Magnetic properties of NpM4Al8−x (M=Cr,Fe, Cu) intermetallics: Mössbauer effect and neutron diffraction studies

Mössbauer effect and neutron diffraction studies on the tetragonal NpM₄Al_8?x (M=Cr, Fe, Cu) of the 14/mmm space group are reported. In NpFe₄Al_8?x, both the Np and Fe sites order magnetically at close temperatures: the Np order ferromagnetically at 115(15) K (μ(Np)) ～ 0.6 μ_B and the Fe moments order antiferromagnetically at 130(10) K (μ(Fe) = 1.05(15) μ_B) with a ++?? sequence. In NpCr₄Al_8?x, the Np order magnetically around 50K. From the susceptibility data we conclude possible antiferromagnetic order of both Np and Cr sites. NpCu₄Al_8?x does not order magnetically down to at least 2 K. The magnetic hyperfine splitting observed below 45 K is explained by slow paramagnetic relaxation. The Np isomer shifts and also its magnetic behavior point to a trivalent ion (⁵I₄ Hund's rule ground state). The observed relaxation and magnetic phenomena are discussed in terms of crystalline electric field effects. In contrast to the isostructural rare-earth RM₄Al₈ compounds with practically independent order of R and M magnetic sublattices, we show that Np and M sublattices in NpM₄Al₈ are strongly coupled. This is caused by hybridization of both Np and M atoms with Al.     

Observation of paramagnetic relaxation in the NpCu4Al8 intermetallic compound

²³⁷Np Mössbauer spectroscopy between 77 and 4.2 K was carried out in connection with neutron diffraction studies between 300 and 2 K on the tetragonal intermetallic NpCu₄Al₈. The Mössbauer spectra give an isomer shift of + 14.3 mm/s vs. NpAl₂ indicating the non-Kramers Np³⁺(⁵I₄)-ion to be present. Below 45 K the onset of magnetic hyperfine splitting is observed. It develops into a fully resolved Zeeman pattern at 4.2 K with B_eff≈330 T. Neutron diffraction finds no evidence for magnetic order over the whole temperature range scanned. All these results can consistently be explained by paramagnetic relaxation phenomena involving a low lying Γ^t₅ doublet closely followed by a Γ^t₄ singlet as the tetragonal crystalline field states of the Np³⁺ ion.     

Crystal structure magnetic properties and hyperfine interactions in RFe4Al8 (R = rare earth) systems

X-ray, magnetic susceptibility and ⁵⁷Fe, ¹⁵¹Eu, ¹⁵⁵Gd and ¹⁷⁰Yb Mössbauer studies were performed. Detailed analysis of X-ray intensities yields all ion locations and interatomic distances in the body centered tetragonal structure (space group I4/MMM). The unit cell contains two formula units. The rare earth, iron and aluminum occupy the 2(a), 8(f) and 8(i) and 8(j) crystallographic sites, respectively. The susceptibility and Mössbauer studies indicate the existence of two independent magnetic sublattices. The iron sublattice orders into an antiferromagnetic structure at about 120 K, whereas the rare earth sublattice orders (excluding those with La, Ce, Eu, Y and Lu) antiferromagnetically at about 20 K. The ⁵⁷Fe, ¹⁵¹Eu, ¹⁵⁵Gd and ¹⁷⁰Yb Mössbauer studies yield, in addition to the hyperfine interaction parameters, also the direction along which the moments are aligned. In EuFe₄Al₈ the Eu ion is in a mixed valent state.     

Mixed valency of europium in magnetically ordered EuFe4Al8

X-ray, susceptibility and Mössbauer effect (ME) studies of EuFe₄Al₈ and EuFe_3.5Cu_0.5Al₈ were performed. The susceptibility and the ⁵⁷FeME studies indicate an antiferromagnetic phase transition of the iron sublattic at 140 K. The ¹⁵¹EuME studies show a temperature dependent isomer shift typical of a mixed valent state with an interconfiguration excitation energy (ICE) of 1100 K and width 400 K. At temperatures below 140 K also the Eu ions become magnetically ordered. In EuFe_3.5Cu_0.5Al₈ the europium ICE is strongly dependent on local environment.     

