Ignition and combustion of bulk metals under elevated, normal and reduced gravity conditions

NASA Technical Reports Server (NTRS)

Abbud-Madrid, Angel; Branch, Melvyn C.; Daily, John W.

1995-01-01

This research effort is aimed at providing further insight into this multi-variable dependent phenomena by looking at the effects of gravity on the ignition and combustion behavior of metals. Since spacecraft are subjected to higher-than-1g gravity loads during launch and reentry and to zero-gravity environments while in orbit, the study of ignition and combustion of bulk metals at different gravitational potentials is of great practical concern. From the scientific standpoint, studies conducted under microgravity conditions provide simplified boundary conditions since buoyancy is removed, and make possible the identification of fundamental ignition mechanisms. The effect of microgravity on the combustion of bulk metals has been investigated by Steinberg, et al. on a drop tower simulator. However, no detailed quantitative work has been done on ignition phenomena of bulk metals at lower or higher-than-normal gravitational fields or on the combustion characteristics of metals at elevated gravity. The primary objective of this investigation is the development of an experimental system capable of providing fundamental physical and chemical information on the ignition of bulk metals under different gravity levels. The metals used in the study, iron (Fe), titanium (Ti), zirconium (Zr), magnesium (Mg), zinc (Zn), and copper (Cu) were selected because of their importance as elements of structural metals and their simple chemical composition (pure metals instead of multi-component alloys to avoid complication in morphology and spectroscopic studies). These samples were also chosen to study the two different combustion modes experienced by metals: heterogeneous or surface oxidation, and homogeneous or gas-phase reaction. The experimental approach provides surface temperature profiles, spectroscopic measurements, surface morphology, x-ray spectrometry of metals specimens and their combustion products, and high-speed cinematography of the heating, ignition and combustion

Lamellar zirconium phosphates to host metals for catalytic purposes.

PubMed

Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

2018-02-27

In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

Biocompatibility evaluation of sputtered zirconium-based thin film metallic glass-coated steels.

PubMed

Subramanian, Balasubramanian; Maruthamuthu, Sundaram; Rajan, Senthilperumal Thanka

2015-01-01

Thin film metallic glasses comprised of Zr48Cu36Al8Ag8 (at.%) of approximately 1.5 μm and 3 μm in thickness were prepared using magnetron sputtering onto medical grade 316L stainless steel. Their structural and mechanical properties, in vitro corrosion, and antimicrobial activity were analyzed. The amorphous thin film metallic glasses consisted of a single glassy phase, with an absence of any detectable peaks corresponding to crystalline phases. Elemental composition close to the target alloy was noted from EDAX analysis of the thin film. The surface morphology of the film showed a smooth surface on scanning electron microscopy and atomic force microscopy. In vitro electrochemical corrosion studies indicated that the zirconium-based metallic glass could withstand body fluid, showing superior resistance to corrosion and electrochemical stability. Interactions between the coated surface and bacteria were investigated by agar diffusion, solution suspension, and wet interfacial contact methods. The results indicated a clear zone of inhibition against the growth of microorganisms such as Escherichia coli and Staphylococcus aureus, confirming the antimicrobial activity of the thin film metallic glasses. Cytotoxicity studies using L929 fibroblast cells showed these coatings to be noncytotoxic in nature.

Biocompatibility evaluation of sputtered zirconium-based thin film metallic glass-coated steels

PubMed Central

Subramanian, Balasubramanian; Maruthamuthu, Sundaram; Rajan, Senthilperumal Thanka

2015-01-01

Thin film metallic glasses comprised of Zr48Cu36Al8Ag8 (at.%) of approximately 1.5 μm and 3 μm in thickness were prepared using magnetron sputtering onto medical grade 316L stainless steel. Their structural and mechanical properties, in vitro corrosion, and antimicrobial activity were analyzed. The amorphous thin film metallic glasses consisted of a single glassy phase, with an absence of any detectable peaks corresponding to crystalline phases. Elemental composition close to the target alloy was noted from EDAX analysis of the thin film. The surface morphology of the film showed a smooth surface on scanning electron microscopy and atomic force microscopy. In vitro electrochemical corrosion studies indicated that the zirconium-based metallic glass could withstand body fluid, showing superior resistance to corrosion and electrochemical stability. Interactions between the coated surface and bacteria were investigated by agar diffusion, solution suspension, and wet interfacial contact methods. The results indicated a clear zone of inhibition against the growth of microorganisms such as Escherichia coli and Staphylococcus aureus, confirming the antimicrobial activity of the thin film metallic glasses. Cytotoxicity studies using L929 fibroblast cells showed these coatings to be noncytotoxic in nature. PMID:26491304

METHOD OF PREPARING SINTERED ZIRCONIUM METAL FROM ITS HYDRIDES

DOEpatents

Angier, R.P.

1958-02-11

The invention relates to the preparation of metal shapes from zirconium hydride by powder metallurgical techniques. The zirconium hydride powder which is to be used for this purpose can be prepared by rendering massive pieces of crystal bar zirconium friable by heat treatment in purified hydrogen. This any then be ground into powder and powder can be handled in the air without danger of it igniting. It may then be compacted in the normal manner by being piaced in a die. The compact is sintered under vacuum conditions preferably at a temperature ranging from 1200 to 1300 deg C and for periods of one to three hours.

Recent advances in bulk metallic glasses for biomedical applications.

PubMed

Li, H F; Zheng, Y F

2016-05-01

With a continuously increasing aging population and the improvement of living standards, large demands of biomaterials are expected for a long time to come. Further development of novel biomaterials, that are much safer and of much higher quality, in terms of both biomedical and mechanical properties, are therefore of great interest for both the research scientists and clinical surgeons. Compared with the conventional crystalline metallic counterparts, bulk metallic glasses have unique amorphous structures, and thus exhibit higher strength, lower Young's modulus, improved wear resistance, good fatigue endurance, and excellent corrosion resistance. For this purpose, bulk metallic glasses (BMGs) have recently attracted much attention for biomedical applications. This review discusses and summarizes the recent developments and advances of bulk metallic glasses, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based alloying systems for biomedical applications. Future research directions will move towards overcoming the brittleness, increasing the glass forming ability (GFA) thus obtaining corresponding bulk metallic glasses with larger sizes, removing/reducing toxic elements, and surface modifications. Bulk metallic glasses (BMGs), also known as amorphous alloys or liquid metals, are relative newcomers in the field of biomaterials. They have gained increasing attention during the past decades, as they exhibit an excellent combination of properties and processing capabilities desired for versatile biomedical implant applications. The present work reviewed the recent developments and advances of biomedical BMGs, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based BMG alloying systems. Besides, the critical analysis and in-depth discussion on the current status, challenge and future development of biomedical BMGs are included. The possible solution to the BMG size limitation, the brittleness of BMGs has been

A Fundamental Approach to Developing Aluminium based Bulk Amorphous Alloys based on Stable Liquid Metal Structures and Electronic Equilibrium - 154041

DTIC Science & Technology

2017-03-28

AFRL-AFOSR-JP-TR-2017-0027 A Fundamental Approach to Developing Aluminium-based Bulk Amorphous Alloys based on Stable Liquid -Metal Structures and...to 16 Dec 2016 4.  TITLE AND SUBTITLE A Fundamental Approach to Developing Aluminium-based Bulk Amorphous Alloys based on Stable Liquid -Metal...including Al, Cu, Ni, Zr, Mg, Pd, Ga , Ca. Many new Al-based amorphous alloys were found within the numerous alloy systems studied in this project, and

Dual Role of Water in Heterogeneous Catalytic Hydrolysis of Sarin by Zirconium-Based Metal-Organic Frameworks.

