Authors:J. Fan, S. Zhang, J. Lu, J. Liu, X. Zhang, Y. Ding, and Y. Chang
In order to measure 182Hf by accelerator mass spectrometry (AMS), a chemical procedure for separation of hafnium from tungsten has been developed
by extraction chromatography. The extraction chromatographic behavior of hafnium and tungsten has been studied using tri-n-octylamine (TOA) as the stationary phase, HCl–H2O2 mixture and NH3·H2O as the mobile phase. The effects of H2O2 concentration, column loading and column dimensions are investigated. Hf and W with microgram amounts are successfully separated
on a chromatographic column (Ø5 × 196 mm), on which Hf is hardly retained after completely eluted with 6 M HCl–1% H2O2 and W strongly adsorbed is then eluted with 3 M NH3·H2O. The decontamination factor for tungsten is 3.0 × 105 and the recovery of hafnium is better than 99% using a single column separation.
The cross sections for formation of metastable state of 178Hf (178m2Hf, 574.215 keV, 31 y) and 179Hf (179m2Hf, 362.55 keV, 25.05 d) through reactions induced by 14.8 ± 0.2 MeV neutrons on natural hafnium were measured for the first
time. The monoenergetic neutron beam was produced via the 3H(d, n)4He reaction on ZF-300-II Intense Neutron Generator at Lanzhou University. Induced gamma activities were measured by a gamma-ray
spectrometer with high-purity germanium (HPGe) detector. Measurements were corrected for gamma-ray attenuations, random coincidence
(pile-up), dead time and fluctuation of neutron flux. The neutron fluence were determined by the cross section of 93Nb(n, 2n)92mNb reaction. The neutron energy in the measurement were by the cross section ratios of 90Zr(n, 2n)89m+gZr and 93Nb(n, 2n)92mNb reactions.
Authors:Tsutomu Miura, Hideaki Matsue, and Takayoshi Kuroiwa
Instrumental neutron activation analysis with the internal standard correction was applied to determination Hf in high purity
Zr metal. Zirconium, which was a matrix element, was used as an internal standard to compensate for inhomogeneity of the neutron
flux through an irradiation capsule and to improve the gamma ray measurement uncertainty. It was found that the linearity
of the calibration curves of Hf was improved with using an internal standard. The analytical result of Hf in Zr metal was
in good agreement with that obtained by ICP-SFMS. The relative expanded uncertainty (k = 2) was 2.1%, and it was comparable to that of ICP-SFMS.
175, 181Hafnium(IV) was extracted by HDBP in 2-ethylhexanol from 1–10M solutions of HClO4, HCl and HNO3, and 1–8M H2SO4. As with low polar organic phase diluents, the acidity dependence of the distribution ratio of Hf, D, passes through a minimum
for HClO4, HCl, and H2SO4 whereas only an increase of D can be observed with increasing HNO3 concentration. From the slope analysis the following complexes were found to be extracted (HDBP=HA): HfA4 at <4M HClO4 and <5M HCl, lg Kextr=9, HfX4(HA)4 (X=ClO
, Cl− or NO
) at >5M HClO4, >7M HCl and 1–10M HNO3, Hf(SO4)A2(HA)3–4 at <3M H2SO4, and Hf(SO4)2 (HA)4 at >6M H2SO4. Coextraction of sulphate with hafnium from H2SO4 solutions was evidenced in experiments with macro concentrations of Hf(IV) and35SO
The separation of zirconium and hafnium by fractional precipitation as pyrophosphate1 has been extended for the preparation of pure hafnium. The favourable uptake of hafnium, in spite of the decreasing tendency
of partition factor when hafnium concentration is high, is maintained for all concentration of hafnium (relative to zirconium).
Particularly significant is the fact that at very high concentrations of hafnium (at≈84%) the uptake of zirconium sharply
falls. So pure hafnium can be prepared from natural zirconium by a simple process of eight or nine stages of fractional precipitations
as pyrophosphate. This process yields reactor grade zirconium on the one side and pure hafnium on the other side.
