Mössbauer and magnetic study of mechanical alloying of Fe3Si

Using Mössbauer spectroscopy and measurement of hysteresis loops and thermomagnetic curves, phase composition and magnetic parameters of Fe₃Si mechanically alloyed powders were studied in dependence on milling time and subsequent heat treatment at a thermomagnetic experiment. Samples of as-prepared powders show high value of coercivity, the saturation magnetization and the content of amorphous Fe₃Si phase raise with increasing time of milling, the content of α-Fe diminishes. Heat treatment of samples with long enough milling time can produce almost perfect Fe₃Si alloy.     

A structural,magnetic and microwave study on mechanically milled Fe-based alloy powders

Fe₉₀M₁₀ powders with M=Fe, Co, Ni, Si, Al, Gd, Dy and Nd were prepared by mechanical milling. Their structure and magnetic properties were investigated. Microwave measurements were performed on the mechanically milled Fe₉₀M₁₀ powders. The results were compared with those of carbonyl Fe powders and coarse Fe powder. It has been shown that fine nanocrystalline Fe-based alloy powders prepared by mechanical milling are promising for microwave applications.     

Temperature dependence of the hyperfine fields of 111In in sapphire (Al2O3) single crystals

Cr has been added to FeCo substituting 10 at.% of Co or Fe in the alloy. The alloys Fe₅₀Co₄₀Cr₁₀, Fe₄₀Co₅₀Cr₁₀ and Fe₅₀Co₅₀ were prepared by mechanical alloying for 2, 5, 10, 20, 40 and 60 h. The formation of the alloy and the incorporation of the elements have been followed by X-Ray Diffraction (XRD) and Mössbauer Spectroscopy. The kinetics of mixing occurs by incorporation of Co and Cr into the Fe structure. After prolonged milling it seems that Cr incorporates itself into both $\upalpha $ -Fe and $\upalpha $ -FeCo structures and a mixture of FeCoCr rich in Cr and FeCoCr rich in Co solid solutions is obtained.     

Amorphization of the intermetallic compounds Co2Zr and Fe2Zr under mechanical grinding

The crystalline intermetallic compounds Co₂Zr and Fe₂Zr were produced in the stoichiometric composition and milled in a planetary ball mill for different milling periods. The samples were investigated in respect to the question if a crystal-to-glass transition occurs due to the milling process. Three different experimental methods were used for this study: X-ray diffraction, Mößbauer spectroscopy, and measurements of the specific heat capacityc _p . The intermetallic compound Fe₂Zr is very suitable for this study since it is ferromagnetic at room temperature. Thus it shows characteristic features in the Mößbauer spectrum and in the measurement of the specific heat capacityc _p . The investigation shows that the intermetallic compounds Co₂Zr and Fe₂Zr undergo a crystal-to-glass transition under mechanical grinding but the X-ray diffraction patterns show that the transformation is not complete. Even after long milling periods always an amount of a crystalline phase is present in the milled samples. In comparison the mechanically ground samples show the same properties as mechanically alloyed powder mixtures of the two elements of the same chemical composition. A probable explanation for the development of an amorphous phase by mechanical grinding of the crystalline compounds Co₂Zr and Fe₂Zr is the accumulation of internal strain in the crystalline grains. Another possible explanation, the addition of iron impurities to the crystalline compounds due to the wear debris of the milling equipment, seems to be improbable since the intermetallic phases Co₂Zr and Fe₂Zr show extended existance ranges in the equilibrium phase diagrams and hence are stable in respect to a variation in the composition.     