PubMed

Momeni, Mohammad R; Cramer, Christopher J

2018-05-22

Recent experimental studies on Zr IV -based metal-organic frameworks (MOFs) have shown the extraordinary effectiveness of these porous materials for the detoxification of phosphorus-based chemical warfare agents (CWAs). However, pressing challenges remain with respect to characterizing these catalytic processes both at the molecular and crystalline levels. We here use theory to compare the reactivity of different zirconium-based MOFs for the catalytic hydrolysis of the CWA sarin, using both periodic and cluster modeling. We consider both hydrated and dehydrated secondary building units, as well as linker functionalized MOFs, to more fully understand and rationalize available experimental findings as well as to enable concrete predictions for achieving higher activities for the decomposition of CWAs.

Ignition and Combustion Characteristics of Pure Bulk Metals: Normal-Gravity Test Results

NASA Technical Reports Server (NTRS)

Abbud-Madrid, A.; Fiechtner, G. J.; Branch, M. C.; Daily, J. W.

1994-01-01

An experimental apparatus has been designed for the study of bulk metal ignition under elevated, normal and reduced gravity environments. The present work describes the technical characteristics of the system, the analytical techniques employed, the results obtained from the ignition of a variety of metals subjected to normal gravity conditions and the first results obtained from experiments under elevated gravity. A 1000 W xenon short-arc lamp is used to irradiate the top surface of a cylindrical metal specimen 4 mm in diameter and 4 mm high in a quiescent pure-oxygen environment at 0.1 MPa. Iron, titanium, zirconium, magnesium, zinc, tin, and copper specimens are investigated. All these metals exhibit ignition and combustion behavior varying in strength and speed. Values of ignition temperatures below, above or in the range of the metal melting point are obtained from the temperature records. The emission spectra from the magnesium-oxygen gas-phase reaction reveals the dynamic evolution of the ignition event. Scanning electron microscope and x-ray spectroscopic analysis provide the sequence of oxide formation on the burning of copper samples. Preliminary results on the effect of higher-than-normal gravity levels on the ignition of titanium specimens is presented.

Shear band evolution in zirconium/hafnium-based bulk metallic glasses under static and dynamic indentations

NASA Astrophysics Data System (ADS)

Zhang, Hongwen

In this thesis, a detailed investigation of thermal stability and mechanical deformation behavior of Zr/Hf-based Bulk Metallic Glasses is conducted. First, systematic studies had been implemented to understand the influence of relative compositions of Zr and Hf on thermal stability and mechanical property evolution. Second, shear band evolution under indentations were investigated experimentally and theoretically. It was found in the present work that gradually replacing Zr by Hf remarkably increases the density and improves the mechanical properties. However, a slight decrease in glass forming ability with increasing Hf content has also been identified through thermodynamic analysis although all the materials in the current study were still found to be amorphous. Many indentation studies have revealed only a few shear bands surrounding the indent on the top surface of the specimen. This small number of shear bands cannot account for the large plastic deformation beneath the indentations. Therefore, a bonded interface technique has been used to observe the slip-steps due to shear band evolution. Vickers indentations were performed along the interface of the bonded split specimen at increasing loads. At small indentation loads, the plastic deformation was primarily accommodated by semi-circular primary shear bands surrounding the indentation. At higher loads, secondary and tertiary shear bands were formed inside this plastic zone. A modified expanding cavity model was then used to predict the plastic zone size characterized by the shear bands and to identify the stress components responsible for the evolution of the various types of shear bands. The applicability of various hardness - yield-strength (H-sigma y) relationships currently available in the literature for bulk metallic glasses (BMGs) is also investigated. Experimental data generated on ZrHf-based BMGs in the current study and those available elsewhere on other BMG compositions were used to validate the

Systems and Methods for Implementing Bulk Metallic Glass-Based Strain Wave Gears and Strain Wave Gear Components

NASA Technical Reports Server (NTRS)

Hofmann, Douglas C. (Inventor); Wilcox, Brian (Inventor)

2016-01-01

Bulk metallic glass-based strain wave gears and strain wave gear components. In one embodiment, a strain wave gear includes: a wave generator; a flexspline that itself includes a first set of gear teeth; and a circular spline that itself includes a second set of gear teeth; where at least one of the wave generator, the flexspline, and the circular spline, includes a bulk metallic glass-based material.

Hafnium-Based Bulk Metallic Glasses for Kinetic Energy Penetrators

DTIC Science & Technology

2004-12-01

uranium -based (DU) and tungsten- nickel -iron (W-Ni-Fe) composite kinetic energy (KE) munitions is primarily ascribed to their high densities (U: ρ...based on an invariant point identified in the hafnium- copper- nickel ternary system. They are denser than zirconium-based glass-forming compositions...depleted- uranium penetrators. 1. INTRODUCTION 1.1 Criterion for Effective Kinetic Energy Penetrator Performance The lethality of depleted

Composition formulas of Fe-based transition metals-metalloid bulk metallic glasses derived from dual-cluster model of binary eutectics.

PubMed

Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang

2017-08-22

It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3  + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.

Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

NASA Astrophysics Data System (ADS)

Karahan, Aydın

2011-07-01

Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other

Friction stir welding of Zr-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Ji, Y. S.; Fujii, H.; Maeda, M.; Nakata, K.; Kimura, H.; Inoue, A.; Nogi, K.

2009-05-01

A Zr55Cu30Al10Ni5 bulk metallic glass plate was successfully welded below its crystallization temperature by friction stir welding. The flash formation and heat concentration at the shoulder edge was minimized using a wider tool and the angle of the recessed shoulder surface was 3°. To analyze the crystallization of the base material and stir zone, the microstructure and mechanical properties were analyzed using DSC, XRD, TEM, and micro-hardness. As a result, it was found that the amorphous structure and original mechanical properties were maintained in the whole joints.