Hyperfine Fields of 181Ta in UFe4Al8

The γ–γ Perturbed Angular Correlation technique was used to study the hyperfine interaction of ¹⁸¹Ta at the Hf site(s) in UFe₄Al₈ at room temperature and 12 K. The data at room temperature are well described by two electric field gradients, while at low temperature two combined hyperfine interactions have to be considered, one with the magnetic hyperfine field collinear with the c-axis and another with the magnetic hyperfine field in the basal plane. The results are compared with previous Mössbauer and neutron diffraction experiments and the lattice site of Hf is discussed.

     

Structural and magnetic properties of Sc1.1Fe3.9Al8 alloy

The crystallochemical and magnetic nature of ternary Sc_1+δFe_4−δAl₈ intermetallic with a small Sc excess δ=0.1 was investigated by scanning electron microscope, X-ray powder diffraction, neutron diffraction, Mössbauer effect and superconducting quantum interference device techniques. The sample crystallizes in a tetragonal ThMn₁₂ type structure. The excess of Sc atoms substitute Fe at the (8f) positions and have a pronounced effect on the magnetic properties. The experiments carried out in temperature range 4-320 K show that below 120 K the magnetic structure of the alloy forms a double cycloid with magnetic moments rotating according to the incommensurate in-plane wave vector, which is temperature independent up to 160 K. The value of Fe magnetic moment is close to 0.9 μ_B atom⁻¹ at 4 K. Temperature dependence of unit cell dimensions can be explained within the Debye-Grüneisen approximation.     

A comparative first-principles study on electronic structures and mechanical properties of ternary intermetallic compounds Al8Cr4Y and Al8Cu4Y: Pressure and tension effects

An investigation into the bulk properties, elastic properties and Debye temperature under pressure, and deformation mode under tension of Al₈Cu₄Y and Al₈Cr₄Y compounds was investigated by using first principles calculations based on density functional theory. The calculated lattice constants for the ternary compounds (Al₈Cu₄Y and Al₈Cr₄Y) are in good agreement with the experimental data. It can be seen from interatomic distances that the bonding between Al1 atom and Cr, Y, and Al2 atoms in Al₈Cr₄Y are stronger than Al₈Cu₄Y. The results of cohesive energy show that Al₈Cr₄Y should be easier to be formed and much stronger chemical bonds than Al₈Cu₄Y. The bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν can be obtained by using the Voigt–Reuss–Hill averaging scheme. From the results of elastic properties, Al₈Cr₄Y has the stronger mechanical behavior than Al₈Cu₄Y. Our calculations also show that pressure has a greater effect on mechanical behavior for both compounds. The ideal tensile strength are obtained by stress-strain relationships under [001](001) uniaxial tensile deformation, which are 15.4 and 23.4 GPa for Al₈Cu₄Y and Al₈Cr₄Y, respectively. The total and partial density of states and electron charge density under uniaxial tensile deformations for Al₈Cu₄Y and Al₈Cr₄Y compounds are also calculated and discussed in this work.     

Ferrimagnetism and hyperfine interactions in RFe5Al7(R = rare earth)

Magnetization and Mössbauer (⁵⁷Fe, ¹⁵⁵Gd) studies of RFe₅Al₇(R = Y, Sm to Lu, ThMn₁₂ crystal structure) in magnetic fields up to 50 kOe and temperatures 4.1 to 500 K have been performed. The Mössbauer studies yield the distribution of the iron ions among the various inequivalent crystallographic and magnetic sites, the hyperfine fields and their temperature dependence. The magnetization curves display a great variety of unusual magnetic phenomena. Among those; strong anisotropy, magnetic and thermal hysteresis (H_c = 24 kOe for DyFe₅Al₇ at 4.1 K), negative magnetization at low temperatures when the sample is cooled in a magnetic field (even in 1 Oe), compensation points, maxima points and time-dependent magnetization. Most of the phenomena observed can be explained in terms of a spin structure previously suggested for the RFe₆Al₆ compounds, composed of 4 magnetic sublattices. The rare earth moments lie antiparallel to the iron moments in the (j) site and to the ferromagnetic component of a canted antiferromagnetic structure of iron in the (f) site. Iron in the (i) site is nonmagnetic.     