Study of nanocrystalline and amorphous powders prepared by mechanical alloying

The process of mechanical alloying consists of intimate mixing and mechanical working of elemental powders in a high-energy ball mill. It has been well established that this process is able to produce nanocrystalline and amorphous material. In this study, the structural effects of mechanical alloying of pure Fe, Fe₅₀W₅₀ and Fe₅₀Mo₅₀ powders were investigated by X-ray diffraction and Mössbauer spectroscopy. For all cases, nanocrystalline and/or amorphous fractions were found after milling. The resulting particle size was determined by X-ray diffraction. Pure Fe does not amorphize even after prolonged milling times. For the nanocrystalline powder, significant changes in the linewidth and the hyperfine field are found. Powder mixtures of Fe₅₀Mo₅₀ and Fe₅₀W₅₀ are completely amorphous after milling times of 10 h, as seen by Mössbauer spectroscopy, but nanocrystalline fractions of the non-iron part are still found in X-ray diffraction. Also in the amorphous state, further changes in the hyperfine parameters are found with increasing milling time.     

Ball milling of Fe40Ni40P20-xSix (x = 6, 10 and 14): production and characterization

Progress in the ball milling amorphization of elemental powders with the overall composition Fe₄₀Ni₄₀P_{20 ? x}Si_x (X = 6, 10 and 14) and thermally induced crystallization of obtained alloys were characterized by differential scanning calorimetry, X-ray diffraction and transmission Mössbauer spectroscopy (TMS). Diffusion of Si into Fe and Ni alloys promotes the formation of the amorphous phase, via previous formation of (Fe, Ni) phosphides. After milling for 32–64 h, most of the powders are amorphous but bcc Fe(Si) crystallites remain (about 5% in volume). TMS results indicate that homogenization of the amorphous phase occurs by interdiffusion of Ni and Fe in Fe(Si,P)-rich and Ni(Si,P)-rich zones respectively. Annealing induces structural relaxation of stresses induced by milling, growth of bcc Fe(Si) crystallites, precipitation of bcc Fe(Si) and fcc Ni–Fe, and minor phases of Ni-rich silicides and (Fe, Ni) phosphides. The main ferromagnetic phase is bcc Fe(Si) for Fe₄₀Ni₄₀P₁₀Si₁₀ powders obtained after milling for 32 h. However, it is fcc Fe–Ni for the same alloy after milling for 64 h. In the later powders, as well as for alloys with x = 6 and 14 milled for 32 h, the fcc Fe–Ni shows the Invar magnetic collapse.     

Crystallization of Fe-B amorphous alloy powders produced by chemical reduction

The crystallization behaviour of the Fe?B amorphous alloy powders prepared by the chemical reduction method has been investigated by Mössbauer spectroscopy. In comparison to amorphous ribbons prepared by melt-spinning, a different crystallization behaviour has been observed. After annealing the amorphous samples entirely crystallized into three crystalline phases: α-Fe, Fe₃B, and Fe₂B. In the case of Fe₈₀B₂₀ amorphous alloy ribbons produced by melt-spinning technique eutectic crystallization is commonly observed and results in the crystalline phases: α-Fe and Fe₃B. This kind of crystallization was not observed in the chemically prepared samples. The metastable tetragonal Fe₃B phase transformed completely into α-Fe and Fe₂B after annealing at 973 K for one hour.     

Mössbauer study on Zn1 − x Fe x O semiconductors prepared by high energy ball milling

We present the preparation of massive Zn_1???x Fe _x O ternary oxides using the mechanical mill. The Fe atom is a particular dopant since it presents two different oxidation states which allow us to vary the starting materials: Fe₂O₃, $\upalpha $ -Fe or FeO. Parameters such as initial concentrations, atmosphere and milling times were varied. X-ray diffraction and ⁵⁷Fe Mössbauer spectrometry (MS) were applied in order to analyze the structure evolution and iron incorporation in the wurtzite crystalline structure with milling time. At final stages, Fe atoms seem to be incorporated in the ZnO structure for those samples milled under Ar atmosphere. In all cases, two paramagnetic components, attributed to Fe atoms in both valence states, were observed by MS.     