Microgravity metal processing: from undercooled liquids to bulk metallic glasses

PubMed Central

Hofmann, Douglas C; Roberts, Scott N

2015-01-01

Bulk metallic glasses (BMGs) are a novel class of metal alloys that are poised for widespread commercialization. Over 30 years of NASA and ESA (as well as other space agency) funding for both ground-based and microgravity experiments has resulted in fundamental science data that have enabled commercial production. This review focuses on the history of microgravity BMG research, which includes experiments on the space shuttle, the ISS, ground-based experiments, commercial fabrication and currently funded efforts. PMID:28725709

Mechanical relaxation in a Zr-based bulk metallic glass: Analysis based on physical models

NASA Astrophysics Data System (ADS)

Qiao, J. C.; Pelletier, J. M.

2012-08-01

The mechanical relaxation behavior in a Zr55Cu30Ni5Al10 bulk metallic glass is investigated by dynamic mechanical analysis in both temperature and frequency domains. Master curves can be obtained for the storage modulus G' and for the loss modulus G'', confirming the validity of the time-temperature superposition principle. Different models are discussed to describe the main (α) relaxation, e.g., Debye model, Havriliak-Negami (HN) model, Kohlrausch-Williams-Watt (KWW) model, and quasi-point defects (QPDs) model. The main relaxation in bulk metallic glass cannot be described using a single relaxation time. The HN model, the KWW model, and the QPD theory can be used to fit the data of mechanical spectroscopy experiments. However, unlike the HN model and the KWW model, some physical parameters are introduced in QPD model, i.e., atomic mobility and correlation factor, giving, therefore, a new physical approach to understand the mechanical relaxation in bulk metallic glasses.

A New Class of Metal-Cyclam-Based Zirconium Metal-Organic Frameworks for CO2 Adsorption and Chemical Fixation.

PubMed

Zhu, Jie; Usov, Pavel M; Xu, Wenqian; Celis-Salazar, Paula J; Lin, Shaoyang; Kessinger, Matthew C; Landaverde-Alvarado, Carlos; Cai, Meng; May, Ann M; Slebodnick, Carla; Zhu, Dunru; Senanayake, Sanjaya D; Morris, Amanda J

2018-01-24

Metal-organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr 6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO 2 uptake capacity (up to ∼9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO 2 with epoxides, including sterically hindered epoxides. The MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.

Separation of Zirconium and Hafnium: A Review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium. This paper provides an overview of the processes for separating hafnium from zirconium. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The current dominant zirconium production route involves pyrometallurgical ore cracking, multi-step hydrometallurgical liquid-liquid extraction for hafnium removal and the reduction of zirconium tetrachloride to the pure metal by the Kroll process. The lengthy hydrometallurgical Zr-Hf separation operations leads to high production cost, intensive labour and heavy environmental burden. Using a compact pyrometallurgical separation method can simplify the whole production flowsheet with a higher process efficiency. The known separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt extraction. The commercially operating extractive distillation process is a significant advance in Zr-Hf separation technology but it suffers from high process maintenance cost. The recently developed new process based on molten salt-metal equilibrium for Zr-Hf separation shows a great potential for industrial application, which is compact for nuclear grade zirconium production starting from crude ore. In the present paper, the available separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

Enhancement of yield strength in zirconium metal through high-pressure induced structural phase transition

NASA Astrophysics Data System (ADS)

Zhao, Yusheng; Zhang, Jianzhong

2007-11-01

We report here a high-pressure phase-transition induced strengthening in ultrapure zirconium metal. The determined yield strength shows more than sixfold abrupt increase at the transition pressure of Pc=6GPa, from σyα≈180MPa in the low-pressure phase of α-Zr to σyω≈1180MPa in the high-pressure phase of ω-Zr. The observed enhancement provides an alternate route for material strengthening and is the most significant among the known strengthening techniques for metals. Our findings support the theoretical simulations of the substantial covalent bonding and "rougher" corrugation of slip planes for dislocations in the ω-phase of zirconium.

Tribological characterisation of Zr-based bulk metallic glass in simulated physiological media

NASA Astrophysics Data System (ADS)

Chen, Q.; Chan, K. C.; Liu, L.

2011-10-01

Due to their excellent wear resistant properties and high strength, as well as a low Young's modulus, Zr-based bulk metallic glasses (BMGs) are potentially suitable biomaterials for low-friction arthroplasty. The wear characteristics of the Zr60.14Cu22.31Fe4.85Al9.7Ag3 bulk amorphous alloy against ultra-high-molecular-weight polyethylene (UHMWPE) compared to a CoCrMo/UHMWPE combination were investigated in two different wear screening test devices, reciprocating and unidirectional. Hank's solution and sterile calf bovine serum were selected as the lubricant fluid media. It was found that different fluid media had insignificant effect on polyethylene wear against BMG counterfaces. The wear behaviour obtained on both test devices demonstrated that Zr-based BMG achieved UHMWPE counterface wear rates superior to conventional cast CoCrMo alloy, where the wear rate of UHMWPE is decreased by over 20 times. The tribological performance of these joints is superior to that of conventional metal-on-polymer designs. Contact angle measurements suggested that the advantage of BMG over a CoCrMo alloy counterface is attributed to its highly hydrophilic surfaces.

Degradation of Zr-based bulk metallic glasses used in load-bearing implants: A tribocorrosion appraisal.

PubMed

Zhao, Guo-Hua; Aune, Ragnhild E; Mao, Huahai; Espallargas, Nuria

2016-07-01

Owing to the amorphous structure, Bulk Metallic Glasses (BMGs) have been demonstrating attractive properties for potential biomedical applications. In the present work, the degradation mechanisms of Zr-based BMGs with nominal compositions Zr55Cu30Ni5Al10 and Zr65Cu18Ni7Al10 as potential load-bearing implant material were investigated in a tribocorrosion environment. The composition-dependent micro-mechanical and tribological properties of the two BMGs were evaluated prior to the tribocorrosion tests. The sample Zr65-BMG with a higher Zr content exhibited increased plasticity but relatively reduced wear resistance during the ball-on-disc tests. Both BMGs experienced abrasive wear after the dry wear test under the load of 2N. The cross-sectional subsurface structure of the wear track was examined by Focused Ion Beam (FIB). The electrochemical properties of the BMGs in simulated body fluid were evaluated by means of potentiodynamic polarization and X-ray Photoelectron Spectroscopy (XPS). The spontaneous passivation of Zr-based BMGs in Phosphate Buffer Saline solution was mainly attributed to the highly concentrated zirconium cation (Zr(4+)) in the passive film. The tribocorrosion performance of the BMGs was investigated using a reciprocating tribometer equipped with an electrochemical cell. The more passive nature of the Zr65-BMG had consequently a negative influence on its tribocorrosion resistance, which induced the wear-accelerated corrosion and eventually speeded-up the degradation process. It has been revealed the galvanic coupling was established between the depassivated wear track and the surrounding passive area, which is the main degradation mechanism for the passive Zr65-BMG subjected to the tribocorrosion environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Explosive Welding of Aluminum, Titanium and Zirconium to Copper Sheet Metal

NASA Technical Reports Server (NTRS)

Hegazy, A. A.; Mote, J. D.

