Magnetic properties of mechanically alloyed nanocrystalline Ni3Fe

Disordered nanocrystalline Ni3Fe alloy was prepared by mechanical alloying of elemental powders. X-ray diffractograms show the formation of Ni3Fe single phase. The chemical composition and morphology of the powder have been obtained by using EDAX and SEM analysis respectively. While the saturation magnetisation decreases with milling time, the coercivity increases. The width of the hyperfine field distributions obtained from Mossbauer studies shows that the alloy is highly disordered Atomic ordering is found to take place at a faster rate compared to that in the bulk alloy. (C) 1999 Acta Metallurgica Inc.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Mossbauer spectroscopic study of R3Fe29-xCrx and R3Fe29-xCrxH,(y)(R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

Fe-57 Mossbauer spectra for the series of R3Fe29-xCrx (R = Y,Ce, Nd, Sm, Gd, Tb, and Dy) compounds and their hydrides have been measured at 4.2 K. The weighted average hyperfine field at the Fe sites was separated into a 3d-electron contribution, proportional to the average Fe moment, and a transferred contribution due to rare earth moments. The latter was found to increase with the rare earth effective spin (g(J) - 1) J. Hyperfine fields in the hydrides were only slightly larger than in the corresponding alloys.

Fe-57 Mossbauer spectroscopic and magnetic studies of R3Fe29-xVx (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

Mossbauer spectra for Fe atoms in the series of R3Fe29-xVx (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) compounds were collected at 4.2 K. The ratio of 14.5 T/mu(B) between the average hyperfine field B-hf and the average Fe magnetic moment mu(Fe)(MS), obtained from our data, in Y3Fe29-xVx is in agreement with that deduced from the RxTy alloys by Gubbens et al. The average Fe magnetic moments mu(Fe)(MS) in these compounds at 4.2 K, deduced from our Mossbauer spectroscopic studies, are in accord with the results of magnetization measurement. The average hyperfine field of the Fe sites for R3Fe29-xVx at 4.2 K increases with increasing values of the rare earth effective spin (g(J) - 1) J, which indicates that there exists a transferred spin polarization induced by the neighboring rare earth atom.

Mossbauer spectroscopy study of Fe-57 in R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

Fe-57 Mossbauer spectra for the Fe atoms in the R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb, Dy; T=V, Cr) compounds were collected at 4.2 K. The analysis of Mossbauer spectra was based on the results of magnetization and neutron powder diffraction measurements. The average Fe magnetic moments at 4.2 K, deduced from our data, are in accord with magnetization measurements. The average hyperfine field of Tb3Fe29-xCrx (x=1.0, 1.5, 2.0, and 3.0) decreases with increasing Cr concentration, which is also in accordance with the variation of the average Fe magnetic moment in the Tb3Fe29-xCrx compounds.

Fe-57 Mossbauer spectroscopic and magnetic studies of R3Fe29-xVx (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

Mossbauer spectra for Fe atoms in the series of R3Fe29-xVx (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) compounds were collected at 4.2 K. The ratio of 14.5 T/mu(B) between the average hyperfine field B-hf and the average Fe magnetic moment mu(Fe)(MS), obtained from our data, in Y3Fe29-xVx is in agreement with that deduced from the RxTy alloys by Gubbens et al. The average Fe magnetic moments mu(Fe)(MS) in these compounds at 4.2 K, deduced from our Mossbauer spectroscopic studies, are in accord with the results of magnetization measurement. The average hyperfine field of the Fe sites for R3Fe29-xVx at 4.2 K increases with increasing values of the rare earth effective spin (g(J) - 1) J, which indicates that there exists a transferred spin polarization induced by the neighboring rare earth atom.

Mossbauer spectroscopy study of Fe-57 in R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

Fe-57 Mossbauer spectra for the Fe atoms in the R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb, Dy; T=V, Cr) compounds were collected at 4.2 K. The analysis of Mossbauer spectra was based on the results of magnetization and neutron powder diffraction measurements. The average Fe magnetic moments at 4.2 K, deduced from our data, are in accord with magnetization measurements. The average hyperfine field of Tb3Fe29-xCrx (x=1.0, 1.5, 2.0, and 3.0) decreases with increasing Cr concentration, which is also in accordance with the variation of the average Fe magnetic moment in the Tb3Fe29-xCrx compounds.

