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At least 19 recordsLinked to original sources
PubMed1998

Hafnium Germanate from a Hydrous Hafnium Germanium Oxide Gel.

The gel chemistry of germanium is explored through the formation and composition of a hydrous metal oxide precursor gel used in the preparation of the HfGeO(4) and HfGeO(4):Ti X-ray phosphors. The enhanced solubility of hexagonal GeO(2) in dilute ammoniacal solutions is exploited to give a convenient and high-yield precipitation. The precursor gel is shown by FT-IR to be a diphasic mixture of hydrous hafnia and an ammonium germanate gel. Thermal treatment drives the crystallization of a hafnium-rich, simple tetragonal Hf(1)(-)(x)()Ge(x)()O(2) structure at 893 degrees C, that upon further heating to 1200 degrees C yields scheelite HfGeO(4).

Journal Article↗
PubMed2002

Dose estimate of inhaled hafnium tritide using the ICRP 66 lung model.

Metal tritide is widely used for research, purification, compression, and storage of tritium. The current understanding of metal tritide and its radiation dosimetry for internal exposure is limited, and ICRP publications do not provide the tritium dosimetry for hafnium tritide. The current radiation protection guidelines for metal tritide particles (including hafnium tritide) are based on the assumption that their biological behavior is similar to tritiated water, which is completely absorbed by the body. However, the solubility of metal tritide particles depends on the chemical form of the material. The biological half-live of hafnium tritide particles and the dosimetry of an inhalation exposure to those particles could be quite different from tritiated water. This paper describes experiments on the dissolution rate of hafnium tritide particles in a simulated lung fluid. The results showed that less than 1% of the tritium was dissolved in the simulated lung fluid for hafnium tritide particles after 215 d. The short-term and long-term dissolution half times were 46 and 4.28 x 10(5) d, respectively. This indicates that hafnium tritide is an extremely insoluble material. Self-absorption of beta rays in the hafnium tritide particles was estimated by a numerical method. The dose coefficients were calculated as a function of particle size using in vitro solubility data and a calculated self-absorption factor. The dose coefficient decreased with aerodynamic diameters in the range of 0.25 to 10 microm, mainly because the self-absorption factor decreased with increasing particle size. For a particle 1 microm in aerodynamic diameter, the dose coefficient of a hafnium tritide particle was about 10 times higher than that of tritiated water but was about 1.4 times lower than that calculated by ICRP Publication 71 for Type S tritiated particles. The ICRP estimate did not include a self-absorption factor and thus might have overestimated the dose. This finding has significant implications for current health protection guidelines.

Air Pollutants, Radioactive↗
PubMed2004

Structure of the hydrated, hydrolysed and solvated zirconium(IV) and hafnium(IV) ions in water and aprotic oxygen donor solvents. A crystallographic, EXAFS spectroscopic and large angle X-ray scattering study.

The tetrameric hydrolysis products of zirconium(IV) and hafnium(IV), the zirconyl(IV) and hafnyl(IV) ions, [M(4)(OH)(8)(OH(2))(16)(8+)], often labelled MO(2+).5H(2)O, are in principle the only zirconium(IV) and hafnium(IV) species present in aqueous solution without stabilising ligands and pH larger than zero. These complexes are furthermore kinetically very stable and do not become protonated even after refluxing in concentrated acid for at least a week. The structures of these complexes have been determined in both solid state and aqueous solution by means of crystallography, EXAFS and large angle X-ray scattering (LAXS). Each metal ion in the [M(4)(OH)(8)(OH(2))(16)](8+) complex binds four hydroxide ions in double hydroxo bridges, and four water molecules terminally. The M-O bond distance to the hydroxide ions are markedly shorter, ca. 0.12 A, than to the water molecules. The hydrated zirconium(IV) and hafnium(IV) ions only exist in extremely acidic aqueous solution due to their very strong tendency to hydrolyse. The structure of the hydrated zirconium(IV) and hafnium(IV) ions has been determined in concentrated aqueous perchloric acid by means of EXAFS, with both ions being eight-coordinated, most probably in square antiprismatic fashion, with mean Zr-O and Hf-O bond distances of 2.187(3) and 2.160(12) A, respectively. The dimethyl sulfoxide solvated zirconium(IV) and hafnium(IV) ions are square antiprismatic in both solid state and solution, with mean Zr-O and Hf-O bond distances of 2.193(1) and 2.181(6) A, respectively, in the solid state. Hafnium(IV) chloride does not dissociate in N,N'-dimethylpropyleneurea, dmpu, a solvent with good solvating properties but with a somewhat lower permittivity (epsilon= 36.1) than dimethyl sulfoxide (epsilon= 46.4), and an octahedral HfCl(4)(dmpu)(2) complex is formed.