1985-01-01

The main material properties affecting the explosive weldability of a certain metal combination are the yield strength, the ductility, the density and the sonic velocity of the two metals. Successful welding of the metal combination depends mainly on the correct choice of the explosive welding parameters; i.e., the stand off distance, the weight of the explosive charge relative to the weight of the flyer plate and the detonation velocity of the explosive. Based on the measured and the handbook values of the properties of interest, the explosive welding parameters were calculated and the arrangements for the explosive welding of the Al alloy 6061-T6, titanium and zirconium to OFHC copper were determined. The relatively small sheet metal thickness (1/8") and the fact that the thickness of the explosive layer must exceed a certain minimum value were considered during the determination of the explosive welding conditions. The results of the metallographic investigations and the measurements of the shear strength at the interface demonstrate the usefulness of these calculations to minimize the number of experimental trials.

Economic manufacturing of bulk metallic glass compositions by microalloying

DOEpatents

Liu, Chain T.

2003-05-13

A method of making a bulk metallic glass composition includes the steps of:a. providing a starting material suitable for making a bulk metallic glass composition, for example, BAM-11; b. adding at least one impurity-mitigating dopant, for example, Pb, Si, B, Sn, P, to the starting material to form a doped starting material; and c. converting the doped starting material to a bulk metallic glass composition so that the impurity-mitigating dopant reacts with impurities in the starting material to neutralize deleterious effects of the impurities on the formation of the bulk metallic glass composition.

Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

SK, Mostakim; Grzywa, Maciej; Volkmer, Dirk

2015-12-15

The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr{sub 6}O{sub 4}(OH){sub 4}(DMTDC){sub 6}]·4.8DMF·10H{sub 2}O (1) (H{sub 2}DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl{sub 4}, H{sub 2}DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl{sub 4}/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achievedmore » by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N{sub 2} and CO{sub 2} sorption analyses suggest that the material possesses remarkably high microporosity (S{sub BET}=1236 m{sup 2} g{sup −1}; CO{sub 2} uptake=3.5 mmol g{sup −1} at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N{sub 2} and CO{sub 2} sorption experiments

Plastic deformation behaviors of Ni- and Zr-based bulk metallic glasses subjected to nanoindentation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weizhong, Liang, E-mail: wzliang1966@126.com; Zhiliang, Ning; Zhenqian, Dang

2013-12-15

Plastic deformation behaviors of Ni{sub 42}Ti{sub 20}Zr{sub 21.5}Al{sub 8}Cu{sub 5}Si{sub 3.5} and Zr{sub 51}Ti{sub 5}Ni{sub 10}Cu{sub 25}Al{sub 9} bulk metallic glasses at room temperature were studied by nanoindentation testing and atomic force microscopy under equivalent indentation experimental conditions. The different chemical composition of these two bulk metallic glasses produced variant tendencies for displacement serrated flow to occur during the loading process. The nanoindentation strain rate was calculated as a function of indentation displacement in order to verify the occurrence of displacement serrated flow at different loading rates. Atomic force microscopy revealed decreasing numbers of discrete shear bands around the indentationmore » sites as loading rates increased from 0.025 to 2.5 mNs{sup −1}. Variations in plastic deformation behaviors between Ni and Zr-based glasses materials can be explained by the different metastable microstructures and thermal stabilities of the two materials. The mechanism governing plastic deformation of these metallic glasses was analyzed in terms of an established model of the shear transformation zone. - Highlights: • Plastic deformation of Ni- and Zr-based BMG is studied under identical conditions • Zr-based BMG undergoes a greater extent of plastic deformation than Ni-based BMG • Nanoindentation strain rate is studied to clarify variation in plastic deformation • Metastable microstructure, thermal stability affect BMG plastic deformation.« less

Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

NASA Astrophysics Data System (ADS)

Meier, R.; Souček, P.; Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P.; Fanghänel, Th.

2016-04-01

A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An-Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An-Al alloys using a LiCl-KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions.

Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

PubMed Central

Qin, Chunling; Zhao, Weimin; Inoue, Akihisa

2011-01-01

This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni) and Cu–Zr–Ag–Al–(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance. PMID:21731441

Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework

DOE PAGES

Wang, Hao; Wang, Qining; Teat, Simon J.; ...

2017-02-15

Porous metal-organic framework (MOF) materials with high thermal and water stability are desirable for various adsorption based applications. Early transition metal based MOFs such as those built on zirconium metal have been well recognized for their excellent stability toward heat and/or moisture. However, the difficulty growing large single crystals makes their structural characterization challenging. Herein we report a porous Zr-MOF, [Zr 6O 4(OH) 4(cca) 6] (Zr-cca), which is assembled from zirconium and 4-carboxycinnamic acid (H 2cca) under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the structure of Zr-cca is isoreticular to the prototype zirconium based MOF, UiO-66. Zr-ccamore » shows permanent porosity upon removal of solvent molecules initially residing inside the pores, with a BET surface area of 1178 m 2/g. As expected, it exhibits good thermal stability (stable up to 400 °C) and high resistance to acidity over a wide pH range. Evaluation of its gas adsorption performance on various hydrocarbons and fluorocarbons indicates that it preferentially adsorbs C 3 and C 4 hydrocarbons over C 2 analogues. At 30°C Zr-cca takes up more than 50 wt % of perfluorohexane and the adsorption-desorption process is fully recyclable. We have compared this material with UiO-66 and studied the underlying reasons for the difference in their adsorption performance toward perfluorohexane.« less

Piezoelectric coefficients of bulk 3R transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Konabe, Satoru; Yamamoto, Takahiro

2017-09-01

The piezoelectric properties of bulk transition metal dichalcogenides (TMDCs) with a 3R structure were investigated using first-principles calculations based on density functional theory combined with the Berry phase treatment. Values for the elastic constant Cijkl , the piezoelectric coefficient eijk , and the piezoelectric coefficient dijk are given for bulk 3R-TMDCs (MoS2, MoSe2, WS2, and WSe2). The piezoelectric coefficients of bulk 3R-TMDCs are shown to be sufficiently large or comparable to those of conventional bulk piezoelectric materials such as α-quartz, wurtzite GaN, and wurtzite AlN.

Method for Manufacturing Bulk Metallic Glass-Based Strain Wave Gear Components

NASA Technical Reports Server (NTRS)

Hofmann, Douglas C. (Inventor); Wilcox, Brian H. (Inventor)

2017-01-01

Systems and methods in accordance with embodiments of the invention implement bulk metallic glass-based strain wave gears and strain wave gear components. In one embodiment, a method of fabricating a strain wave gear includes: shaping a BMG-based material using a mold in conjunction with one of a thermoplastic forming technique and a casting technique; where the BMG-based material is shaped into one of: a wave generator plug, an inner race, an outer race, a rolling element, a flexspline, a flexspline without a set of gear teeth, a circular spline, a circular spline without a set of gear teeth, a set of gear teeth to be incorporated within a flexspline, and a set of gear teeth to be incorporated within a circular spline.

