Determination of the crystallographic texture of sintered PrFeB magnets based on X-ray diffraction patterns

An alternative method for determining the degree of crystallographic alignment (cos Θ) of the magnetic Pr₂Fe₁₄B phase (Φ) is proposed. The method is based on the relative X-ray diffracted intensities of the Φ planes of sintered magnets with and without texture. The degree of crystallographic alignment is also determined by X-ray pole figures using the (0 0 4) reflection and considered as a standard reference for comparison. The method is applied to Pr₁₆Fe₇₆B₈ magnets with 0.51cos Θ0.97. The difference between the crystallographic alignments determined by these two methods is 3% within the experimental error. The advantages and limitations of using X-ray diffraction patterns to quantitatively evaluate the texture of sintered magnets are also discussed.     

Comparison of the Kerr effect and X-ray pole figure methods for determining crystallographic texture in PrFeB magnets

In this study, magnetic domains in Pr₁₆Fe₇₆B₈ sintered magnets have been observed by Kerr effect and a histogram of the angular distribution of domain orientations has been used to determine the magnetic texture (cos Φ). The degree of easy-axis alignment of Pr₂Fe₁₄B matrix grains in these magnets has been also determined by X-ray pole figure analysis using the (0 0 4) reflection. The (0 0 4) pole figure measurements were carried out by the Schultz's reflection method. The (0 0 4) normalized intensity data has been fitted for a Gaussian distribution and the degree of crystal alignment, cos Θ, has been calculated using the Stoner–Wohlfarth model. Comparison of these methods has been carried out. It has been shown that in magnets with medium and high degrees of crystallographic alignment, the pole figure values are higher than that obtained by the Kerr effect method. Conversely, in magnets with low degrees of alignment, cos Θ is lower than cos Φ.     

The use of polarization modulation and amplitude-sensitive optical heterodyne interferometry for linear birefringence parameters measurement

A novel common-path polarization modulation and amplitude-sensitive optical heterodyne polarimeter is setup in order to characterize a phase retardation plate (PRP) in real time. The phase retardation ΔΦ and fast-axis angle β of the linear birefringence parameters (LBP) of a PRP are measured simultaneously. Meanwhile, the dynamic ranges of 0° < ΔΦ < 180° and 0° < β < 180° are demonstrated experimentally. In order to measure LBP in real time, a polarization modulation is introduced by continuously rotating the tested PRP such that ΔΦ and β are able to be obtained in terms of the ratio of the amplitudes of S polarization and the ratio of P polarization of the heterodyne signals, respectively. Consequently, this novel method, which combines optical heterodyne interferometry with a polarization modulation technique, not only improves the detection sensitivity, but also provides a real time capability to measure LBP. In addition, the error in the LBP measurement is derived and analyzed.     

EPR and optical measurements of weakly doped LiNbO3: Er

Optical spectroscopy measurements of the congruent LiNbO₃ (LN) single crystals, weakly doped with Er (0.1–0.3 wt%) and Er (0.3 wt%) and Yb (0.5 wt%), have been carried out. The shape of the optical absorption and additional absorption bands registered after γ-irradiation suggests the presence of Er³⁺ ion pairs. EPR investigations were performed for LN single crystal doped with Er (0.1 wt%). Unusual behaviour of the temperature dependence of the intensity and linewidth of the main EPR line—corresponding to the fine transition of ^evenEr³⁺—ions, is reported. The main EPR line appears to be a superposition of several paramagnetic centres originating from isolated ^evenEr³⁺ ions and ^evenEr³⁺–^evenEr³⁺ pairs of ions. In low temperature region (below 20 K), the main EPR signal is dominated by signals arising from ^evenEr³⁺–^evenEr³⁺ pairs of ions. The inverse intensity of the EPR line at low temperature region fulfils the Curie–Weiss law and enabled to determine the Curie–Weiss constant Θ=1.5±0.5 K. The positive sign of Θ suggests that the ferromagnetic interactions arise in the system of ^evenEr³⁺–^evenEr³⁺ ion pairs in LN. Our results suggest that the distribution of Er ions in congruent LN is not homogeneous and Er impurity ions can form clusters in host lattice even in the case of weak erbium doping.     