Journal Article↗
PubMed2001

Internal dosimetry for inhalation of hafnium tritide aerosols.

Metal tritides with low dissolution rates may have residence times in the lungs which are considerably longer than the biological half-time normally associated with tritium in body water, resulting in long-term irradiation of the lungs by low energy beta particles and bremsstrahlung X rays. Samples of hafnium tritide were placed in a lung simulant fluid to determine approximate lung dissolution rates. Hafnium hydride samples were analysed for particle size distribution with a scanning electron microscope. Lung simulant data indicated a biological dissolution half-time for hafnium tritide on the order of 10(5) d. Hafnium hydride particle sizes ranged between 2 and 10 microns, corresponding to activity median aerodynamic diameters of 5 to 25 microns. Review of in vitro dissolution data, development of a biokinetic model, and determination of secondary limits for 1 micron AMAD particles are presented and discussed.

Aerosols↗
PubMed2003

Dose assessment for inhaling hafnium particles based on laboratory rats study.

Internal radiation from inhalation of hafnium tritide aerosols may be a significant radiation protection problem encountered by nuclear facility workers. Based on experimental results of the rat intratracheally instilled with hafnium tritide particles and on a self-absorption factor of beta particles determined by a numerical method, a biokinetic model was developed for inhaled particles of hafnium tritide. Results show that lung burdens of the tritide are well represented by a two-component exponential equation; biological half-lives derived for the retention of 3H in lung were 4.9 d and 1,257 d for the short- and long-term clearance, respectively. The tritium clearance rate via urine or feces was described by bi-phase exponential components. At the end of the experiment (180 d after instillation), only approximately 30% of the initial lung burden of 3H had been eliminated, of which approximately 98% was excreted via feces and 2% in urine, but none through exhaled air. Results also showed that a large percentage (70%) of the hafnium tritide initially present in lung still remained in the organ 6 mo after the exposure. The calculation of the radiation dose indicates that the cumulative dose to the lung directly from the tritide particles was approximately 10(6) times the lung dose from the dissolved tritium in the lung region. The committed effective dose to the lung was estimated to be 5.41 x 10(-10) Sv Bq(-1), which is over 99% of that to the whole body. The dose to the liver was 6.00 x 10(-15) Sv Bq(-1). This information will be useful in developing new guidelines for radiation protection purposes.

Administration, Inhalation↗
PubMed1999

Hafnium isotope stratigraphy of ferromanganese crusts

A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

Journal Article↗
PubMed1986

In vivo and in vitro studies of hafnium-binding to rat serum transferrin.

The binding of hafnium to rat serum transferrin was studied using the time differential perturbed angular correlation (TDPAC) technique. Hafnium is interesting as a toxic metal binding to transferrin because it behaves metabolically similarly to plutonium. The isotope 181Hf offers favorable access to the TDPAC-method. Samples were prepared in vivo by intravenous injection of Hf-NTA, Hf-citrate, and Hf-oxalate solutions, respectively, into Sprague-Dawley rats and in vitro by adding Hf-NTA solution to fresh rat serum. In both cases two specific electric quadrupole interactions were observed, which correspond to two well-defined binding configurations. They may be attributed to the N-terminal and the C-terminal binding site in the transferrin molecule. The 181Hf-distribution between these two binding states depends on pH, salt and hafnium concentrations, temperature, and incubation time. With a fast TDPAC-setup of four BaF2-detectors a time resolution of about 600 ps could be achieved. The specific binding configurations of 181Hf and the comparatively slow relaxation times lead to spectra of considerable accuracy.

Animals↗
PubMed2001

Biocompatibility and osteogenesis of refractory metal implants, titanium, hafnium, niobium, tantalum and rhenium.

To evaluate the biocompatibility of refractory metals, titanium, hafnium, niobium, tantalum and rhenium were implanted in rats, and histological observation and elemental mapping were performed by X-ray scanning analytical microscope (XSAM) and electron probe microanalyzer (EPMA). The titanium, hafnium, niobium, tantalum and rhenium wires were implanted in the subcutaneous tissue of the abdominal region and in femoral bone marrow of rats for either 2 or 4 weeks. No inflammatory response was observed around the implants, and all the implants were encapsulated with thin fibrous connective tissue. No dissolution of these metals was detected by XSAM in the soft tissue. Histological examination of the hard tissue showed that the amount of new bone formation decreased slightly from the second to the fourth week after implantation, and that the percentage of bone in contact with the implant increased markedly over the same period. No dissolution of these metals was detected by EPMA in the hard tissue. The Ca and P intensities in the mapping images of newly formed bone were higher after 4 weeks than those after 2 weeks, which suggests that the newly formed bone continued to mature from 2 to 4 weeks after implantation. These results indicate that titanium, hafnium, niobium, tantalum and rhenium have good biocompatibility and osteoconductivity.