Production of nuclear grade zirconium: A review

NASA Astrophysics Data System (ADS)

Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

2015-11-01

Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium as a fuel cladding material. This paper provides an overview of the processes for nuclear grade zirconium production with emphasis on the methods of Zr-Hf separation. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The known pyrometallurgical Zr-Hf separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt-metal equilibrium. In the present paper, the available Zr-Hf separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

Elastic Anomaly and Polyamorphic Transition in (La, Ce)-based Bulk Metallic Glass under Pressure

DOE PAGES

Qi, Xintong; Zou, Yongtao; Wang, Xuebing; ...

2017-04-07

In this paper, we discovered that in association with the polyamorphism of La 32Ce 32Al 16Ni 5Cu 15 bulk metallic glass, the acoustic velocities, measured up to 12.3 GPa using ultrasonic interferometry, exhibit velocity minima at 1.8 GPa for P wave and 3.2 GPa for S wave. The low and high density amorphous states are distinguished by their distinct pressure derivatives of the bulk and shear moduli. The elasticity, permanent densification, and polyamorphic transition are interpreted by the topological rearrangement of solute-centered clusters in medium-range order (MRO) mediated by the 4f electron delocalization of Ce under pressure. The precisely measuredmore » acoustic wave travel times which were used to derive the velocities and densities provided unprecedented data to document the evolution of the bulk and shear elastic moduli associated with a polyamorphic transition in La 32Ce 32Al 16Ni 5Cu 15 bulk metallic glass and can shed new light on the mechanisms of polyamorphism and structural evolution in metallic glasses under pressure.« less

Magnetocaloric effect in heavy rare-earth elements doped Fe-based bulk metallic glasses with tunable Curie temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jiawei; Huo, Juntao; Chang, Chuntao, E-mail: ctchang@nimte.ac.cn, E-mail: dujun@nimte.ac.cn

2014-08-14

The effects of heavy rare earth (RE) additions on the Curie temperature (T{sub C}) and magnetocaloric effect of the Fe-RE-B-Nb (RE = Gd, Dy and Ho) bulk metallic glasses were studied. The type of dopping RE element and its concentration can easily tune T{sub C} in a large temperature range of 120 K without significantly decreasing the magnetic entropy change (ΔS{sub M}) and refrigerant capacity (RC) of the alloys. The observed values of ΔS{sub M} and RC of these alloys compare favorably with those of recently reported Fe-based metallic glasses with enhanced RC compared to Gd{sub 5}Ge{sub 1.9}Si{sub 2}Fe{sub 0.1}. The tunable T{submore » C} and large glass-forming ability of these RE doped Fe-based bulk metallic glasses can be used in a wide temperature range with the final required shapes.« less

Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

DOEpatents

Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

2017-02-07

A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

Development of Self-Healing Zirconium-Silicide Coatings for Improved Performance Zirconium-Alloy Fuel Cladding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sridharan, Kumar; Mariani, Robert; Bai, Xianming

Zirconium-alloy fuel claddings have been used successfully in Light Water Reactors (LWR) for over four decades. However, under high temperature accident conditions, zirconium-alloys fuel claddings exhibit profuse exothermic oxidation accompanied by release of hydrogen gas due to the reaction with water/steam. Additionally, the ZrO 2 layer can undergo monoclinic to tetragonal to cubic phase transformations at high temperatures which can induce stresses and cracking. These events were unfortunately borne out in the Fukushima-Daiichi accident in in Japan in 2011. In reaction to such accident, protective oxidation-resistant coatings for zirconium-alloy fuel claddings has been extensively investigated to enhance safety margins inmore » accidents as well as fuel performance under normal operation conditions. Such surface modification could also beneficially affect fuel rod heat transfer characteristics. Zirconium-silicide, a candidate coating material, is particularly attractive because zirconium-silicide coating is expected to bond strongly to zirconium-alloy substrate. Intermetallic compound phases of zirconium-silicide have high melting points and oxidation of zirconium silicide produces highly corrosion resistant glassy zircon (ZrSiO 4) and silica (SiO 2) which possessing self-healing qualities. Given the long-term goal of developing such coatings for use with nuclear reactor fuel cladding, this work describes results of oxidation and corrosion behavior of bulk zirconium-silicide and fabrication of zirconium-silicide coatings on zirconium-alloy test flats, tube configurations, and SiC test flats. In addition, boiling heat transfer of these modified surfaces (including ZrSi 2 coating) during clad quenching experiments is discussed in detail.« less

Zirconium and hafnium

USGS Publications Warehouse

Jones, James V.; Piatak, Nadine M.; Bedinger, George M.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Zirconium and hafnium are corrosion-resistant metals that are widely used in the chemical and nuclear industries. Most zirconium is consumed in the form of the main ore mineral zircon (ZrSiO4, or as zirconium oxide or other zirconium chemicals. Zirconium and hafnium are both refractory lithophile elements that have nearly identical charge, ionic radii, and ionic potentials. As a result, their geochemical behavior is generally similar. Both elements are classified as incompatible because they have physical and crystallochemical properties that exclude them from the crystal lattices of most rock-forming minerals. Zircon and another, less common, ore mineral, baddeleyite (ZrO2), form primarily as accessory minerals in igneous rocks. The presence and abundance of these ore minerals in igneous rocks are largely controlled by the element concentrations in the magma source and by the processes of melt generation and evolution. The world’s largest primary deposits of zirconium and hafnium are associated with alkaline igneous rocks, and, in one locality on the Kola Peninsula of Murmanskaya Oblast, Russia, baddeleyite is recovered as a byproduct of apatite and magnetite mining. Otherwise, there are few primary igneous deposits of zirconium- and hafnium-bearing minerals with economic value at present. The main ore deposits worldwide are heavy-mineral sands produced by the weathering and erosion of preexisting rocks and the concentration of zircon and other economically important heavy minerals, such as ilmenite and rutile (for titanium), chromite (for chromium), and monazite (for rare-earth elements) in sedimentary systems, particularly in coastal environments. In coastal deposits, heavy-mineral enrichment occurs where sediment is repeatedly reworked by wind, waves, currents, and tidal processes. The resulting heavy-mineral-sand deposits, called placers or paleoplacers, preferentially form at relatively low latitudes on passive continental margins and supply 100 percent of

Bulk assembly of organic metal halide nanotubes

DOE PAGES

Lin, Haoran; Zhou, Chenkun; Tian, Yu; ...

2017-10-16

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb 2Br 9 5–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C 6H 13N 4 +). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resultingmore » in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.« less

Oxidized zirconium on ceramic; Catastrophic coupling.

