Hafnium

Al were cyclic oxidation tested at 1050°C in air on Inconel-718 substrates for up to 4370h. The Pt-diffused specimen failed most quickly, < 100 h, while the simple-NiAl aluminide maintained a positive weight change for ~1300 h. The Pt-modified aluminides clearly improved the cyclic oxidation behavior of both simple and Hf-modified aluminides, sustaining a zero weight change only after 3600 and 4000 h, respectively. The Hf additions did not immediately appear to produce as strong an improvement as expected, however, they were more highly ranked when normalized by coating thickness. They also decreased surface rumpling, important for TBC durability. Hf-rich NiAl grain boundaries, formed during coating processing, resulted in HfO2 particles in the scales and oxide pegs at the metal interface, all suggesting some level of over-doping. The high sulfur content of the substrate influenced spalling to bare metal and re-healing to less protective Ni(Al,Cr)2O4 spinel-type and (Ti,Cr,Nb)O2 rutile scales. The evolution of these surface features have been documented over 100 to 4370 h of exposure. The coating aluminum content near failure was ~2-3 wt. %.

Layered anorthosite complexes are typical components of Archean crustal domains. However, the geodynamic settings in which they were emplaced are still discussed as geological relationships are often ambiguous. Here we report major, trace element and high-precision high-field-strength-element (HFSE) data for the recently discovered well preserved Naajat Kuuat Anorthosite Complex from the inner Ameralik fjord region, southern West Greenland. The dataset is complemented by the first combined Hf–Nd isotope analyses for Archean layered anorthosite complexes and U–Pb zircon geochronology. The data contribute to the small database on Archean layered anorthosite complexes and are used to unravel the origin of these complexes and the tectonic regime involved. Fractional crystallisation of olivine, pyroxene, plagioclase and possibly amphibole controls major and trace element variations in the layered intrusion. There are two groups of amphibolites: (1) a group with primitive mantle normalized trace element patterns are similar to those of MORB-like basalts and (2) typical island-arc tholeiites (IAT), apparently indicating an island-arc setting. Lu–Hf regression lines yield an age of 2985 ± 59 Ma (MSWD 4) within the error of the Sm–Nd regression age of 2929 ± 110 Ma (MSWD 17). The initial ɛHf(2985) for the Naajat Kuuat rocks range from +1.6 to +5.8 and the initial ɛNd(2985) range from +0.4 to +3.9, either indicating variably depleted mantle sources or variable degrees of crustal contamination. In contrast to most mafic assemblages, ratios of Nb/Ta are highly variable (7.85 to 18.6), reflecting fractionation and accumulation of amphibole, ilmenite and pyroxene. The MORB-like parental liquids have the highest Nb/Ta of ca. 18, consistent with a mantle source overprinted by melt-like components from subducting oceanic crust with high Nb/Ta. The accumulation of plagioclase forming the anorthosites and the primary fractionation of amphibole as well as the occurrence of high-Al basalts within the Naajat Kuuat complex argue for hydrous parental liquids in support of an island-arc related setting. Zircon U–Pb geochronology from the anorthosite and adjacent tonalites reveal major tonalite intrusion into the complex at ca. 2802 Ma and a second regional event at ca. 2710 Ma, in accord with crustal heating due to micro-continent amalgamation and crustal thickening. Altogether, the geochemical data can be interpreted with a geodynamic model, where anorthosite-complex associated rocks intrude into tectonically thickened island-arc crust. Crustal thickening is possibly triggered by island-arc accretion, leading to the emplacement of TTG bodies that further thickened the crustal pile. Further collision and amalgamation with other proto-crustal assemblages might have led to enhanced crustal magmatism and granulite facies metamorphism.

Archaeological glass contains information about the movement of goods and ancient economies, yet our understanding of critical aspects of the ancient glass industry is fragmentary. During Roman times, distinct glass types produced in coastal regions of Egypt and the Levant used evaporitic soda (natron) mixed with Nile-derived sands. In the Levant, furnaces for producing colourless Roman glass by addition of manganese have been uncovered, whereas the source of the desirable antimony-decolourised Roman glass remains an enigma. In the Edict of Diocletian, this colourless glass is listed as “Alexandrian” referring to Egypt, but its origin has been ambiguous. Previous studies have found overlapping strontium and neodymium isotope ratios for Levantine and Egyptian glass. Here, we confirm these findings and show for the first time, based on glasses from the ancient city of Gerasa, that hafnium (Hf) isotopes are different in Egyptian and Levantine natron glasses, and that Sb Roman glass is ...