Effects of powder flowability on the alignment degree and magnetic properties for NdFeB sintermagnets

The magnetic powders for sintered NdFeB magnets have been prepared by using the strip casting (SC), hydrogen decrepitation (HD) and jet milling (JM) techniques. The effects of powder flowability and addition of a lubricant on the alignment degree and the hard magnetic properties of sintered magnets have been studied. The results show that the main factor affecting powder flowability is the aggregation of magnetic particles for powders in a loose state, but it is the friction between the powder particles for powders that are in a compact state. The addition of a lubricant with suitable dose can slightly prevent the congregating of powders, obviously decrease the friction between the powder particles, improve the powder flowability, and increase the alignment degree, remanence and energy product density of sintered magnets. Mixing a suitable dose of lubricant and adopting rubber isostatic pressing (RIP) with a pulse magnetic field, we have succeeded in producing the sintered NdFeB magnet with high hard magnetic properties of B_r=14.57 KG, _jH_c=14.43 KOe, (BH)_max=51.3 MGOe.     

Magnetic properties of YCo5 (70%wt)+Y2Co17 (30%wt) nanocomposite powders at low temperatures

Nanostructured YCo₅ (70%wt)+Y₂Co₁₇ (30%wt) composite powders were prepared by mechanical milling and subsequent annealing at 1073 K for 1.5 min. The average grain size D of the YCo₅ and Y₂Co₁₇ phases, obtained from XRD data, was 14 and 12 nm, respectively. The temperature dependence of the magnetic properties was studied by DC magnetization measurements at temperatures T ranging from 3 to 300 K. Hysteresis loops (H_max=70 kOe) show that both the coercivity H_C and the squareness σ_r/σ_max are temperature-dependent. The coercivity increases from 12 kOe at room temperature to 18 kOe at T=3 K. The observed enhanced remanence (σ_r/σ_max>0.5) indicates that a strong exchange coupling is present at all temperatures used in this study. The maximum magnetization σ_max changes little with temperature and has a value of about 70% of the effective saturation magnetization of the title compound.     

Adsorption of oxygen on Au(111) by exposure to ozone

Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O₃ at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at Θ_O=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f_7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O₂ to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O₂ desorption peak at 520 K at low Θ_O, and the peak shifts to higher temperatures for increasing oxygen coverages up to Θ_O=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at Θ_O=1.2 ML. Analysis of the TPD data indicates that the desorption of O₂ from Au(111) can be described by first-order kinetics with an activation energy for O₂ desorption of 30 kcal mol⁻¹ near saturation coverage. We estimate a value for the Au–O bond dissociation energy D(Au–O) to be 56 kcal mol⁻¹.     

A molecular beam study of the adsorption dynamics of CO on Ru(0001), Cu(111) and a pseudomorphic Cu monolayer on Ru(0001)

We have investigated the sticking coefficient of CO on Ru(0001), a pseudomorphic Cu monolayer on Ru(0001), and a fully relaxed Cu(111) multilayer as function of kinetic energy, surface coverage, and surface temperature. At a low kinetic energy of 0.09 eV, the initial sticking coefficients, S₀, on these surfaces are determined to be 0.92, 0.96 and 0.87, respectively. In all cases, a decrease of S₀ with increasing beam energy was observed, yielding values of 0.58, 0.14 and 0.07, respectively, at a kinetic energy of 2.0 eV. For all three surfaces the coverage dependent sticking coefficients, S(Θ), display very characteristic behavior at low kinetic energies: S(Θ) remains more or less constant up to coverages close to saturation, indicative of precursor adsorption kinetics. However, characteristic minima at intermediate coverages are observed, which are correlated to the formation of well ordered adsorbate phases. For high kinetic energies we observe a transition towards a linear decrease of S(Θ) for Ru(0001). In contrast, for the pseudomorphic Cu monolayer and for Cu(111) we find an increase in the sticking coefficients at low coverages, followed by a decrease close to saturation. This behavior is attributed to adsorbate assisted sticking, that is, to a higher sticking coefficient on adsorbate covered regions than on the bare surface. The comparison between the pseudomorphic monolayer and Cu(111) reveals that the CO bond strength to the former is larger by 40%. The initial sticking coefficients for both surfaces are very similar at low kinetic energies; at high kinetic energies, S₀ for the pseudomorphic Cu monolayer is, however, larger by a factor of two.     