Structural evolutions of the mechanically alloyed Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> powders

Elemental mixtures of Al, Cu, Fe powders with the nominal composition of Al₇₀Cu₂₀Fe₁₀ were mechanically alloyed in a planetary ball mill for 80 h. Subsequent annealing of the as-milled powders were performed at 600–800°C temperature range for 4 h. Structural characteristics of the mechanically alloyed Al₇₀Cu₂₀Fe₁₀ powders with the milling time and the heat treatment were investigated by X-ray diffraction (XRD), differential scanning calorimeter (DSC) and differential thermal analysis (DTA). Mechanical alloying of the Al₇₀Cu₂₀Fe₁₀ did not result in the formation of icosahedral quasicrystalline phase (i-phase) and a long time milling resulted in the formation of β-Al(Cu,Fe) solid solution phase (β-phase). The i-phase was observed only for short-time milled powders after heat treatment above 600°C. The β-phase was one of the major phases in the Al₇₀Cu₂₀Fe₁₀ alloy. The w-Al₇Cu₂Fe₁ phase (w-phase) was obtained only after heat treatment of the short-time milled and unmilled samples. The present investigation indicated that a suitable technique to obtain a large amount of quasicrystalline powders is to use a combination of short-time milling and subsequent annealing.     

{\gamma}-Fe phase plasma-induced on the surface of thin S3A alloy ribbons

Amorphous alloy ribbons of Fe₇₇Cr₂B₁₆Si₅ were exposed to cold plasmas of N₂ and Ar?CN₂ at temperatures lower than T_x?=?808?K. The conversion X-ray M?ssbauer spectra of the plasma-exposed ribbons consist of a singlet and a broadened magnetic sextet. The singlet with isomer shift $\updelta = -0.11$ ?mm/s can be assigned to $\upgamma $ -Fe austenite phase. Minor bulk magnetic changes in the alloy were measured as a consequence of these treatments; e.g. the relative intensities A23 of the transmission M?ssbauer spectra of the untreated and treated samples, were 3.22 and 3.56, respectively, the B_hf values changed from 22.9?T (untreated sample) to 22.4?T (plasma treated samples). Unexpectedly, the $\upgamma $ -Fe phase can also be produced by simply heating the alloy ribbons under N₂ flux at temperatures as low as 423?K. M?ssbauer data of the crystallized samples are also reported, and a qualitative assessment on the mechanical properties of the Fe₇₇Cr₂B₁₆Si₅ alloy associated with the plasma and/or temperature surface induced $\upgamma $ -Fe phase is given.     

Formation of Fe-Nb-X (X=Zr, Ti) amorphous alloys from pure metal elements by mechanical alloying

Fe-based amorphous powders of Fe₅₆Nb₆Zr₃₈ and Fe₆₀Nb₆Ti₃₄ based on binary eutectic were prepared by mechanical alloying starting from mixtures of pure metal powders. The amorphization behavior and thermal stability were examined by x-ray diffraction, scanning electron microscopy, transmission electron microscopy and differential scanning calorimetry. Results show that Fe₅₆Nb₆Zr₃₈ alloy has a better glass forming ability and a relatively lower thermal stability comparing with Fe₆₀Nb₆Ti₃₄ alloy. The prepared amorphous powders have homogeneous element distribution and no obvious contaminants coming from mechanical alloying. The synthesized amorphous powders offer the potential for consolidation to full density with desirable mechanical properties through the powder metallurgy methods.     

Synthesis and characterization of Fe3AlC0.5 by mechanical alloying

Double iron and aluminum carbides were prepared by mechanical alloying from elemental powders, with a ball-to-powder weight ratio 20:1. The samples were milled for 1, 3, 5, 10, 15, 20 and 25 h. The alloy progress for each milling time was evaluated by X-ray diffraction (XRD) and ⁵⁷Fe Mössbauer spectroscopy. Once the alloy was consolidated two sorts of paramagnetic sites and a magnetic distribution were detected according to the Mössbauer fit. The majority doublet could correspond to Fe₃AlC_0.5 carbide as X-ray diffraction suggest, and the other could be Fe₃AlC_0.69; the magnetic distribution corresponding to Fe₃Al phase, Fe₇C₃ and Fe₅C₂ single carbides. The hyperfine parameters are reported.     