Films of Hf0.5Z0.5O2 (HZO) contain a network of grain boundaries. In (111) HZO epitaxial films on (001) SrTiO3, for instance, twinned orthorhombic (o-HZO) ferroelectric crystallites coexist with grain boundaries between o-HZO and a residual paraelectric monoclinic (m-HZO) phase. These grain boundaries contribute to the resistive switching response in addition to the genuine ferroelectric polarization switching and have detrimental effects on device performance. Here, it is shown that, by using suitable nanometric capping layers deposited on HZO film, a radical improvement of the operation window of the tunnel device can be achieved. Crystalline SrTiO3 and amorphous AlOx are explored as capping layers. It is observed that these layers conformally coat the HZO surface and allow to increase the yield and homogeneity of functioning ferroelectric junctions while strengthening endurance. Data show that the capping layers block ionic-like transport channels across grain boundaries. It is suggested that they act as oxygen suppliers to the oxygen-getters grain boundaries in HZO. In this scenario it could be envisaged that these and other oxides could also be explored and tested for fully compatible CMOS technologies.

Computational materials science based on ab initio calculations has become an important partner to experiment. This is demonstrated here for the effect of impurities and alloying elements on the strength of a Zr twist grain boundary, the dissociative adsorption and diffusion of iodine on a zirconium surface, the diffusion of oxygen atoms in a Ni twist grain boundary and in bulk Ni, and the dependence of the work function of a TiN-HfO(2) junction on the replacement of N by O atoms. In all of these cases, computations provide atomic-scale understanding as well as quantitative materials property data of value to industrial research and development. There are two key challenges in applying ab initio calculations, namely a higher accuracy in the electronic energy and the efficient exploration of large parts of the configurational space. While progress in these areas is fueled by advances in computer hardware, innovative theoretical concepts combined with systematic large-scale computations will be needed to realize the full potential of ab initio calculations for industrial applications.

Abstract The hard coatings application on cutting tools improves the lifetime, performance and also quality of the workpiece, usually by increasing the wear resistance. Hafnium nitride and vanadium nitride multilayer coatings [HfN/VN]n present mechanical, tribological and physical-chemical properties that have been identified previously by other authors and are desirable for cutting tools. With physical vapor deposition (PVD) of hafnium nitride/vanadium nitride [HfN/VN]n multilayer coatings were deposited with bilayer numbers n  = 1, n  = 50 and n  = 80 onto High-speed steel (HSS) cutting tools by using the Multi-target Magnetron Sputtering technique, the machining tools used as a substrate were burin ASSAB 17 steel. The uncoated tools and coated tools with HfN/VN multilayers were used to machine AISI 1020 steel bars at the same turning parameters by using a CNC machine. The cutting efficiency, machining quality, and tool wear are influenced by coating nature and the temperature, therefore, as an evaluation method the tool temperature, the steel temperature, and the machining chip temperature were measured by means an infrared sensor. The data analyses were carried out in MatLab, to identify average temperature and temperature rate for all machining tools. The superficial roughnesses ( Ra ) of workpieces were evaluated by using a roughness tester. Tool wear and surface wear mechanism were analyzed through Scanning Electron Microscopy (SEM). In this work it was found that temperature rates on machining tools and on machined workpieces were decreased, in relation to chip temperatures which exhibit an increasing. The workpiece roughness was reduced around 28%, and the wear rate was reduced around 50%, in relation to the uncoated and coated tools with [HfN/VN]n multilayers. Results showed in this research reveal that [HfN/VN]n multilayers, as function of bilayer number (n), improve the lifetime of the cutting tools due to the reduction of energy transfer and the increase in wear resistance, with low friction coefficient between cutting tool and workpiece evidenced in the surface roughness associated to the workpiece.