Animals↗
PubMed2003

Cationic hafnium silyl complexes and their enhanced reactivity in sigma-bond metathesis processes with Si-H and C-H bonds.

Reaction of the mixed-ring silyl methyl complex CpCp*Hf[Si(SiMe3)3]Me (4) with B(C6F5)3 in bromobenzene-d5 yielded the zwitterionic hafnium silyl complex [CpCpHfSi(SiMe3)3][MeB(C6F5)3] (7), which is stable for at least 12 h in solution. Addition of PhSiH3 to 7 rapidly produced HSi(SiMe3)3, CpCp*HfH(mu-H)B(C6F5)3, and oligomeric silane products. Reactions of CpCp*Hf(SiR3)Me (SiR3 = SitBuPh2, SiHMes2) with B(C6F5)3 rapidly produced HSiR3 in quantitative yield along with unidentified hafnium-containing species. However, reactions of Cp2Hf(SiR3)Me (SiR3 = Si(SiMe3)3 (8), SitBuPh2 (9), SiPh3 (10)) with B(C6F5)3 quantitatively produced the corresponding cationic hafnium silyl complexes 12-14. The complex Cp2Hf(SitBuPh2)(mu-Me)B(C6F5)3 (13) was isolated by crystallization from toluene at -30 degrees C and fully characterized, and its spectroscopic properties and crystal structure are compared to those of its neutral precursor 9. The sigma-bond metathesis reaction of 13 with Mes2SiH2 yielded HSitBuPh2 and the reactive species Cp2Hf(eta(2)-SiHMes2)(mu-Me)B(C6F5)3 (16, benzene-d6), which was also generated by reaction of Cp2Hf(SiMes2H)Me (11) with B(C6F5)3. Spectroscopic data provide evidence for an unusual alpha-agostic Si-H interaction in 16. At room temperature, 16 reacts with benzene to form Cp2Hf(Ph)(mu-Me)B(C6F5)3 (17), and with toluene to give isomers of Cp2Hf(C6H4Me)(mu-Me)B(C6F5)3 (18-20) and Cp2Hf(CH2Ph)(mu-Me)B(C6F5)3 (21). The reaction with benzene is first order in both 16 and benzene. Kinetic data including activation parameters (deltaH = 19(1) kcal/mol; deltaS = -17(3) eu), a large primary isotope effect (kH/kD = 6.9(7)), and the experimentally determined rate law are consistent with a mechanism involving a concerted transition state for C-H bond activation.

Journal Article↗
PubMed2001

Calibration of the lutetium-hafnium clock.

Well-defined constants of radioactive decay are the cornerstone of geochronology and the use of radiogenic isotopes to constrain the time scales and mechanisms of planetary differentiation. Four new determinations of the lutetium-176 decay constant (lambda176Lu) made by calibration against the uranium-lead decay schemes yield a mean value of 1.865 +/- 0.015 x 10(-11) year(-1), in agreement with the two most recent decay-counting experiments. Lutetium-hafnium ages that are based on the previously used lambda176Lu of 1.93 x 10(-11) to 1.94 x 10(-11) year(-1) are thus approximately 4% too young, and the initial hafnium isotope compositions of some of Earth's oldest minerals and rocks become less radiogenic relative to bulk undifferentiated Earth when calculated using the new decay constant. The existence of strongly unradiogenic hafnium in Early Archean and Hadean zircons implies that enriched crustal reservoirs existed on Earth by 4.3 billion years ago and persisted for 200 million years or more. Hence, current models of early terrestrial differentiation need revision.

Journal Article↗
PubMed2000

Direct condensation of carboxylic acids with alcohols catalyzed by Hafnium(IV) salts.

In order to promote atom efficiency in synthesis and to avoid the generation of environmental waste, the use of stoichiometric amounts of condensing reagents or excess substrates should be avoided. In esterification, excesses of either carboxylic acids or alcohols are normally needed. We show that the direct condensation of equimolar amounts of carboxylic acids and alcohols can be achieved with the use of hafnium(IV) salts, such as commercially available hafnium(IV) chloride and hafnium(IV) tert-butoxide. The present method can be applied to direct polyesterification and may be suitable for large-scale operations.

Journal Article↗
PubMed1992

Preferential localization of hafnium in nodular lymphatic cells. Study by electron microprobe.

In a previous work we used the electron microprobe to study the intracellular localization of zirconium after administration of soluble salt at low doses. That element was concentrated in nodular lymphatic cells. In the present work using the same methods we studied hafnium, another element in group IVb of the periodic table, which has chemical properties similar to zirconium. After administration at low doses of soluble salt of hafnium, this element was similarly concentrated in nodular lymphatic cells and was as zirconium uniquely localized in the lysosomes of macrophages where it is associated with phosphorus.