Effect of Ti-C and Cr Additions on Magnetic Properties of Nanocrystalline (Pr,Nd)-Fe-B Alloys

The addition of both Ti-C and Cr as grain refiners in Nd-Fe-B nanocomposites substantially increases the coercive field Hc. This motived our investigation of the effect of Ti-C and Cr on Pr-Fe-B nanocomposites. Melt-spun ribbons of composition (Pr(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0; 0.25; 0.5; 0.75; 1) and (Nd(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0.5 and 1) were produced for study. For a Pr nanocomposite with 1% Cr, Hc = 12.5 kOe. However, the energy product was limited to 13.6 MGOe by the remanence value. Rietveld analysis of X-ray spectra showed the ribbons to consist of predominantly hard (similar to 70 wt%) R(2)Fe(14)B, the soft phase being (similar to 30 wt%) alpha-Fe. Mossbauer measurements at 300 K are consistent with a reduced hyperfine field for the hard magnetic phase due to the Cr addition. Analysis of transmission electron microscopy images showed the Pr nanocomposite with 1% Cr to have an increased average grain size.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Isotope shifts and hyperfine structure in the 555.8-nm S-1(0) -> P-3(1) line of Yb

We apply our technique of using a Rb-stabilized ring-cavity resonator to measure the frequencies of various spectral components in the 555.8-nm 1S0-->3P1 line of Yb. We determine the isotope shifts with 60 kHz precision, which is an order-of-magnitude improvement over the best previous measurement on this line. There are two overlapping transitions, 171Yb(1/2-->3/2) and 173Yb(5/2-->3/2), which we resolve by applying a magnetic field. We thus obtain the hyperfine constants in the 3P1 state of the odd isotopes with a significantly improved precision. Knowledge of isotope shifts and hyperfine structure should prove useful for high-precision calculations in Yb necessary to interpret ongoing experiments testing parity and time-reversal symmetry violation in the laws of physics.

Hyperfine structure in the ESR spectra of exchange-coupled pairs—copper diethyidithiocarbamate

A study of the hyperfine interaction in the ESR of coupled Cu---Cu pairs in single crystals of copper diethyldithiocarbamate as a function of temperature has shown distinct differences in the hyperfine structure in the two fine-structure transitions at 20 K; the spectrum does not have the usual binomial hyperfine pattern for the fine-structure transition of the low field in contrast to that of the high field. The details of the structure of both fine-structure transitions in the 20-K spectrum can be explained by recognizing the fact that the mixing of the nuclear spin states caused by the anisotropic hyperfine interaction affects the electron spin states |+1 and |−1 differently. The anomalous hyperfine structure is found to become symmetric at 77 and 300 K. It is proposed that the reason for this lies in the dynamics of spin-lattice interaction, which limits the lifetime of the spin states in each of the electronic levels |−1 , |0 , and |+1 . The estimate of spin-lattice relaxation time in the temperature range where the changes are observed agrees with those indicated by other studies. The model proposed here for the hyperfine interaction of pairs in the electronic triplet state is of general validity.

ESR study of exchange coupled pairs in copper diethyldithiocarbamate—explanation of the low temperature hyperfine anomaly

A study of the hyperfine interaction in the ESR of Cu-Cu pairs in single crystals of copper diethyldithiocarbamate as a function of temperature has shown distinct differences in the hyperfine structure in the two fine structure transitions at 20 K, the spectrum not having the same hyperfine intensity pattern in the low field fine structure transition in contrast to that of the high field transition. The details of the structure of both the fine structure transitions in the 20 K spectrum have now been explained by recognizing the fact that the mixing of the nuclear spin states caused by the anisotropic hyperfine interaction affects the electron spin states | + 1 > and | −> differently. This has incidentally led to a determination of the sign ofD confirming the earlier model. The anomalous hyperfine structure is found to become symmetric at 77 K and 300 K. It is proposed that the reason for this lies in the dynamics of spin-lattice interaction which limits the lifetime of the spin states in each of the electronic levels | − 1 >, | 0 > and | + 1 > The estimate of spin-lattice relaxation time agrees with those indicated from other studies. The model proposed here for the hyperfine interaction of pairs in the electronic triplet state is of general validity.