Hafnium binding to rat serum transferrin

Using the TDPAC-technique binding parameters for Hf were determined afterin vivo uptake of¹⁸¹Hf in rat plasma. As much as 98.5% of the metal ions proved to be bound to protein, essentially to transferrin. The main fraction of the¹⁸¹Hf ions experiences a well defined electric quadrupole perturbation frequency (vQ1=(1516 ± 15)MHz, δ₁=(5.3 ± 0.8)%) connected with a marked relaxation damping (λ = (46 ± 8)MHz). The remaining Hf nuclei are subject to a fairly broad distribution of electric field gradients (v_Q2=(1014 ± 37)MHz, δ₂=(16±3)%). The results are compared with data obtained within vitro ¹⁸¹Hf-labeled human transferrin.     

Static electric quadrupole interaction of Ta- and Hf-ions in barium and lead titanate

The static electric quadrupole interaction of¹⁸¹Ta and¹⁷⁸Hf in polycrystalline barium and lead titanate at the site of titanium has been measured using time differential PAC and the Mössbauer effect. The electric field gradients (EFG) at room temperature at the¹⁸¹Ta nucleus are ¦V _zz¦=(3.6±0.2)·10¹⁷V/cm² in BaTiO₃ and ¦V _zz¦=(14.6±0.6)·10¹⁷ V/cm² in PbTiO₃. The temperature dependence of the quadrupole interaction has been studied giving the following EFG values: ¦V _zz¦=(2.4±0.2)·10¹⁷ V/cm² in the monoclinic and ¦V _zz¦=(1.1±0.3)·10¹⁷ V/cm² in the rhomboedral phase of BaTiO₃, and ¦V _zz¦=(15.7±0.6)·10¹⁷ V/cm² for¹⁸¹Ta/PbTiO ₃ at 77 °K. The EFG of¹⁷⁸Hf in PbTiO₃ has been derived from a Mössbauer effect experiment to beV _zz=+(10.7±0.5)·10¹⁷ V/cm². The results are compared with EFG's calculated in a point charge model and with experimental EFG's measured at⁴⁴Sc and⁵⁷Fe in the same titanates by other authors. Contributions of covalent bonds to the effective EFG's in perovskit crystals are discussed.     

The electric field gradient at Ta in HfB2

Using the time-differential perturbed-angular correlation technique, we have observed the nuclear electric quadrupole interaction at ¹⁸¹Ta (482 keV) as an impurity in the refractory compound HfB₂. The measured interaction frequency is ν_Q=730±5 MHz which corresponds to an electric field gradient of |eq|=(1·19±0·05)×10¹⁸ V/cm² at room temperature. By considering a second measurement at 4·2°K, which yields the same results as above, and by comparison with available results for Hf in HfB₂, we conclude that the d-electron density of states at the Fermi level is quite small in agreement with trends observed by others.     

Magnetic hyperfine fields at Ta in Co and Fe hosts measured by the e−-γ time-differential perturbedangular-correlation method

The radioactivity¹⁸¹Hf was implanted into pure Co and Fe hosts with the help of an isotope separator. The ferromagnetic hosts produce very strong magnetic hyperfine interactions at the nuclear site of Ta atoms. These hyperfine interactions were studied by time-differential measurements of the 133 keV conversion electron — 482 keV γ angular correlation. It is found that in both hosts an appreciable fraction of Hf atoms occupies regular lattice sites after the implantation. Using the knowng-factor of the 482 keV state of¹⁸¹Ta the magnetic hyperfine fieldsH _hf=±362.4(5.0) and ±596(18) kG for the Co and Fe hosts, respectively, were deduced These fields fit nicely into the systematics of the hyperfine fields for the 5d transition elements but are not well accounted by the existing theoretical models.     

The temperature dependence of the magnetic hyperfine field of tantalum in dysprosium

The temperature dependence of the magnetic and electric hyperfine interactions at the site of ¹⁸¹Ta impurities in polycrystalline Dy has been measured between 4.2 and 178 K using the time differential perturbed angular correlation technique. The value of the magnetic hyperfine field at 4.2 K is: |H_hf(TaDy)| = 212(9) kG The temperature dependence of the magnetic hyperfine field follows closely the prediction of the molecular field model.     

The magnetic hyperfine field and the electric field gradient at181Ta impurities in Gd metal

The magnetic hyperfine fieldH _hf and the electric field gradientV _zz at¹⁸¹Ta impurties in metallic Gd were determined by time differential perturbed angular correlation measurements with the 133 keV K-conversion electron 482 keV -cascade of¹⁸¹Ta. The sources for these measurements were prepared by implantation of radioactive¹⁸¹Hf ions into Gd. The results are: |H _hf(TaGd; 77 K)|=285(14)kG, and |V _zz(TaGd; 330 K)|=5.32(15)·10¹⁷V/cm². The value ofH _hf fits well into the systematics for 5d impurities in Gd and indicates a positive core polarisation contribution, which is expected if the conduction electrons of Gd have to a large extent d-character. The electric field gradients of the 5d impurities in Gd are not consistent with a proportionality between the ionic and the electronic contribution.     