Magnetic properties of rare-earth transition metal aluminides R6T4Al43 with Ho6Mo4Al43-type structure

The magnetic properties of 53 aluminium-rich intermetallic compounds R₆T₄Al₄₃ with R=rare-earth elements and T=Ti, V, Nb, Ta, Cr, Mo, W were investigated using polycrystalline samples and a SQUID magnetometer in the temperature range from 2 to 300 K with magnetic flux densities up to 5.5 T. The yttrium and lutetium compounds are Pauli paramagnetic, indicating that the transition metal atoms do not carry magnetic moments. The samarium compounds show van Vleck behavior and antiferromagnetic order with Néel temperatures of less than 12 K. Of these Sm₆Ti₄Al₄₃ becomes metamagnetic. The ytterbium compounds show a mixed or intermediate valent behavior and no magnetic order down to 2 K. All other compounds obey the Curie–Weiss law above 30 K. Their effective magnetic moments correspond to the theoretical moments of the rare-earth ions. They show ferromagnetic or metamagnetic behavior with ordering temperatures all below 20 K. The magnetization curves of most compounds (recorded up to 5.5 T) reach about 50% of the theoretical magnetization already at 0.5 T. The gadolinium compounds are exceptional in that they reach at 0.5 T only about 10% of their theoretical magnetization. The crystal structures of the isotypic compounds Yb₆V₄Al₄₃ and Yb₆Ta₄Al₄₃ were refined from single-crystal X-ray data.     

Magnetic and electronic properties of the antiferromagnetic YbFe4Al8 compound

The magnetic, electrical and electronic properties of the tetragonal ternary YbFe₄Al₈ compound have been investigated. This compound was supposed to be an antiferromagnetic superconductor due to the negative magnetization signal appearing at a low field of the field cooling mode, however, based on the measurements of the temperature dependence of magnetization and resistivity we do not confirm the presence of superconductivity in this material and we ascribe the negative magnetization to the complicated non-collinear magnetic structure. A switch to the antiferromagnetic order at about 150 K has been visible both on the M(T) and ρ(T) curves. The valence state of the Yb ions has been studied by X-ray photoemission spectroscopy. The valence band spectrum at the Fermi level exhibits the domination of the hybridized Yb(4f) and Fe(3d) states.     

Magnetism,spin relaxation and hyperfine interactions of rare earths in RM6Al6(M = Cr,Mn, Cu)

The systems RM₆Al₆ (R = rare earth or Y, M = Cr, Mn, Cu, Rh) were studied by magnetization measurements and by Mossbauer spectroscopy of ¹⁵⁵Gd, ¹⁶¹Dy, ¹⁶⁶Er and ¹⁷⁰Yb. The magnetization studies show weak R-R antiferromagnetic exchange interactions in RCu₆Al₆(T_n)Gd) = 21 K, less than 4 K for all other R and strong crystalline field effects. Similar phenomena are observed in RMn₆Al₆ and RCr₆Al₆, however, due to the presence of a Mn or Cr local moment the systems order ferrimagnetically. In RCr₆Al₆the order temperatures are low T_c ～ 25 K, yet T_c(GdCr₆Al₆) = 170 K. The Mossbauer studies observations are consistent with the magnetiza results. In the case where Er and Yb are not ordered at 4.1 K, the spectra still show magnetic hyperfine structure however of paramagnetic nature. The spectra yield the hyperfine interaction spin Hamiltonian parameters and the spin relaxation rates. These turn out to be extremely slow (1O⁸–1O⁹ sec^?1, a very uncommon phenomenon for a concentrated Er or Yb metallic system.     

Magnetic properties of RM6Al6 (R = light rare earth,M = Cu,Mn, Fe)2

The systems RM₆Al₆ were studied by X-ray, magnetization and Mossbauer spectroscopy (⁵⁷Fe and ¹⁵¹Eu) measurements. The RCu₆Al₆ which crystallize in the f.c.c. NaZn₁₃ structure order ferromagnetically at low temperatures (T_c = 16KforR = Eu). The RMn₆Al₆ systems which crystallize in the rhombohedral Th₂Zn₁₇ structure order antiferromagnetically ($\text{T}{}_{\mathrm{<mtext>n</mtext>}}\text{= 25K for R = Nd}$and Eu). LaFe₆Al₆ has the NaZn₁₃ structure and orders antiferromagnetically at a relatively low temperature, 38K. The correlation of crystal structure and magnetic properties of these systems and those of RM₆Al₆ (R = heavy rare earth, tetragonal ThMn₁₂ structure) are discussed.     