Animals↗
PubMed1985

Antitumor activity of 1.3-diketonato zirconium (IV) and hafnium (IV) complexes.

Ten six-coordinate dihalogenobis (1.3-diketonato)zirconium (IV) and hafnium (IV) complexes as well as seven halogenotris(1.3-diketonato) zirconium(IV) and hafnium(IV) species were prepared and characterized by their elemental analysis, IR- and NMR-spectra. Their antitumor activity was tested using the intraperitoneally transplanted Sarcoma 180 tumor system in mice. Cisplatin was used in several doses as positive control compound. Seven complexes were highly active. The ratio of median survival time of treated to untreated control animals ranged up to 3 (T/C = 300%; the experiment was interrupted after that time) for these compounds. Significance according to Kruskal-Wallis test, long-time survivors, and animals which are dead on day 5 and day 30 are given. The possible mechanism of action compared to cisplatin is discussed.

Animals↗
PubMed2002

Synthesis of nanoparticles of barium lanthanum hafnium oxide by a modified combustion process.

Barium lanthanum hafnium oxide, a complex perovskite ceramic, has been synthesized as nanoparticles by a modified combustion process for the first time. The Ba, La, and Hf ions required for the formation of Ba2LaHfO5.5 were obtained in solution by dissolving in boiling nitric acid a stoichiometric mixture of BaCO3, La2O3, and HfO2 that had been heated at 1200 degrees C for 4 h. By complexing the ions with citric acid and using ammonia as fuel, it was possible to get Ba2LaHfO5.5 as nanoparticles in a single-step combustion process. The powder obtained by the present combustion process was characterized by X-ray diffraction, BET surface area analysis, differential thermal analysis, thermogravimetric analysis, infrared spectroscopy, and scanning and high-resolution transmission electron microscopy. According to the results of X-ray and electron diffraction, the powder synthesized through the combustion process showed single-phase barium lanthanum hafnium oxide. The transmission electron microscopic investigations showed a grain size of 42 nm, with a standard deviation of 8 nm. The nanoparticles of Ba2LaHfO5.5 synthesized by the present combustion technique could be sintered to > 97% of the theoretical density at a relatively low temperature of 1425 degrees C. Scanning electron microscopic studies on the sintered Ba2LaHfO5.5 samples showed that the final grain size of the sintered specimen was < 500 nm.

Calcium Compounds↗
PubMed1987

Efficacy of beta-diketonato complexes of titanium, zirconium, and hafnium against chemically induced autochthonous colonic tumors in rats.

Bis-beta-diketonato complexes of titanium, zirconium, and hafnium were tested against autochthonous colorectal tumors in rats. The model was found to reflect the clinical situation most closely. Of the compounds tested, budotitane was the most effective in terms of decrease in tumor weight and number and in increasing the lifespan of the treated animals. The therapeutic efficiency was superior to that of 5-fluorouracil, which so far has been the drug with the best activity in patients suffering from colon cancer.

Animals↗
PubMed2003

Synthesis of cubic zirconium and hafnium nitride having Th3P4 structure.

High-pressure synthesis is a powerful method for the preparation of novel materials with high elastic moduli and hardness. Additionally, such materials may exhibit interesting thermal, optoelectronic, semiconductuing, magnetic or superconducting properties. Here, we report on the high-pressure synthesis of zirconium and hafnium nitrides with the stoichiometry M3N4, where M = Zr, Hf. Synthesis experiments were performed in a laser-heated diamond anvil cell at pressures up to 18 GPa and temperatures up to 3,000 K. We observed formation of cubic Zr3N4 and Hf3N4 (c-M3N4) with a Th3P4-structure, where M-cations are eightfold coordinated by N anions. The c-M3N4 phases are the first binary nitrides with such a high coordination number. Both compounds exhibit high bulk moduli around 250 GPa, which indicates high hardness. Moreover, the new nitrides, c-Zr3N4 and c-Hf3N4, may be the first members of a larger group of transition metal and/or lanthanide nitrides with interesting ferromagnetic or superconducting behaviour.

Crystallization↗
PubMed2003

Vibrational frequencies and structural determination of hafnium tetrahydroborate.

The normal mode frequencies and corresponding vibrational assignments of of hafnium tetrahydroborate in T symmetry are examined theoretically using the Gaussian 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of to one of six types of motion (B-H stretch, Hf-B stretch, B-Hf-B bend, H-B-H bend, BH4 wag, and BH4 twist) predicted by a group theoretical analysis. By comparing the vibrational frequencies with IR and Raman spectra available in the literature, a set of scaling factors is derived. Theoretical IR and Raman intensities are reported. Quantum chemical calculations predict that the molecule does not possess strict Td symmetry. The Td structure possesses one negative eigenvalue. The minimum energy structure possesses T symmetry.

Borates↗