and 15 % of the original values, respectively. The rust consists mainly of goethite with admixtures of magnetite, lepidocrocite and akaganeite, which is thought to be a major carrier of chlorine, probably together with iron chlorides. Much of the goethite is so fine-grained that it does not split magnetically at RT. Annealing converts the rust mainly to maghemite at 350 ^°C, to magnetite at 550 ^°C and to wüstite plus magnetite and metallic iron at 750 ^°C. Pure akaganeite behaves in nearly the same manner.     

Celtic gold coins in the light of Mössbauer spectroscopy, electron microprobe analysis and X-ray diffraction

Celtic gold coins found in Southern Germany were studied by Mössbauer spectroscopy, electron microprobe analysis and X-ray diffraction with special attention to coins rich in silver and copper. In such coins the electron microprobe analyses reveal a gold enrichment in a surface layer of more than 100 μm thickness. ¹⁹⁷Au conversion electron Mössbauer spectroscopy also shows that the surface of the coins consists of two phases, one of which is strongly enriched in gold compared to the bulk composition. In comparison with laboratory experiments the observed phenomena suggest that coin production in Celtic times may have involved deliberate heating and etching steps to enrich the surface layer in gold by depleting it of silver and copper.     

Mössbauer spectroscopy,X-ray diffraction and magnetic measurements of iron-nickel ultrafine particles

Iron-nickel ultrafine particles with a composition in the Invar region (38–50% Ni) were prepared by the gas-evaporation-coalescence technique. The chemical composition was checked by electronprobe microanalysis, while X-ray diffraction Rietveld refinement was used to characterize the structure as well as to estimate the particle size. The temperature and field dependence of the magnetizationM(B, T) was measured for 0B25 kOe in the temperature range 4.2 KT400 K. Transmission Mössbauer spectra were taken at room temperature and at liquid helium temperature. The results obtained show that the predominant phase is a disordered Ni-rich alloy.On leave from Physics Department, University of Khartoum, P.O. Box 321, Khartoum, Sudan.     

Characterization of Maghsail meteorite from Oman by Mössbauer spectroscopy, X-ray diffraction and petrographic microscopy

The meteorite found at Maghsail (16 55 70 N–53 46 69 E) west of Salalah Oman, has been studied by ⁵⁷Fe Mössbauer spectroscopy, X-diffractometry and petrographic microscopy. In the polished section the meteorite exhibits a porphyritic texture consisting of pyroxene and olivine phenocrysts in a fine to medium grained ground mass in addition to minor phases possibly skeletal chromite, troilite and minute amount of iron oxides. X-ray diffraction supports the existence of these compounds. The Mössbauer spectra of powdered material from the core of the rock at 298 K and 78 K exhibit a mixture of magnetic and paramagnetic components. The paramagnetic components are assigned to the silicate minerals olivine and pyroxene. On the other hand, the magnetic spectra reveal the presence of troilite and iron oxides. The petrographic analyses indicate that the iron oxides are terrestrial alteration products.     

Kinetic study of the thermal transformation of limonite to hematite by X-ray diffraction, ��-Raman and M?ssbauer spectroscopy

A kinetic study about the phase limonite (FeO(OH)-nH₂O) was performed through X-ray diffraction, ??-Raman spectroscopy and Mössbauer spectroscopy. The oxide powder sample was extracted from Taraco district, Huancané province of Puno (Peru). X-ray diffraction identified the phase goethite as the main mineralogical component, and then the sample was subjected to in-situ heat treatment in the temperature range: 100 to 500°C in oxidizing (air) and inert (nitrogen) atmospheres. The goethite phase remains stable in this range: room temperature to 200°C. Between 200°C to 250°C there is a phase transition: ??-Fe^3?+?O(OH) ?? ??-Fe₂O₃, i.e., from goethite to hematite phase, taking as evidence the evolution of the diffraction profiles. At 200°C spectra shows the start of broadened magnetic component and it was adjusted through of a magnetic distribution giving a mean field of 38.6T and a relative area of 52.9%, which is a characteristic of goethite. Also, it is noticed the presence of a small amount of hematite with a mean field of 49.0T linked with a superparamagnetic broadened doublet of relative area of 47.1% where the domains of the particles have sizes smaller than 100 Å and it is evidence the superparamagnetic limit; i.e., the superparamagnetic effect tends toward a distribution of magnetic fields. Moreover, the Raman spectra of the in-situ thermal treatment, support the transition at 290°C through the transformation of characteristic bands of goethite to hematite phase at the frequency range from 200 to 1,800 cm^???1.     