Metamagnetism in Ce(Ga,Al)2

Effect of Al substitution on the magnetic properties of Ce(Ga_1−x Al _x )₂ (x=0, 0.1 and 0.5) system has been studied. The magnetic state of CeGa₂ is found to be FM with a T _C of 8 K, whereas the compounds with x=0.1 and 0.5 are AFM and possess T _N of about 9 K. These two compounds undergo metamagnetic transition and the critical fields are about 1.2 T and 0.5 T. respectively at 2 K. These variations are explained on the basis of helical spin structure in these compounds.     

Investigation of TmFe4Al8 and DyFe4Al8 by means of 169Tm and 161Dy Mössbauer spectroscopy

We have performed ¹⁶⁹Tm and ¹⁶¹Dy Mössbauer spectroscopy on TmFe₄Al₈ and DyFe₄Al₈. From the temperature dependence of the electric quadrupole splitting of the ¹⁶⁹Tm spectra of TmFe₄Al₈ we have determined the second order crystal field potential V⁰₂ = (100 ± 10) K and the exchange field term g_Jμ_BH_M = (1 ± 1) K. The temperature dependence of the hyperfine field of the ¹⁶¹Dy spectrum of DyFe₄Al₈ gives g_Jμ_BH_M = (15 ± 3) K. With these exchange fields magnetic transition temperatures of the rare earth sublattices were found, which are consistent with experiment. The relaxation behaviour of the Tm sublattice below T_N = 187 K is discussed.     

Non-Fermi-liquid behavior in UCu4+xAl8−x compounds

We report on experimental studies of the Kondo physics and the development of non-Fermi-liquid scaling in UCu_4+xAl_8−x family. We studied 7 different compounds with compositions between x=0 and 2. We measured electrical transport (down to 65 mK) and thermoelectric power (down to 1.8 K) as a function of temperature, hydrostatic pressure, and/or magnetic field.Compounds with Cu content below x=1.25 exhibit long-range antiferromagnetic order at low temperatures. Magnetic order is suppressed with increasing Cu content and our data indicate a possible quantum critical point at x_cr≈1.15. For compounds with higher Cu content, non-Fermi-liquid behavior is observed. Non-Fermi-liquid scaling is inferred from electrical resistivity results for the x=1.25 and 1.5 compounds. For compounds with even higher Cu content, a sharp kink occurs in the resistivity data at low temperatures, and this may be indicative of another quantum critical point that occurs at higher Cu compositions.For the magnetically ordered compounds, hydrostatic pressure is found to increase the Néel temperature, which can be understood in terms of the Kondo physics. For the non-magnetic compounds, application of a magnetic field promotes a tendency toward Fermi-liquid behavior. Thermoelectric power was analyzed using a two-band Lorentzian model, and the results indicate one fairly narrow band (10 meV and below) and a second broad band (around hundred meV). The results imply that there are two relevant energy scales that need to be considered for the physics in this family of compounds.     

Coexistence of superconductivity and magnetic order in YBa2Cu4O8

⁵⁷Fe Mössbauer spectroscopy, magnetic susceptibility and powder x-ray-diffraction measurements were used to study superconductivity and magnetic order in YBa₂(Cu_1?xFe_x)₄O_8+δ. T_c is decreasing with x, disappearing for x>x_c≈0.04. For xc iron substitutes Cu, predominantly in the Cu(1) site exhibiting a single quadrupole Mössbauer spectrum at 90 K. For x>x_c magnetic order is observed in the Cu(2) site, T_N=380 (5) K for x=0.1 and H_eff (Cu(2), 4.2 K)=510(2) kOe. However, the most surprising discovery is that for x=0.025, for which T_c=27(2) K, the Fe in the Cu(1) site orders magnetically at T_N=30(2) K and H_eff (Cu(1), 4.2 K)=461(2) kOe. The coexistence and competition between superconductivity and magnetic order in the Cu(1) and Cu(2) sites in YBa₂Cu₄O₈ are discussed in terms of the previously observed phase diagrams for Y_1?xPr_xBa₂(Cu_1?yFe_y)₃O_z.     

