CONTRIBUTION TO THE STUDY OF ZIRCONIUM AND HAFNIUM ALPHA-HYDROXYCARBOXYLATES

A study of both zirconium and hafnium alpha-hydroxycarboxylates for analytical applications is presented, These compounds are studied by infrared spectroscopy, thermal analysis and X-ray diffractometry. dl-Mandelic, dl-p-bromomandelic and dl-2-naphthylglycolic acids are the more adequate reagents for gravimetric determinations of zirconium and hafnium, the ligands dl-2-hydroxyhexanoic and dl-2-hydroxydodecanoic acids were used for the first time and the results showed that they are also adequate reagents for the same purpose.

High-frequency global navigation satellite system’s receivers for airborne gravimetry

The development of global navigation satellite systems (GNSS) provides a solution of many applied problems with increasingly higher quality and accuracy nowadays. Researches that are carried out by the Bavarian Academy of Sciences and Humanities in Munich (BAW) in the field of airborne gravimetry are based on sophisticated data processing from high frequency GNSS receiver for kinematic aircraft positioning. Applied algorithms for inertial acceleration determination are based on the high sampling rate (50Hz) and on reducing of such factors as ionosphere scintillation and multipath at aircraft /antenna near field effects. The quality of the GNSS derived kinematic height are studied also by intercomparison with lift height variations collected by a precise high sampling rate vertical scale [1]. This work is aimed at the ways of more accurate determination of mini-aircraft altitude by means of high frequency GNSS receivers, in particular by considering their dynamic behaviour.

Thermal activation parameters for low temperature deformation of alpha-hafnium

Abstract is not available.

Growth of hafnium and zirconium suicides by reactive diffusion

Diffusion controlled growth of the phases in Hf-Si and Zr-Si systems are studied by bulk diffusion couple technique. Only two phases grow in the interdiffusion zone, although several phases are present in both the systems. The location of the Kirkendall marker plane, detected based on the grain morphology, indicates that disilicides grow by the diffusion of Si. Diffusion of the metal species in these phases is negligible. This indicates that vacancies are present mainly on the Si sublattice. The activation energies for integrated diffusion coefficients in the HfSi2 and ZrSi2 are estimated as 394 +/- 37 and 346 +/- 34 kJ mol(-1), respectively. The same is calculated for the HfSi phase as 485 +/- 42 kJ mol(-1). The activation energies for Si tracer diffusion in the HfSi2 and ZrSi2 phases are estimated as 430 +/- 36 and 348 +/- 34 kJ mol(-1), respectively. (C) 2013 Elsevier B.V. All rights reserved.

Growth of hafnium and zirconium suicides by reactive diffusion

Diffusion controlled growth of the phases in Hf-Si and Zr-Si systems are studied by bulk diffusion couple technique. Only two phases grow in the interdiffusion zone, although several phases are present in both the systems. The location of the Kirkendall marker plane, detected based on the grain morphology, indicates that disilicides grow by the diffusion of Si. Diffusion of the metal species in these phases is negligible. This indicates that vacancies are present mainly on the Si sublattice. The activation energies for integrated diffusion coefficients in the HfSi2 and ZrSi2 are estimated as 394 +/- 37 and 346 +/- 34 kJ mol(-1), respectively. The same is calculated for the HfSi phase as 485 +/- 42 kJ mol(-1). The activation energies for Si tracer diffusion in the HfSi2 and ZrSi2 phases are estimated as 430 +/- 36 and 348 +/- 34 kJ mol(-1), respectively. (C) 2013 Elsevier B.V. All rights reserved.

Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

High-density remote plasma sputtering of high-dielectric-constant amorphous hafnium oxide films

Hafnium oxide (HfOx) is a high dielectric constant (k) oxide which has been identified as being suitable for use as the gate dielectric in thin film transistors (TFTs). Amorphous materials are preferred for a gate dielectric, but it has been an ongoing challenge to produce amorphous HfOx while maintaining a high dielectric constant. A technique called high target utilization sputtering (HiTUS) is demonstrated to be capable of depositing high-k amorphous HfOx thin films at room temperature. The plasma is generated in a remote chamber, allowing higher rate deposition of films with minimal ion damage. Compared to a conventional sputtering system, the HiTUS technique allows finer control of the thin film microstructure. Using a conventional reactive rf magnetron sputtering technique, monoclinic nanocrystalline HfOx thin films have been deposited at a rate of ∼1.6nmmin-1 at room temperature, with a resistivity of 1013Ωcm, a breakdown strength of 3.5MVcm-1 and a dielectric constant of ∼18.2. By comparison, using the HiTUS process, amorphous HfOx (x=2.1) thin films which appear to have a cubic-like short-range order have been deposited at a high deposition rate of ∼25nmmin-1 with a high resistivity of 1014Ωcm, a breakdown strength of 3MVcm-1 and a high dielectric constant of ∼30. Two key conditions must be satisfied in the HiTUS system for high-k HfOx to be produced. Firstly, the correct oxygen flow rate is required for a given sputtering rate from the metallic target. Secondly, there must be an absence of energetic oxygen ion bombardment to maintain an amorphous microstructure and a high flux of medium energy species emitted from the metallic sputtering target to induce a cubic-like short range order. This HfOx is very attractive as a dielectric material for large-area electronic applications on flexible substrates. A remote plasma sputtering process (high target utilization sputtering, HiTUS) has been used to deposit amorphous hafnium oxide with a very high dielectric constant (∼30). X-ray diffraction shows that this material has a microstructure in which the atoms have a cubic-like short-range order, whereas radio frequency (rf) magnetron sputtering produced a monoclinic polycrystalline microstructure. This is correlated to the difference in the energetics of remote plasma and rf magnetron sputtering processes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Discovery of Highly Excited Long-Lived Isomers in Neutron-Rich Hafnium and Tantalum Isotopes through Direct Mass Measurements

A study of cooled Au-197 projectile-fragmentation products has been performed with a storage ring. This has enabled metastable nuclear excitations with energies up to 3 MeV, and half-lives extending to minutes or longer, to be identified in the neutron-rich nuclides Hf-183,Hf-184,Hf-186 and Ta-186,Ta-187. The results support the prediction of a strongly favored isomer region near neutron number 116.