The Electric Field Gradients in (Zr/Hf)Al3 and (Zr/Hf)2Al3 Intermetallic Compounds Studied by 181Ta- and 111Cd-PAC Spectroscopy

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline ZrAl₃ and Zr₂Al₃ compounds were measured in the temperature range 30–1100 K and compared with the results for isostructural hafnium aluminides. On the basis of the similarities of the numbers, sizes and asymmetries of electric field gradients, lattice site allocations were made. In all matrices, ¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr site. The ¹¹¹In/¹¹¹Cd impurities were also assigned to the Hf/Zr site in the compounds (Zr/Hf)Al₃, but appear to substitute the two non-equivalent Al sites in the Zr₂Al₃ and Hf₂Al₃ phases. This revised version was published online in September 2006 with corrections to the Cover Date.     

Perturbed angular correlation study of a nanostructured HfO2 film

The hyperfine field at ¹⁸¹Ta lattice sites in a nanostructured HfO₂ thin film was studied by the perturbed angular correlation (PAC) technique. The thin oxide film was deposited by pulsed laser ablation on a silicon substrate kept at 673 K. The thickness was about 25 nm. The radioactive ¹⁸¹Hf ions were produced by neutron activation of the very thin film in the Portuguese research reactor by the reaction ¹⁸⁰Hf(n,γ)¹⁸¹Hf. PAC measurements were carried out at room temperature after annealing at different temperatures up to 1,473 K in air. The PAC technique allows determining the electric field gradient at the ¹⁸¹Ta probe sites. The ¹⁸¹Ta isotopes appear in the sample as disintegration product of ¹⁸¹Hf.     

Isomer shift of the electrically split 6.2 keV nuclear transition of Ta181 in CuTaS3

The isomer shift of the 6.2 keV nuclear transition of Ta181 in CuTaS₃RAIN was investigated by nuclear gamma resonance spectroscopy. Relative to tantalum metal the isomer shift in CuTaS₃ corresponds to +37.95±0.1 mm/s. The z component of the electric field gradient at the nuclear site of Ta181 was found to be V_zz = (−1.29±0.01)·10¹⁸ v/cm². The close correlation between the isomer shift in CuTaS₃ and the electronegativity of the Ta-ligands is pointed out.     

Magnetic and electric hyperfine interactions of181Ta implanted in thulium

The magnetic and electric hyperfine interaction at the site of dilute¹⁸¹Ta impurities in the rare earth metal Tm has been investigated as a function of temperature by TDPAC measurements. The samples were prepared by ion implantation of radioactive¹⁸¹Hf. In the paramagnetic phase between 100 K and 700 K the electric fieldgradient is a linear function of temperature: V_zz(T)=V_zz(O)·(1-A·T) with A=4.6·10^?4K^?1 and V_zz(293K)=6.4 (4)·10¹⁷v/cm². The TDPAC spectrum observed at 4.2 K reflects the 4 magnetically non-equivalent sites for an impurity in magnetically ordered Tm. The relative values and amplitudes of the corresponding 4 magnetic hyperfine fields are consistent with the predictions of the RKKY theory.     

PAC study of nuclear relaxation in solids:181Ta in hafnium hydrides

The electric quadrupole interaction (QI) at the site of¹⁸¹Ta in different hafnium hydrides HfH_x has been investigated as a function of temperature by TDPAC measurements. Below 300 K the QI is static within a 300 nsec time window. Above 300 K a dynamic QI related to the diffusion of hydrogen atoms leads to relaxation effects in the TDPAC spectra. The average residence time between hydrogen jumps, evaluated on the basis of the theory of stochastic perturbations, ranges from 100 nsec at 400 K in the ɛ-phase to 1 nsec at 700 K in the α-phase of the hafnium-hydrogen system. The activation energy for hydrogen jumps was found to be independent of the hydrogen concentration: E_a=0.53(12) eV.     

The electric field gradient at tantalum in yttrium

A uniform, axially symmetric electric field gradient at ¹⁸¹Ta in hcp Y of |eq| = (5.9 ± 0.3) × 10¹⁷V/cm² at 300 K, increasing by 11% upon cooling to 4.2 K, was found using the time differential perturbed angular correlation technique.     

Temperature dependence of the quadrupole interaction of100Rh in a Cd lattice

The quadrupole interaction frequency |v _q| = |eQV _zz /h|0 = 8.71 ± 0.11 MHz was measured for the 75 keV state of¹⁰⁰Rh in a polycrystalline cadmium matrix by use of the γ-e^? and γ-γ time differential perturbed angular correlation (TDPAC) techniques. The temperature dependence of the electric quadrupole coupling constant for¹⁰⁰Rh in Cd is similar to those of other impurities in Cd metal.     