Investigation in thorium phosphate by NMR II-phosphorus dipolar networks

With through space and through bond experiments in two-dimensional NMR we analyze the transformation from the thorium phosphate-hydrogen phosphate hydrate (TPHPH) to the β form of the thorium phosphate diphosphate (β-TPD) in relation with the phosphorus networks. These techniques are complementary: the through space coupling gives an insight on the dipolar phosphorus networks while the through bond coupling is particularly efficient in the detection of the P₂O₇ groups. With these experiments we show that in a first step, by heating the precursor TPHPH above 250 °C, it transforms into an form of TPD. This transformation is due to the complete condensation of hydrogen phosphate groups HPO₄ into P₂O₇ entities. By heating -TPD above 950 °C it transforms into its well-known β form. The form is characterized by a hygroscopic behavior: some water molecules are present near the P₂O₇ groups that makes non-equivalent their phosphorus nuclei. PO₄ dipolar networks are always present in the form. The main effect of these PO₄ and P₂O₇ units is to give the system a channel structure and the water enters in them.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.     

Optical second-harmonic investigations of the isothermal desorption of SiO from the Si(100) and Si(111) surfaces

The isothermal desorption of SiO from the Si(100) and Si(111) surfaces was investigated by means of optical second-harmonic generation (SHG). Due to the high adsorbate sensitivity of this method, desorption rates could be measured over a wide range from 10⁻¹ to 10⁻⁶ ML s⁻¹. From their temperature dependence between 780 and 1000 K, activation energies of E_A=3.4±0.2 eV and E_A=4.0±0.3 eV and pre-exponential factors of ν₀=10^16±1 s⁻¹ and ν₀=10^20±1 s⁻¹ for SiO desorption were obtained for Si(100) and Si(111), respectively. In the case of the Si(100) surface, a pronounced decrease of the first-order rate constants was observed upon increasing the initial coverage from 0.02 to 0.6 ML. The results are interpreted in terms of coverage-dependent oxygen-binding configurations, which influence the stability of the oxide layer.     

Effects of terbium sulfide addition on magnetic properties,microstructure and thermal stability of sintered Nd-Fe--B magnets

To increase coercivity and thermal stability of sintered Nd–Fe–B magnets for high-temperature applications, a novel terbium sulfide powder is added into(Pr_(0.25)Nd_(0.75))_(30.6)Cu_(0.15)Fe_(bal)B_1(wt.%) basic magnets. The effects of the addition of terbium sulfide on magnetic properties, microstructure, and thermal stability of sintered Nd–Fe–B magnets are investigated.The experimental results show that by adding 3 wt.% Tb_2S_3, the coercivity of the magnet is remarkably increased by about 54% without a considerable reduction in remanence and maximum energy product. By means of the electron probe microanalyzer(EPMA) technology, it is observed that Tb is mainly present in the outer region of 2:14:1 matrix grains and forms a well-developed Tb-shell phase, resulting in enhancement of HA, which accounts for the coercivity enhancement.Moreover, compared with Tb_2S_3-free magnets, the reversible temperature coefficients of remanence(α) and coercivity(β) and the irreversible flux loss of magnetic flow(hirr) values of Tb_2S_3-added magnets are improved, indicating that the thermal stability of the magnets is also effectively improved.     