The interplay between the lattice and magnetism in La（Fe11.4Al1.6）C0.02 studied by powder neutron diffraction

The crystallographic structure and magnetic properties of La（Fell.4Alz.6）C0.02 are studied by magnetic measurernent and powder neutron diffraction with temperature and applied magnetic field. Rietveld refinement shows that La（Fe11.4Al1.6）C0.02 crystallizes into the cubic NaZn13-type with two different Fe sites： FeI （8b） and FeII （96i）, and that A1 atoms preferentially occupy the FeII site. A ferromagnetic state can he induced at a medial temperature of 39 K-139 K by an external magnetic field of 0.7 T, and a large lattice is correspondingly found at 100 K and 0.7 T. In all other conditions, La（Fe11.4Al1.6）C0.02 has no net magnetization in the paramagnetic （T 〉 TN = 182 K） or antifer- romagnetic states, and thus keeps its small lattice. Analysis of the Fe Fe bond length indicates that the ferromagnetic state prefers longer Fe-Fe distances.     

Synthesis,crystal structure and magnetic properties of Yb8Ag18.5Al47.5, Yb2Pd2Cd and Yb1.35Pd2Cd0.65

We report the synthesis of three new Yb-based compounds, Yb₈Ag_18.5Al_47.5 (Yb₈Cu₁₇Al₄₉-type, tetragonal tI74–I4/mmm), Yb₂Pd₂Cd (Mo₂B₂Fe-type, tetragonal tP10-P4/mbm) and Yb_1.35Pd₂Cd_0.65 (MnCu₂Al-type, cubic cF16–Fm3¯m). The crystal symmetry of these compounds has been determined and the complete structural characterisation carried out by single crystal and powder diffraction techniques. Two symmetry in-equivalent sites are available for the Yb ions in Yb₈Ag_18.5Al_47.5 and Yb_1.35Pd₂Cd_0.65. The 4f levels of the Yb ions are appreciably hybridised in Yb₈Ag_18.5Al_47.5 and to a lesser extent in Yb₂Pd₂Cd as inferred from the magnetisation and heat capacity data. Signatures of heavy fermion behaviour are observed in the heat capacity data of Yb₂Pd₂Cd in which the heat capacity, C/T, increases at low temperatures attaining a value of ≈600 mJ/mol K² at 1.8 K. The electrical resistivity of Yb₂Pd₂Cd follows a linear variation with temperature, T, between 1.4 and 5 K, thus indicating a possible non-Fermi liquid behaviour. In contrast, Yb ions are trivalent in Yb_1.35Pd₂Cd_0.65 and order magnetically near 1.4 K.     

Investigations of a quasi two-dimensional Heisenberg antiferromagnetic system. Nondeuterated and deuterated alkyl-ammonium-tetrachloromanganate

By neutron diffraction and susceptibility measurements the crystallographic and magnetic structures of (CH₃NH₃)₂MnCl₄ and (CD₃ND₃)₂MnCl₄ have been investigated. These compounds belong to a system of quasi two-dimensional Heisenberg antiferromagnets. At 96K a structural first order phase transition from the tetragonal high-temperature structure to an orthorhombic low-temperature structure was found. A magnetic phase transition from a two-dimensional antiferromagnetic preorder to a three-dimensional magnetic order occurs at 44.5K. The three-dimensional magnetic structure is characterized by antiferromagnetic (MnCl₄)^2- — layers perpendicular to the c-axis, with a ferromagnetic coupling between interacting next nearest (MnCl₄)^2- layers. The magnetic moments of the Mn-ions lie in the antiferromagnetic planes.     

Crystal growth,structure, electron paramagnetic resonance and magnetic properties of (NH4)2V3O8

A method to grow single crystals of ammonium vanadate (IV, V) (NH₄)₂V₃O₈ has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are $\text{a = 8.891 ± 0.004}\text{A}\text{?}$ and $\text{c = 5.582 + 0.002}\text{A}\text{?}$. The V⁵⁺ atom lies at the center of a triangular pyramide (VO₄ tetrahedron) while the V⁴⁺ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO₅ whose symmetry point group is almost C_4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g_∥ = 1.9263 et g_τ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T₂ = 0.4 × 10^?7s and for spin-lattice relaxation T₁ = 1.6 × 10^?7s. The magnetic structure is characterized by an exchange narrowing ω_e = 3 × 10¹⁰rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P_2c4bm as the interaction between V⁴⁺ ions from consecutive planes parallel to (001).