Comparison of ball milling of Fe/Cr powders and Fe-Cr crystalline alloy

Using the mechanical attrition technique (MA), we have prepared a Fe-Cr alloy starting with a mixture of elemental iron and chromium powders with a nominal composition of 28 at% of Fe and 72 at% of Cr. MA was also performed on solid solutions of Fe₂₈Cr₇₂ crystalline alloy. The Mössbauer effect of the mechanically alloyed powder from Cr and Fe metals has been compared with that from crystalline alloy.     

CEMS investigation of near surface structure

Conversion Electron Mössbauer Spectroscopy (CEMS) studies are reported for as-cut and laser melted surfaces of single phase crystalline Fe₂Y, Fe₂₃Y₆, Fe₂Zr, Fe₂B and FeB ingots. Disorder and the appearance of a new phase with a low value of the room temperature hyperfine field was observed for the Fe?Y and Fe₂Zr ingots even on the as-cut surfaces due to the mechanical processing. In case of these ingots surface melting by ns laser pulses resulted in the formation of amorphous alloys. In case of the Fe?B ingots the formation of amorphous phase by laser melting was observed for Fe₂B only, while in case of FeB the low temperature α-FeB modification appeared both, for mechanical processing and laser melting.     

Mössbauer study of amorphous (Fe1−x Ga x )84B16

Using the⁵⁷Fe Mössbauer effect the influence of the Ga content in amorphous (Fe_1?x Ga _x )₈₄B₁₆ on the average hyperfine fields \(\bar H\) and isomer shift has been studied. For the sample (Fe_0.98Ga_0.02)₈₄B₁₆ the \(\bar H\) , as well as the recoilless fraction,f _a were measured as functions of temperature ranging from 12 K to 300 K. The experimental results show a linear correlation between Inf _a and δ, and well as between δ andx. In the temperature range \(\bar H(T)\) can be described by the Brillouin function and the second-order Doppler shift is appreciable. The characteristic temperature for such an amorphous alloy is 372 K. the effective vibrating massM _eff=79 a.u.     

Fe-doped TiO2 prepared by mechanical alloying

The effect of different milling conditions on the formation of Fe-doped TiO₂ powders by mechanical alloying was investigated by Mössbauer spectrometry. The milling conditions investigated were ball to powder weight ratio, milling time, rotation velocity of supporting disc, and the type of starting reactive iron and its concentration. X-ray diffraction shows that high energy mechanical milling of undoped anatase TiO₂ induce the anatase to rutile phase transformation via high pressure srilankite. Mössbauer spectra for the majority of the doped samples were decomposed into one sextet and one or two doublets. The sextets was attributed to the presence of α-Fe or hematite impurities. The doublets were assigned to Fe^3?+? incorporated in the TiO₂ structure, and to the Fe^2?+? located either at the surface or the interstitial sites of TiO₂. A greater incorporation of Fe in the TiO₂ structure was observed when samples were prepared from hematite instead of α-Fe.     

Fe-doped SnO 2 nanopowders obtained by sol–gel and mechanochemical alloying with and without thermal treatment

The present work is aimed to compare the physical properties of $\mbox{Sn}_{1-x} \mbox{Fe}_x \mbox{O}_{2-\delta } $ (x?=?0, and 0.05) nanopowders obtained by sol–gel method, mechanochemical alloying, and mechanochemical alloying followed by thermal treatment. The X-ray diffraction of $\mbox{Sn}_{1-x} \mbox{Fe}_x \mbox{O}_{2-\delta } $ samples prepared by sol–gel showed peaks due to the cassiterite phase of SnO₂ and thier Mössbauer spectra showed ferromagnetic and paramagnetic signals. The samples obtained by the milling process of SnO₂ mixed with $\upalpha $ -Fe showed Bragg peaks due to SnO₂ (rutile) with a line broadening caused by the reduction of grain sizes and the presence of microstrains. Mössbauer spectra for these samples revealed the presence of Fe^3?+? as well as unreacted $\upalpha $ -Fe. In the case of mechanochemical alloying with thermal treatment, the incorporation of Fe^3?+? in the SnO₂ structure with the presence of impurities was observed.     