Hydrogen adsorption on Mo1−xRex(110) (x=0–0.25) surfaces

The effects of adsorbed H on the Mo_1−xRe_x(110), x=0, 0.05, 0.15, and 0.25, surfaces have been investigated using low-energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS). For the x=0.15 alloy only, a c(2×2) LEED pattern is observed at a coverage Θ0.25 ML. A (2×2) pattern is observed for H coverages around Θ0.5 ML from surfaces with x=0, 0.05, and 0.15. Both c(2×2) and (2×2) patterns are attributed to reconstruction of the substrate. At higher coverages, a (1×1) pattern is observed. For the alloy surface with x=0.25, only a (1×1) pattern is obtained for all H coverages. Two H vibrations are observed in HREELS spectra for all Re concentrations, which shift to higher energies at intermediate coverages. Both peaks exhibit an isotopic shift, confirming their assignment to hydrogen. For Re concentrations of x=0.15 and higher, a third HREELS peak appears at 50 meV as H (D) coverage approaches saturation. This peak does not shift in energy with isotopic substitution, yet cannot be explained by contamination. The intrinsic width of the loss peaks depends on the Re concentration in the surface region and becomes broader with increasing x. This broadening can be attributed to surface inhomogeneity, but may also reflect increased delocalization of the adsorbed hydrogen atom.     

X-ray and high resolution selenium-77 solid state NMR spectroscopy as complementary probes to structural studies of organophosphorus diselenides

high resolution solid state NMR spectroscopy was employed to study structural properties of bis(diisopropoxyphosphorothioyl) diselenide 1 and bis(dineopentoxyphosphorothioyl) diselenide 2. The principal elements T_ii of effective dipolar/chemical shift tensor were calculated from spinning sideband intensities employing the WIN-MAS program. The values of anisotropy and asymmetry parameters reflect the distortion of the selenium environment. It was found that the T₃₃ component mostly contributes to changes in the isotropic chemical shifts. CP/MAS experiments were used to decide the assignment of space group by counting the number of crystallographically unique selenium centers in the unit cell. Crystals of diselenide 1 are triclinic, space group P with a=8.485(3) Å, b=8.508(1) Å, c=8.511(2) Å, =98.835(15)°, β=111.653(24)°, γ=93.524(21)°, V=559.5(3) ų, D_c=1.544(2) g/cm³ and Z=1. Refinement using 2222 reflections for 157 variables gives R=0.037. Crystals of diselenide 2 are triclinic, space group P1 with a=9.1418(8) Å, b=9.1465(8) Å, c=9.9200(9) Å, =74.751(8)°, β=74.629(7)°, γ=82.216(7)°, V=769.7(1) ų, D_c=1.365(2) g/cm³ and Z=1. Refinement using 3316 reflections for 297 variables gives R=0.0272.     

129Xe NMR study of Xe adsorption on multiwall carbon nanotubes

¹²⁹Xe NMR spectroscopy has been used to study the adsorption of Xe on multi-wall carbon nanotubes (MWCNT). The results obtained have shown the ¹²⁹Xe NMR ability to probe the intercrystalline (aggregate) and the inner porosity of CNT. In particular, the effects on porosity of tubes openings by hydrogen exposure and of ball milling were examined. Dramatic changes observed in the ¹²⁹Xe NMR spectra after moderate ball milling of MWCNTs were attributed to the destruction of the initial intercrystalline pore structure and to the Xe access inside the nanotubes. To examine the exchange dynamics the mixture of as-made and milled MWCNTs was studied with one- and two-dimensional (1D and 2D) ¹²⁹Xe NMR. The exchange between the interior of milled nanotubes and the aggregate pores of as-made MWCNTs was fast on the NMR acquisition time scale. The Xenon exchange between the interior of the as-made MWCNTs and the large aggregate pores occurred on a longer time scale of 10 ms, as was established by 2D ¹²⁹Xe NMR exchange spectroscopy. Variable temperature ¹²⁹Xe NMR data were also discussed and analyzed in terms of the fast exchange approximation.     

Structure and NO reactivity of Zr-deposited Pd surfaces

The structure and NO reactivity of Zr-deposited Pd surfaces were investigated by X-ray photoelectron spectroscopy, low-energy electron diffraction, infrared reflection absorption spectroscopy, and temperature-programmed desorption. Zr on Pd(1 0 0) was oxidized to ZrO₂ by exposure to O₂ at 773 K. Heating at 823 K in a vacuum led to decomposition of ZrO₂ to Zr metal and O₂. The activation energy for ZrO₂ decomposition changed remarkably at Θ_Zr = 0.4. For Θ_Zr > 0.4, a hexagonal structure was observed for ZrO₂/Pd(1 0 0); no ordered structure was observed for Θ_Zr < 0.4. Deposited Zr had no significant effect on the adsorption and decomposition of NO on Pd(1 0 0) but resulted in a creation of new NO dissociation sites on Pd(3 1 1). Zr on Pd(3 1 1) was oxidized to ZrO_X by oxygen produced from NO dissociation. Heating at 823 K in a vacuum led to decomposition of ZrO_X to Zr metal and O₂.     