Momentum dependence of spin polarization for beta emitting nuclei produced through charge exchange reaction at intermediate energy

Hyperfine interactions were studied in the intermetallic compound GdRh₂Si₂ by perturbed angular correlation (PAC) technique using ¹⁸¹Hf(¹⁸¹Ta) probe nuclei. The measurements were performed in the temperature range 15–285 K. The PAC spectra above the antiferromagnetic ordering temperature of the GdRh₂Si₂ compound (T _N ～ 106 K), were analyzed using a model that included only electric quadrupole interactions. The observed major fraction was assigned to the ¹⁸¹Hf(¹⁸¹Ta) probe substituting the Gd atoms. The PAC spectra below Néel temperature were analyzed using combined electric quadrupole and magnetic dipole interactions. The B_hf value at Gd, measured at 15 K was found to be 1.4(1) T which, is smaller, when compared with the values obtained in this compound using other nuclear probes, ¹⁵⁵Gd (B_hf ～ 30 T) and ¹⁴⁰Ce (B_hf ～ 26 T). The present result using ¹⁸¹Hf(¹⁸¹Ta) probe is quite interesting since it shows that the contribution to B_hf at Gd due the host is smaller than other components which contribute to the hyperfine field. The temperature dependence of B_hf shows an anomalous behavior.     

Hf3Al2 and Zr3Al2 Isostructural Aluminides Studied by PAC with 181Ta and 111Cd Probes

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline Zr₃Al₂ and Hf₃Al₂ compounds were measured in the temperature range 24–1100 K. The hyperfine quadrupole interaction parameters were determined after different doping techniques and heat treatments of the samples.¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr sites and the ¹¹¹In/¹¹¹Cd impurities appear to substitute both the 8(j) Al sites and the three nonequivalent Hf/Zr sites.     

Hyperfine interaction experienced by181Ta nuclei at the Hf site in HfFe2−xSix compounds through a decoupling experiment

The time-differential perturbed angular correlation (TDPAC) experiments involving the 133–482 keV γ-γ cascade in¹⁸¹Ta have been performed in the presence of an external magnetic field along the quantization axis to measure the hyperfine magnetic field experienced by¹⁸¹Ta nuclei at the Hf site in the pseudobinary compounds HfFe_2?xSi_x with x=0.1 and x=0.3. The hyperfine magnetic fields measured at 298 K are H_hf=133.1±12.0 kG in the cubic (C15) Laves phase compound HfFe_1.9Si_0.1 and H_hf=76.8±7.0 kG in the hexagonal (C14) Laves phase compound HfFe_1.7Si_0.3. The measured hyperfine fields are discussed within the framework of the Campbell-Blandin model.     

Quadrupole interaction at181Ta in tellurium

The quandrupole interaction at¹⁸¹Ta in tellurium measured at various temperatures revealed two unique sites with an axially symmetric electric field gradient. These are interpreted as a near substitutional site with almost octahedral symmetry and a pure interstitial site in the tellurium lattice. The temperature dependence observed for QI frequencies corresponding to these sites supports this conclusion.     

Aftereffects following β-decay of181Hf1

Time differential perturbed angular correlation spectra of¹⁸¹Ta produced by beta decay of¹⁸¹Hf in monoclinic ZrO₂ have been measured over a temperature range 10K to 1300K. If times near t=0 are excluded, G₂(t) is well fitted by a standard single site model for nuclei subject to an interaction with a static electric field gradient. For high purity samples, the effective anisotropy A₂ is equal to its expected value above 200°C but decreases abruptly by approximately a factor of two for lower temperatures. This unusual decrease, which does not occur in natural crystals or in Nb-doped powders, is attributed to an aftereffect of the beta emission that populates with approximately 50% probability an electron trap located about one eV below the conduction band. At low temperatures, this trapped electron causes the Ta nucleus to relax rapidly and contributes to G₂(t) only near t=0. At high temperatures or in doped samples the electron escapes quickly enough to have negligible effect on G₂(t). Supported in part by USDOE contract DE-FG06-85ER45191     

Investigation of hyperfine interactions in GdCrO3 perovskite oxide using PAC spectroscopy

Perturbed angular correlation (PAC) measurements have been carried out in the antiferromagnetic GdCrO₃ perovskite oxide using ¹¹¹In (¹¹¹Cd) and ¹⁸¹Hf(¹⁸¹Ta) nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the compound through a chemical process during sample preparation. The PAC measurements were carried out in the temperature range 20–300 K. Measurements with the ¹⁸¹Ta indicated a unique quadrupole interaction above 170 K and a combined electric quadrupole and magnetic dipole interactions below this temperature. The observed interaction was assigned to the probe nuclei substituting Cr sites. Measurements with ¹¹¹Cd showed two quadrupole interactions. Only one of the fractions however, showed a combined electric and magnetic interaction in the temperature rage 20–170 K which was assigned to ¹¹¹Cd probe substituting Cr site. The other fraction was attributed to the Gd site. The present results are compared with those of LaCrO₃ and NdCrO₃.     

The quadrupole interaction at181Ta in Zn

The quadrupole interaction (QI) in hexagonal close packed zinc lattice was measured using the 482 keV, 10.6 ns probe state of¹⁸¹Ta employing the time-differential perturbed angular correlation technique. The electric field gradient (EFG) at¹⁸¹Ta in Zn was derived from the measured quadrupole interaction frequency at room temperature asV _zz =12.202×10¹⁷ V/cm². The quadrupole interaction measured at various temperatures displayed normal temperature dependence similar to that seen by this probe in many non-cubic hosts.