Mössbauer spectroscopy of 151 europium dicarboxylates

We have previously reported the stability of europium oxalate compared to ammonium europium bis-salen and europium benzoate. We now extend the dicoarboxylic acid chain of the oxalate by introducing additional-CH₂-groups in the dicarboxylate ligands by using malonate, succinate, glutarate and adipate. Additionally, we have examined the effect of alterations in the succinate dianion by introducing functional groups such as [C = C]in the case of the maleide and-OH group in the case of the malide. This study is an attempt to further characterize these compounds. Infrared spectra were used to characterize bridging and chelating dicarboxylates while Mössbauer spectroscopy measurements were used to gain better insight into the structure of heterocyclic “cages” containing two Eu^3?+? ions and two dianions.     

Mineral identification in Colombian coals using Mössbauer spectroscopy and X-ray diffraction

Minerals were identified in three Colombian coal samples from the Southwest of the country using M?ssbauer spectroscopy and X-ray diffraction. Original and sink separated coal fractions of specific gravity 1.40 and 1.60 with particle size less than 600 μm were used in the study. Using M?ssbauer spectroscopy, the minerals identified in the original coal samples were pyrite jarosite, ankerite, illite and ferrous sulfate, whereas by means of X-ray diffraction, minerals identified were kaolinite, quartz, pyrite, and jarosite. Differences in mineral composition were found in the original and sink separated fractions using both techniques. M?ssbauer spectra show that the mineral phases in low concentrations such as illite, ankerite and ferrous sulfate do not always appear in the spectra of sink coals, despite of those minerals occurring in the original coal, due to the fact that they are associated with the organic matter and not liberated in the grinding process. X-ray results show that the peak intensity grows as the specific gravity is increased indicating that the density separation method could be an effective process to clean coal. This revised version was published online in July 2006 with corrections to the Cover Date.     

X-ray diffraction and Mössbauer spectroscopy studies of cementite dissolution in cold-drawn pearlitic steel

Cementite dissolution in cold-drawn pearlitic steel (0.8 wt.% carbon) wires has been studied by quantitative X-ray diffraction (XRD) and Mössbauer spectroscopy up to drawing strain 1.4. Quantification of cementite-phase fraction by Rietveld analysis has confirmed more than 50% dissolution of cementite phase at drawing strain 1.4. It is found that the lattice parameter of the ferrite phase determined by Rietveld refinement procedure remains nearly unchanged even after cementite dissolution. This confirms that the carbon atoms released after cementite dissolution do not dissolve in the ferrite lattice as Fe-C interstitial solid solution. Detailed analysis of broadening of XRD line profiles for the ferrite phase shows high density of dislocations (～10¹⁵/m²) in the ferrite matrix at drawing strain 1.4. The results suggest a dominant role of ?1?1?1? screw dislocations in the cementite dissolution process. Post-deformation heat treatment leads to partial annihilation of dislocations and restoration of cementite phase. Based on these experimental observations, further supplemented by TEM studies, we have suggested an alternative thermodynamic mechanism of the dissolution process.     

Mössbauer and X-ray phase analysis of carburized steel

⁵⁷Fe backscattering Mössbauer phase analysis of the ASTM A295-70 type chromium bearing steel gas was performed for samples with varying phase composition achieved by gas carburization up to 3 wt% C followed by standard hardening, i.e. austenitizing and quenching procedures. Variations of contents of principal metallographic phases (alloyed martensite, austenite, magnetic and non-magnetic carbides) were determined and compared with reported X-ray data. Results are discussed in connection with the composition and heat treatment. Good mutual agreement of results was found, the Mössbauer phase analysis being superior for distinguishing magnetic and non-magnetic carbides, for finding the dependence on composition and also for detecting alloying element segregation. On the other hand, the Mössbauer method of determination of a small content of alloyed retained austenite suffers from the small difference between its satellites and non-magnetic carbides.     

Effect of titanium ion substitution in the barium hexaferrite studied by M?ssbauer spectroscopy and X-ray diffraction

A series of M-type barium hexaferrite has been synthesized in a glass melt by partially substituting the Fe₂O₃ with TiO₂ for investigation of their structure. The glass melt has the basic composition (mol%): 40 BaO + 33 B₂O₃ + (27-x) Fe₂O₃ + x TiO₂ with x =?0, 3.6, 5.4 and 7.2 mol% TiO₂. The substituted ferrites were studied by means of X-ray diffraction, Mössbauer spectroscopy and vibration sample magnetometer. X-ray diffraction studies revealed that not all samples have a single ferritic phase, a small second phase corresponding to BaTi₆O₁₃ was also observed to form. The Mössbauer spectra changed from magnetically ordered (x =?0) to magnetically ordered with strong line broadening. Moreover, the broadening increases with TiO₂ content. The Mössbauer parameters suggested that Ti^4?+? occupies the 2a and 12k crystal sites, and the Ti^4?+? substitution on the 2b and 4f₂ site also occurs at high melt dopings. Therefore, coercivity and saturation magnetization decreased.     