Evolution under thermal annealing of Mn-doped iron disilicides obtained by ball milling

Phase formation in the Mn doped $\upbeta $ -FeSi₂ system (Fe_1???x Mn _x Si₂, with 0.00 ≤?x?≤ 0.24) was studied using X-ray diffraction and Mössbauer spectroscopy. Samples were prepared by the simultaneous mill of pure Si, Mn and Fe under Ar atmosphere followed by an annealing at 1,123 K during 4 h at 1 × 10^???7 Torr. After milling, an admixture of $\upbeta $ -FeSi₂, $\upalpha $ -FeSi₂ and $\upvarepsilon $ -FeSi phases was present while $\upalpha $ -FeSi₂ disappeared after annealing, resulting $\upbeta $ -FeSi₂ the main phase. Depending on Mn concentration, small amounts of $\upvarepsilon $ -FeSi and Si segregation were also observed. A preferential substitution of Fe atoms by Mn ones in the Fe_II site of the $\upbeta $ -FeSi₂ regular lattice was inferred from the Mössbauer results.     

Preparation,microstructure, and magnetic properties of a nanocrystalline Nd12Fe82B6 alloy by HDDR combined with mechanical milling

Nanocrystalline Nd₁₂Fe₈₂B₆ (atomic ratio) alloy powders with Nd₂Fe₁₄B/α-Fe two-phase structure were prepared by HDDR combined with mechanical milling. The as-cast Nd₁₂Fe₈₂B₆ alloy was disproportionated via ball milling in hydrogen, and desorption–recombination was then performed. The phase and structural change due to both the milling in hydrogen and the subsequent desorption–recombination treatment was characterized by X-ray diffraction (XRD). The desorption–recombination behavior of the as-disproportionated alloy was investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The morphology and microstructure of the final alloy powders subject to desorption–recombination treatment were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. The results showed that, by milling in hydrogen for 20 h, the matrix Nd₂Fe₁₄B phase of the alloy was fully disproportionated into a nano-structured mixture of Nd₂H₅, Fe₂B, and α-Fe phases with average size of about 8 nm, and that a subsequent desorption–recombination treatment at 760 °C for 30 min led to the formation of Nd₂Fe₁₄B/α-Fe two-phase nanocomposite powders with average crystallite size of 30 nm. The remanence B_r, coercivity H_c, and maximum energy product (BH)_max of such nanocrystalline Nd₁₂Fe₈₂B₆ alloy powders achieved 0.73 T, 610 kA/m, and 110.8 kJ/m³, respectively.     

Annealing embrittlement of Fe78Si9B13 (METGLAS-2605S2)

The ductile to brittle transition that occurs in amorphous Fe₇₈Si₉B₁₃ (METGLAS-2605S2) has been investigated using mechanical measurements over the temperature range 250–370 °C. The fracture toughness values, K _Ic , have been determined for a range of annealing times (5–30 min) and cooling rates of 15–45 °C/min. A pronounced ductile to brittle transition is observed around 310(10) °C although no obvious structural changes are evident as indicated by x-ray diffraction. Comparison of transmission and back-scattered conversion electron ⁵⁷Fe Mössbauer spectra for the bulk as-received ribbon in the ductile state ( $K_{Ic}=52~{\rm MPa} \cdot \sqrt{m}$ ) and the ribbon annealed to the brittle state ( $K_{Ic}\sim10~{\rm MPa} \cdot \sqrt{m}$ ) indicates magnetic texture effects in both the bulk and on the surface of these amorphous ribbons, related to the magnetostriction resulting from the quenched-in stress during the ribbon production process, and the ensuing stress-relief upon annealing.