Structural and optical properties of thermally evaporated Bi2Te3 films

Bi₂Te₃ films were prepared by thermal evaporation technique. X-ray diffraction analysis for as-deposited and annealed films in vacuum at 150 °C were polycrystalline with rhombohedral structure. The crystallite size is found to increase as the film thickness increases and has values in the range 67–162 nm. The optical constants (the refractive index, n, and absorption index, k) were determined using transmittance and reflectance data in the spectral range 2.5–10 μm for Bi₂Te₃ films with different thicknesses (25–99.5 nm). Both n and k are independent on the film thickness in the investigated range. It was also found that Bi₂Te₃ is a high refractive index material (n has values of 4.7–8.8 in the wavelength range 2.5–10 μm). The allowed optical transitions were found to be direct optical transitions with energy gap  eV. The optical conductivities σ₁ = ƒ(hν) and σ₂ = f(hν) show distinct peaks at about 0.13 and 0.3 eV, respectively. These two peaks can be attributed to optical interband transitions.     

Scaling behavior of mixed-state hall effect in MgB2 thin films

The Hall resistivity (ρ_xy) and the longitudinal resistivity (ρ_xx) in c-axis-oriented superconducting MgB₂ thin films have been investigated in extended fields up to 18 T. We have observed a scaling behavior between the Hall resistivity and the longitudinal resistivity, , where the exponent (β) is observed to be independent of the temperatures and the magnetic fields. For a wide magnetic field region from 1 to 18 T and a wide temperature region from 10 to 28 K, a universal power law with β = 2.0 ± 0.1 was observed in c-axis-oriented MgB₂ thin films. These results can be well interpreted by using recent models.     

Magnetic phase transition in (Fe,Mn)65Ni35 alloys

Magnetization measurements on the Fe₆₀Mn₅Ni₃₅ and Fe₅₀Mn₁₅Ni₃₅ alloy samples were carried out in the temperature range 80T300 K and in magnetic fields up to 8 kOe. The Fe₆₀Mn₅Ni₃₅ was found to order ferromagnetically with a Curie temperature, T_c, above 300 K. From the temperature dependence of the spontaneous magnetization, M_s, it was concluded that the magnetic behavior of Fe₆₀Mn₅Ni₃₅ follows Wohlfarth theory of weak itinerant ferromagnet. The Fe₅₀Mn₁₅Ni₃₅ sample exhibits a magnetic phase transition from ferromagnetism to paramagnetism at T_c=242 K. The critical amplitudes and critical exponents (β, γ and δ) have been determined by using Arrott plots, Kouvel–Fisher method and scaling plots of the reduced magnetization and reduced magnetic field. The values of β, γ and δ are discussed and compared with the results obtained for various theoretical models and also with the experimentally determined values for related systems obtained by others.     

X-ray diffraction characterization of MBE grown Pr1−xSrxMnO3 thin films on NGO(1 1 0)

Oxygen plasma-assisted molecular beam epitaxial (MBE) growth of Pr_1−xSr_xMnO₃ (PSMO) thin films has been carried out on NdGaO₃(1 1 0) (NGO) substrates. The growth parameters have been optimized to realize 2D layer-by-layer growth. XRD results of the epilayers show that the PSMO/NGO(1 1 0) thin films are of high crystal quality, as clear diffraction peaks can be observed belonging to the film and the substrate, respectively. Based on analysis of the peaks, it was concluded that epitaxial relation is PSMO(1 1 0)//NGO(1 1 0), i.e., the c-axis being parallel to the surface. Both single scans (ω scan, 2θ/ω scan) and 2-axis reciprocal space mapping (RSM) were performed in an effort to assess the crystal structure, crystalline quality, surface and interface properties of the epitaxial layers. High temperature annealing effects on lattice structure and crystal quality have been studied and discussed. Transport property measurement of the PSMO thin film samples has been carried out and main features discussed.