PubMed

Ozden, V E; Saglam, N; Dikmen, G; Tozun, I R

2017-02-01

Oxidized zirconium (Oxinium™; Smith & Nephew, Memphis, TN, USA) articulated with polyethylene in total hip arthroplasty (THA) appeared to have the potential to reduce wear dramatically. The thermally oxidized metal zirconium surface is transformed into ceramic-like hard surface that is resistant to abrasion. The exposure of soft zirconium metal under hard coverage surface after the damage of oxidized zirconium femoral head has been described. It occurred following joint dislocation or in situ succeeding disengagement of polyethylene liner. We reported three cases of misuse of Oxinium™ (Smith & Nephew, Memphis, TN, USA) heads. These three cases resulted in catastrophic in situ wear and inevitable failure although there was no advice, indication or recommendation for this use from the manufacturer. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Lithium Assisted “Dissolution–Alloying” Synthesis of Nanoalloys from Individual Bulk Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkholtz, Heather M.; Gallagher, James R.; Li, Tao

2016-04-12

We report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (similar to 200 degrees C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, which results in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron X-ray adsorption techniques. Then, upon the conversion of metal lithium tomore » LiOH in humid air, the Pd and Pt atoms undergo an alloying process to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted "dissolution-alloying" method bypasses many complications intrinsic to conventional ion reduction-based nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and the presence of segregated phases due to different reduction potentials of the constituent metal ions.« less

Influence of oxide microstructure on corrosion behavior of zirconium-based model alloys

NASA Astrophysics Data System (ADS)

Silva, Marcelo Jose Gomes Da

The extensive utilization of zirconium-based alloys in fuel cladding and other reactor internal components in the nuclear power industry has led to the continuous improvement of these alloys. At the present moment, demands for better performing nuclear fuel cladding materials are increasing. Also, new reactor designs have been proposed that would require the materials to withstand even more rigorous conditions. One of the factors that limit s fuel cladding utilization in nuclear reactors is uniform corrosion and the consequent hydriding of the fuel. In an attempt to develop mechanistic understanding of the role of alloying elements in the growth of a stable protective oxide, a series of model zirconium-based alloys was prepared (Zr-xFe-yCr, Zr-xCu-yMo, Zr-xNb-ySn, for various x and y, pure Zr and Zircaloy-4) and examined with advanced characterization techniques. The alloys were corrosion tested in autoclaves under three different conditions: 360°C water, 500°C steam and 500°C supercritical water in excess of 400 days. These autoclave testing conditions simulate nuclear reactor environment for both current designs (360°C water) and the new supercritical water reactor (500°C steam and 500°C supercritical water) proposed by the generation-IV initiative. The oxide films formed were systematically examined at the Advanced Photon Source using microbeam synchrotron radiation diffraction and fluorescence of cross-sectional samples to determine the oxide phases present and their crystallographic texture as a function of distance from the metal/oxide interface. Also, the overall texture of the oxide layers was investigated using synchrotron radiation diffraction in frontal geometry. The corrosion kinetics is a function of the alloy system and showed a wide range of behaviors, from immediately unstable oxide growth to stable behavior. The corrosion weight gains from testing at high temperature are a factor of five higher than those measured at 360°C but the

Preparation, consolidation, and crystallization of bulk metallic glasses

NASA Astrophysics Data System (ADS)

Holland, Troy

Bulk metallic glasses (BMGs) have been widely researched over the last decade. Research has primarily focused on BMGs of differing compositions and conditions within 3 main subject areas: preparation, consolidation, and crystallization. This work endeavors to show the interrelationships among each area across several types of BMG. Two compositions of zirconium(Zr)-type BMGs were prepared by mechanical attrition using a high-energy ball mill. The thermal and x-ray diffraction show that by milling elemental powders it is possible to obtain metallic powders with a glassy nature. These powders were then consolidated using a novel, high current density hot press. Hot pressing by using a spark plasma sintering (SPS) device has shown itself to be very useful in consolidating hard to produce intermetallics and ceramics. By utilizing high current densities and extremely rapid heating rates, the consolidation of the Zr-type ball milled powders and a gas atomized iron(Fe)-type powder was achieved. Utilizing the Kissinger relationship between reaction temperatures and their heating rates allowed for higher peak consolidation temperatures without fully- or partially-devitrifying the powders. The current densities applied aid in the diffusion and thermodynamics of the devitrification reaction. This affect has had little to no previous research so it was necessary to determine the specific effects of applied currents upon the devitrification of BMGs. To determine the role of applied currents on crystallization, or devitrification, of BMGs required the application of differing currents at fixed annealing temperatures. Once this was achieved it was possible with small-angle neutron scattering (SANS), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM) to show that both the kinetics and thermodynamics of the devitrification reaction were affected.

Inorganic resist materials based on zirconium phosphonate for atomic force microscope lithography

NASA Astrophysics Data System (ADS)

Kang, Mankyu; Kim, Seonae; Jung, JinHyuck; Kim, Heebom; Shin, Inkyun; Jeon, Chanuk; Lee, Haiwon

2014-03-01

New inorganic resist materials based on metal complexes were investigated for atomic force microscope (AFM) lithography. Phosphoric acids are good for self-assembly because of their strong binding energy. In this work, zirconium phosphonate system are newly synthesized for spin-coatable materials in aqueous solutions and leads to negative tone pattern for improving line edge roughness. Low electron exposure by AFM lithography could generate a pattern by electrochemical reaction and cross-linking of metal-oxo complexes. It has been reported that the minimum pattern results are affected by lithographic speed, and the applied voltage between a tip and a substrate.

Thermal properties of zirconium diboride -- transition metal boride solid solutions

NASA Astrophysics Data System (ADS)

McClane, Devon Lee

This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

Zirconium-based conversion film formation on zinc, aluminium and magnesium oxides and their interactions with functionalized molecules

NASA Astrophysics Data System (ADS)

Fockaert, L. I.; Taheri, P.; Abrahami, S. T.; Boelen, B.; Terryn, H.; Mol, J. M. C.

2017-11-01

Zirconium-based conversion treatment of zinc, aluminium and magnesium oxides have been studied in-situ using ATR-FTIR in a Kretschmann geometry. This set-up was coupled to an electrochemical cell, which allowed to obtain chemical and electrochemical information simultaneously as a function of conversion time. This elucidated the strong relation between physico-chemical surface properties and zirconium-based conversion kinetics. Whereas the surface hydroxyl density of zinc and aluminium increased during conversion, magnesium (hydr)oxide was shown to dissolve in the acid solution. Due to this dissolution, strong surface alkalization can be expected, explaining the rapid conversion kinetics. AES depth profiling was used to determine the final oxide thickness and elemental composition. This confirmed that magnesium is most active and forms a zirconium oxide layer approximately 10 times thicker than zinc. On the other hand, the presence of zirconium oxide on aluminium is very low and can be considered as not fully covering the metal oxide. Additionally, the converted oxide chemistry was related to the bonding mechanisms of amide functionalized molecules using ATR-FTIR and XPS. It was shown that inclusion of zirconium altered the acid-base properties, increasing the substrate proton donating capabilities in case of magnesium oxide and increasing hydrogen bonding and Bronsted interactions due to increased surface hydroxide fractions on zinc and aluminium substrates.