Hafnium nitride monolayer coatings were deposited as thin films on high-speed steel by magnetron sputtering physical vapor deposition. Uncoated high-speed steels ASSAB 17 were used as reference systems, for machining on AISI1020 steel by chip removal, measuring the temperature during the process. Wear resistance of the tools was characterized by using scanning electron microscopy, and through of the surfaces of the steel using a roughness tester. It was evidenced that the use of monolayer hafnium coatings on uncoated high-speed steel reduces the adhesive wear of the tool and the energy transfer during the cutting process. Also, hafnium nitride coating offers advantages in its application to chip removal process of ferrous metals, by increasing the life of the tool, improving the quality of the work piece, and reducing cutting process time and cost.

Nanotubes are fabricated by atomic layer deposition (ALD) into nanopore arrays created by anodic aluminum oxide (AAO). A transmission electron microscopy (TEM) methodology is developed and applied to quantify the ALD conformality in the nanopores (thickness as a function of depth), and the results are compared to existing models for ALD conformality. ALD HfO2 nanotubes formed in AAO templates are released by dissolution of the Al2O3, transferred to a grid, and imaged by TEM. An algorithm is devised to automate the quantification of nanotube wall thickness as a function of position along the central axis of the nanotube, by using a cylindrical model for the nanotube. Diffusion-limited depletion occurs in the lower portion of the nanotubes and is characterized by a linear slope of decreasing thickness. Experimentally recorded slopes match well with two simple models of ALD within nanopores presented in the literature. The TEM analysis technique provides a method for the rapid analysis of such nanostructures in general, and is also a means to efficiently quantify ALD profiles in nanostructures for a variety of nanodevice applications.

About 3000 years ago, a major vegetation change occurred in Central Africa, when rainforest trees were abruptly replaced by savannas. Up to this point, the consensus of the scientific community has been that the forest disturbance was caused by climate change. We show here that chemical weathering in Central Africa, reconstructed from geochemical analyses of a marine sediment core, intensified abruptly at the same period, departing substantially from the long-term weathering fluctuations related to the Late Quaternary climate. Evidence that this weathering event was also contemporaneous with the migration of Bantu-speaking farmers across Central Africa suggests that human land-use intensification at that time had already made a major impact on the rainforest.

Nanotubes are fabricated by atomic layer deposition (ALD) into nanopore arrays created by anodic aluminum oxide (AAO). A transmission electron microscopy (TEM) methodology is developed and applied to quantify the ALD conformality in the nanopores (thickness as a function of depth), and the results are compared to existing models for ALD conformality. ALD HfO2 nanotubes formed in AAO templates are released by dissolution of the Al2O3, transferred to a grid, and imaged by TEM. An algorithm is devised to automate the quantification of nanotube wall thickness as a function of position along the central axis of the nanotube, by using a cylindrical model for the nanotube. Diffusion-limited depletion occurs in the lower portion of the nanotubes and is characterized by a linear slope of decreasing thickness. Experimentally recorded slopes match well with two simple models of ALD within nanopores presented in the literature. The TEM analysis technique provides a method for the rapid analysis of such nanostructures in general, and is also a means to efficiently quantify ALD profiles in nanostructures for a variety of nanodevice applications.

... ac et yl f er roc en e with et h yl enedi ami n e , INTRODUCTION Hafnium chemistry has grown ata rapid pace, as evidenced by the diversified applications of hafnium and its cornpcunds 66 1 Copyright 0 1997 by Marcel Dekker, Inc Page 2. 662 MISHRA. ...

In this work we propose a novel method of immobilizing nucleic acids for field effect or high electron mobility transistor-based biosensors. The naturally occurring 5′ terminal phosphate group on nucleic acids was used to coordinate with semiconductor and metal oxide surfaces. We demonstrate that DNA can be directly immobilized onto ZrO2, AlGaN, GaN, and HfO2 while retaining its ability to hybridize to target sequences with high specificity. By directly immobilizing the probe molecule to the sensor surface, as opposed to conventional crosslinking strategies, the number of steps in device fabrication is reduced. Furthermore, hybridization to target strands occurs closer to the sensor surface, which has the potential to increase device sensitivity by reducing the impact of the Debye screening length.

Zirconium, titanium, and hafnium oxide-coated stainless steel surfaces are fabricated by reactive landing of gas-phase ions produced by electrospray ionization of group IVB metal alkoxides. The surfaces are used for in situ enrichment of phosphopeptides before analysis by matrix-assisted laser desorption ionization (MALDI) mass spectrometry. To evaluate this method we characterized ZrO2 (zirconia) surfaces by (1) comparison with the other