A Mössbauer and X-ray diffraction study of nonstoichiometry in magnetite

The paper deals with the applicability of Mössbauer spectroscopy and X-ray diffraction methods for the determination of the deviation of magnetite from stoichiometry. The results show that among the data obtainable by both methods, the ratio of intensities of two partial spectra composing the Mössbauer spectrum of magnetite enables to evaluate the deviation of magnetite from stoichiometry quantitatively.The authors express their gratitude to Prof. Dr. Ing. J.Cirák who enabled them to perform all measurements of Mössbauer spectra at the Department of Nuclear Physics and Technics, Slovak Technical University, Bratislava. The authors are also indebted to Ing. P.Holba (Institute of Solid State Physics, Czechoslovak Academy of Sciences) and to Ing. Z.Drbálek (Research Institute of Sound and Picture) for the preparation of magnetite samples, and to Mr. P.Chaloupek (Faculty of Mathematics and Physics, Charles University, Praha) for computer calculation of lattice constants. The aid provided by members of the G. V. Akimov State Research Institute for the Protection of Materials, Dipl. Chem. K.Jendelová who carried out chemical analysis of the samples and Ing. K.Turecká who took part in X-ray diffraction measurements, is gratefully acknowledged.     

Dynamics of iron in Fe-porphyrin aggregates studied by X-ray absorption and Mössbauer spectroscopy

The iron-porphyrin aggregates were studied by optical absorption and fluorescence method, infrared spectroscopy, X-ray absorption and Mössbauer spectroscopy. The aggregation of porphyrin molecules strengthens the Fe-ligands bonds and accelerates the spin-spin relaxations. A significant speeding-up of relaxation was observed with lowering the temperature down to 25 K. The comparison of the EXAFS (Extended X-ray Absorption Fine Structure) and Mössbauer spectroscopy results enabled some separation of the individual Fe vibration from its collective movement with ligands.     

In situ high-pressure study of LiNbO3-type FeTiO3: X-ray diffraction and Mössbauer spectroscopy

The structure of LiNbO₃-type FeTiO₃ and the oxidation state of Fe have been investigated using X-ray diffraction and Mössbauer spectroscopy in the diamond anvil cell up to 18 GPa at room temperature. A structural phase transition is observed at 15.7 GPa from LiNbO₃-type to perovskite-type, accompanied by a volume collapse of 1.5%. LiNbO₃-type FeTiO₃, which is shown to contain only ferrous iron up to this pressure, and no charge transfer is observed. In addition to the c/a axial ratio that has been used to distinguish between ilmenite and LiNbO₃-type FeTiO₃, the hyperfine parameters (isomer shift and quadrupole splitting) provide an efficient way to discriminate between these two phases.     

Investigation of constitutional and thermal defects in the ordered β-phases CoGa and NiGa alloys by Mössbauer spectroscopy

The constitutional and thermal defect formation in the Co_100-xGa_x alloys (42⩽x⩽53) and Ni_100-xGa_x alloys (47⩽x⩽52) was studied by Mössbauer spectroscopy. The formation of both constitutional and thermal defects in the CoGa alloys was observed by the appearance of resolved quadrupole split spectral components. The influence of these defects in the NiGa system was detected only by the broadening of the absorption line. The ⁵⁷Fe probe atoms were found to populate the Nisublattice in these alloys. The highest concentration of thermal defects was found in the equiatomic composition of the NiGa alloys.     

Mössbauer effect and X-ray diffraction investigation of Si–Fe thin films

An X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy investigation of Si_{100– x} Fe _x (0?<?x?<?80) thin films prepared by combinatorial sputtering methods is reported. Resulting Mössbauer spectra were fit to Voigt-based distributions of quadrupole doublets for paramagnetic spectral components and Zeeman split sextets for ferromagnetic spectral components. In conjunction with the X-ray measurements, these results show that the Si-rich films are a mixture of dilute Fe in amorphous Si and an approximately equiatomic amorphous SiFe phase. Fe-rich films show the presence of a ferromagnetically ordered phase. For x?<?73, this ferromagnetic phase is amorphous or nanostructured and for x?≥?73, the phase is shown to be a crystalline bcc phase. Results are discussed in terms of short-range structural ordering in these alloys.     

Methodological problems of quantitative analysis in Mössbauer spectroscopy

The results from research into the effect of different factors on errors in quantitative determination of the phase composition of studied substances by Mössbauer spectroscopy ion absorption are presented, and ways of using them are suggested. The effectiveness of the suggested methods is verified by an example of analyzing standard and unknown compositions.     

Accelerated mechanosynthesis of high-nitrogen stainless steel: Mössbauer and X-ray diffraction studies

A completely austenitic structure has been obtained ten times faster via the mechanical alloying (MA) of high-nitrogen 25Cr10Mn1N alloy from metal components and manganese nitride than during the MA of similar steels in a nitrogen atmosphere. A mechanism for the bcc → fcc phase transformation that occurs during MA, and where deformation stacking faults of the layer fault type on the {211} atomic planes of the bcc phase play a key role, is considered and proposed.