Processing and characterization of Zr-based metallic glass by laser direct deposition

NASA Astrophysics Data System (ADS)

Bae, Heehun

Bulk Metallic Glass has become famous for its exceptional mechanical and corrosion properties. Especially, Zirconium has been the prominent constituent in Bulk Metallic Glass due to its superior glass forming ability, the ability to form amorphous phase with low cooling rate, thereby giving advantages in structural applications. In this study, Zirconium powder was alloyed with Aluminum, Nickel and Copper powder at an atomic ratio of 65:10:10:15, respectively. Using the ball milling process to mix the powders, Zr65Al10Ni 10Cu15 amorphous structure was manufactured by laser direct deposition. Laser power and laser scanning speed were optimized to increase the fraction of amorphous phase. X-ray Diffraction confirmed the existence of both amorphous and crystalline phase by having a wide halo peak and sharp intense peak in the spectrum. Differential Scanning Calorimetry proved the presence of amorphous phase and glass transition was observed to be around 655 K. Scanning electron microscopy showed the microstructure of the deposited sample to have repetitive amorphous and crystalline phase as XRD examined. Crystalline phase resulted from the laser reheating and remelting process due to subsequent laser scan. Laser direct deposited amorphous/crystalline composite showed Vickers Hardness of 670 Hv and exhibited improved corrosion resistance in comparison to fully-crystallized sample. The compression test showed that, due to the existence of crystalline phase, fracture strain of Zr65Al10Ni10Cu 15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass.

Ignition and combustion of bulk metals in a microgravity environment

NASA Technical Reports Server (NTRS)

Branch, Melvyn C.; Daily, J. W.; Abbud-Madrid, Angel

1994-01-01

Knowledge of the oxidation, ignition, and combustion of bulk metals is important for fire safety in the production, management, and utilization of liquid and gaseous oxygen for ground based and space applications. This report summarizes research under NASA support to investigate the ignition and combustion characteristics of bulk metals under varying gravity conditions. Metal ignition and combustion have not been studied previously under these conditions and the results are important not only for improved fire safety but also to increase knowledge of basic ignition and combustion mechanisms. The studies completed to date have led to the development of a clean and reproducible ignition source and diagnostic techniques for combustion measurements and have provided normal gravity combustion data on ten different pure metals. Metal specimens were ignited using a xenon short-arc lamp and measurements were made of the radiant energy flux, surface temperature history, spectroscopy of surface and gas products, and surface morphology and chemistry. Elevated gravity was provided by the University of Colorado Geotechnical Centrifuge.

Deformation behavior, corrosion resistance, and cytotoxicity of Ni-free Zr-based bulk metallic glasses.

PubMed

Liu, L; Qiu, C L; Chen, Q; Chan, K C; Zhang, S M

2008-07-01

Two Ni-free bulk metallic glasses (BMGs) of Zr(60)Nb(5)Cu(22.5)Pd(5)Al(7.5) and Zr(60)Nb(5)Cu(20)Fe(5)Al(10) were successfully prepared by arc-melting and copper mold casting. The thermal stability and crystallization were studied using differential scanning calorimetry. It demonstrates that the two BMGs exhibit very good glass forming ability with a wide supercooled liquid region. A multi-step process of crystallization with a preferential formation of quasicrystals occurred in both BMGs under continuous heating. The deformation behavior of the two BMGs was investigated using quasi-static compression testing. It reveals that the BMGs exhibit not only superior strength but also an extended plasticity. Corrosion behaviors of the BMGs were investigated in phosphate buffered solution by electrochemical polarization. The result shows that the two BMGs exhibit excellent corrosion resistance characterized by low corrosion current densities and wide passive regions. X-ray photoelectron spectroscopy analysis revealed that the passive film formed after anodic polarization was highly enriched in zirconium, niobium, and aluminum oxides. This is attributed to the excellent corrosion resistance. Additionally, the potential cytotoxicity of the two Ni-free BMGs was evaluated through cell culture for 1 week followed by 3-(4,5-Dimethylthiazol-2-yl-)-2,5-diphenyltetrazolium bromide assay and SEM observation. The results indicate that the two Ni-free BMGs exhibit as good biocompatibility as Ti-6Al-4V alloy, and thus show a promising potential for biomedical applications. (c) 2007 Wiley Periodicals, Inc.

Synthesis and characterization of zirconium titanium phosphate and its application in separation of metal ions.

PubMed

Thakkar, Rakesh; Chudasama, Uma

2009-12-15

An advanced inorganic ion exchanger, zirconium titanium phosphate (ZTP) of the class of tetravalent bimetallic acid (TBMA) salt has been synthesized by sol-gel route. ZTP has been characterized for ICP-AES, TGA, FTIR and XRD. Chemical stability of the material in various media-acids, bases and organic solvents has been assessed. Cation exchange capacity (CEC) and effect of calcination (100-500 degrees C) on CEC has also been studied. Distribution behaviour of metal ions Co2+, Ni2+, Cu2+, Zn2+ (d-block), Cd2+, Hg2+, Pb2+, Bi3+ (heavy) and La3+, Ce3+, Th4+, UO(2)2+ (f-block) towards ZTP has been studied and distribution coefficient (K(d)) determined in aqueous as well as various electrolyte media/concentrations. Based on the differential selectivity, breakthrough capacity (BTC) and elution behaviour of various metal ions towards ZTP, a few binary and ternary metal ion separations have been carried out.

Bulk-surface relationship of an electronic structure for high-throughput screening of metal oxide catalysts

NASA Astrophysics Data System (ADS)

Kweun, Joshua Minwoo; Li, Chenzhe; Zheng, Yongping; Cho, Maenghyo; Kim, Yoon Young; Cho, Kyeongjae

2016-05-01

Designing metal-oxides consisting of earth-abundant elements has been a crucial issue to replace precious metal catalysts. To achieve efficient screening of metal-oxide catalysts via bulk descriptors rather than surface descriptors, we investigated the relationship between the electronic structure of bulk and that of the surface for lanthanum-based perovskite oxides, LaMO3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu). Through density functional theory calculations, we examined the d-band occupancy of the bulk and surface transition-metal atoms (nBulk and nSurf) and the adsorption energy of an oxygen atom (Eads) on (001), (110), and (111) surfaces. For the (001) surface, we observed strong correlation between the nBulk and nSurf with an R-squared value over 94%, and the result was interpreted in terms of ligand field splitting and antibonding/bonding level splitting. Moreover, the Eads on the surfaces was highly correlated with the nBulk with an R-squared value of more than 94%, and different surface relaxations could be explained by the bulk electronic structure (e.g., LaMnO3 vs. LaTiO3). These results suggest that a bulk-derived descriptor such as nBulk can be used to screen metal-oxide catalysts.