Authors:Ksenia Zherikova, Natalia Morozova, Ludmila Zelenina, S. Sysoev, Tamara Chusova, and I. Igumenov
Five volatile hafnium(IV) and zirconium(IV) β-diketonates: hafnium(IV) acetylacetonate, hafnium(IV) trifluoroacetylacetonate,
hafnium(IV) pivaloyltrifluoroacetonate, hafnium(IV) 2,2,6,6-tetramethylheptane-3,5-dionate and zirconium(IV) 2,2,6,6-tetramethylheptane-3,5-dionate
were obtained, purified and identified. Thermal behavior of solid compounds was investigated by thermogravimetry (TG) and
differential scanning calorimetry (DSC) in helium atmosphere and in vacuum. DSC method was also used for definition of thermodynamic
characteristics of melting processes. Using the static method with quartz membrane zero-manometer and the flow method the
temperature dependencies of saturated vapor pressure for hafnium(IV) complexes was obtained. The standard thermodynamic characteristics
ΔHT0 and ΔST0 of sublimation and evaporation processes were calculated from the temperature dependences of saturated vapor pressure.
A simple, rapid method for the separation of hafnium from aqueous solutions has been investigated using(175+181)Hf tracer. Cationic hafnium complex ions were floated from dilute acid solutions with sodium lauryl sulfate (SLS) and anionic hafnium complexes were floated from basic and oxalic acid solutions with hexadecyltrimethyl ammonium bromide (HTMAB). The conditions necessary for quantitative recovery of the metal and mechanisms of flotation are described.
Authors:L. Szirtes, J. Megyeri, L. Riess, and E. Kuzmann
The thermal decomposition of hafnium phosphate (both in amorphous and crystalline forms), molybdate and tungstate was investigated.
Hafnium phosphate has a layered structure, that of molybdate and of tungstate are tetragonal one. On investigating these materials
two main endothermic processes with mass loss were observed in the temperature range of 298–1023 K. These processes were identified
as crystal and structural water loss of the materials. The total mass loss of hafnium phosphate, molybdate and tungstate was
11,35 and 6.0%, respectively. In the case of mixed hafnium-titanium salts various crystal water quantities were found, depending
on the titanium content of the sample.
The sorption of hafnium on hydrous titanium oxide (TiO2·1.94 H2O) has been studied in detail. Maximum sorption of hafnium can be achieved from a pH 7 buffer solution containing boric acid and sodium hydroxide using 50 mg of the oxide after 30 minutes shaking. The value ofkd, the rate constant of intraparticle transport for hafnium sorption, from 0.01M hydrochloric and perchloric acid and pH 7 buffer solutions has been found to be 17 mmole·g–1·min–2. The kinetics of hafnium sorption follows Lagergren equation in 0.01M HCl solution only. The values of the overall rate constantK
=6.33·10–2 min–1 and of the rate constant for sorptionk1=6.32·10–2 min–1 and desorptionk2=2.28·10–5 min–1 have been evaluated using linear regression analysis. The value of correlation factor() is 0.9824. The influence of hafnium concentration on its sorption has been examined from 4.55·10–5 to 9.01·10–4 M from pH 7 buffer solution. The sorption data followed only the Langmuir sorption isotherm. The saturation capacity of 9.52 mmole·g–1 and of a constant related to sorption energy have been estimated to be 2917 dm3·mole–1. Among all the additional anions and cations tested only citrate ions reduce the sorption significantly. Under optimal experimental conditions selected for hafnium sorption, As(III), Sn(V), Co(II), Se(IV) and Eu(III) have shown higher sorption whereas Mn(II), Ag(I) and Sc(III) are sorbed to a lesser extent. It can be concluded that a titanium oxide bed can be used for the preconcentration and removal of hafnium and other metal ions showing higher sorption from their very dilute solutions. The oxide can also be employed for the decontamination of radioactive liquid waste and for pollution abatement studies.