Molecular precursor routes to transition metal sulfides

NASA Astrophysics Data System (ADS)

Dinnage, Christopher Walker

This thesis is primarily concerned with the synthesis of homoleptic early transition meta thiolates and the subsequent preparation of bulk and thin-film metal disulfides from these compounds. Chapter 1 gives an introduction into the properties, preparation procedures and uses of bulk and thin-film transition metal disulfides as well as giving an overview of early transition metal thiolates synthesied so far in the literature (for titanium, zirconium, tantalum and niobium). Chapter 2 is concerned with the synthesis of a number of ionic and neutral transition metal thiolates. The main synthetic methodologies discussed in this chapter include substitution reactions of transition metal amides and alkyls with thiols, salt metathesis reactions of transition metal chlorides with alkali metal thiolates or with a base / thiol and the use of Grignard reagents. Chapter 3 discusses the preparation of bulk transition metal disulfides using the thiolates prepared in the previous chapter via a thio "sol-gel" route. The preparation of a range of bulk metal and mixed-metal disulfides using transition metal chlorides and hexamethyldisilathiane is also discussed in this chapter. Finally, chapter 4 is concerned with the attempted preparation of thin-films of some transition metal disulfides. Decomposition studies of some of the thiolates prepared in chapter 2 are discussed using thermal gravimetric analysis. Vapour-phase deposition studies are also explored in order to test the potential of the transition metal thiolates as precursors to the disulfides. Experiments using low-pressure chemical vapour deposition and aerosol-assisted chemical vapour deposition are also described.

Fracture Behavior of Zr-BASED Bulk Metallic Glass Under Impact Loading

NASA Astrophysics Data System (ADS)

Shin, Hyung-Seop; Kim, Ki-Hyun; Oh, Sang-Yeob

The fracture behavior of a Zr-based bulk amorphous metal under impact loading using subsize V-shaped Charpy specimens was investigated. Influences of loading rate on the fracture behavior of amorphous Zr-Al-Ni-Cu alloy were examined. As a result, the maximum load and absorbed fracture energy under impact loading were lower than those under quasi-static loading. A large part of the absorbed fracture energy in the Zr-based BMG was consumed in the process for crack initiation and not for crack propagation. In addition, fractographic characteristics of BMGs, especially the initiation and development of shear bands at the notch tip were investigated. Fractured surfaces under impact loading are smoother than those under quasi-static loading. The absorbed fracture energy appeared differently depending on the appearance of the shear bands developed. It can be found that the fracture energy and fracture toughness of Zr-based BMG are closely related with the extent of shear bands developed during fracture.

Nanopatterned bulk metallic glass-based biomaterials modulate macrophage polarization.

PubMed

Shayan, Mahdis; Padmanabhan, Jagannath; Morris, Aaron H; Cheung, Bettina; Smith, Ryan; Schroers, Jan; Kyriakides, Themis R

2018-06-01

Polarization of macrophages by chemical, topographical and mechanical cues presents a robust strategy for designing immunomodulatory biomaterials. Here, we studied the ability of nanopatterned bulk metallic glasses (BMGs), a new class of metallic biomaterials, to modulate murine macrophage polarization. Cytokine/chemokine analysis of IL-4 or IFNγ/LPS-stimulated macrophages showed that the secretion of TNF-α, IL-1α, IL-12, CCL-2 and CXCL1 was significantly reduced after 24-hour culture on BMGs with 55 nm nanorod arrays (BMG-55). Additionally, under these conditions, macrophages increased phagocytic potential and exhibited decreased cell area with multiple actin protrusions. These in vitro findings suggest that nanopatterning can modulate biochemical cues such as IFNγ/LPS. In vivo evaluation of the subcutaneous host response at 2 weeks demonstrated that the ratio of Arg-1 to iNOS increased in macrophages adjacent to BMG-55 implants, suggesting modulation of polarization. In addition, macrophage fusion and fibrous capsule thickness decreased and the number and size of blood vessels increased, which is consistent with changes in macrophage responses. Our study demonstrates that nanopatterning of BMG implants is a promising technique to selectively polarize macrophages to modulate the immune response, and also presents an effective tool to study mechanisms of macrophage polarization and function. Implanted biomaterials elicit a complex series of tissue and cellular responses, termed the foreign body response (FBR), that can be influenced by the polarization state of macrophages. Surface topography can influence polarization, which is broadly characterized as either inflammatory or repair-like. The latter has been linked to improved outcomes of the FBR. However, the impact of topography on macrophage polarization is not fully understood, in part, due to a lack of high moduli biomaterials that can be reproducibly processed at the nanoscale. Here, we studied

Fine-grained zirconium-base material

DOEpatents

Van Houten, G.R.

1974-01-01

A method is described for making zirconium with inhibited grain growth characteristics, by the process of vacuum melting the zirconium, adding 0.3 to 0.5% carbon, stirring, homogenizing, and cooling. (Official Gazette)

Ruthenium(ii)-polypyridyl zirconium(iv) metal-organic frameworks as a new class of sensitized solar cells.

PubMed

Maza, W A; Haring, A J; Ahrenholtz, S R; Epley, C C; Lin, S Y; Morris, A J

2016-01-01

A series of Ru(ii)L 2 L' (L = 2,2'-bipyridyl, L' = 2,2'-bipyridine-5,5'-dicarboxylic acid), RuDCBPY, -containing zirconium(iv) coordination polymer thin films have been prepared as sensitizing materials for solar cell applications. These metal-organic framework (MOF) sensitized solar cells, MOFSCs, each are shown to generate photocurrent in response to simulated 1 sun illumination. Emission lifetime measurements indicate the excited state quenching of RuDCBPY at the MOF-TiO 2 interface is extremely efficient (>90%), presumably due to electron injection into TiO 2 . A mechanism is proposed in which RuDCBPY-centers photo-excited within the MOF-bulk undergo isotropic energy migration up to 25 nm from the point of origin. This work represents the first example in which a MOFSC is directly compared to the constituent dye adsorbed on TiO 2 (DSC). Importantly, the MOFSCs outperformed their RuDCBPY-TiO 2 DSC counterpart under the conditions used here and, thus, are solidified as promising solar cell platforms.

Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal-organic framework

NASA Astrophysics Data System (ADS)

SK, Mostakim; Grzywa, Maciej; Volkmer, Dirk; Biswas, Shyam

2015-12-01

The modulated synthesis of the thienothiophene based zirconium metal-organic framework (MOF) material having formula [Zr6O4(OH)4(DMTDC)6]·4.8DMF·10H2O (1) (H2DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl4, H2DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl4/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achieved by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N2 and CO2 sorption analyses suggest that the material possesses remarkably high microporosity (SBET=1236 m2 g-1; CO2 uptake=3.5 mmol g-1 at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu2+ over Co2+ and Ni2+ ions.

Combinatorial Strategies for the Development of Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Ding, Shiyan

The systematic identification of multi-component alloys out of the vast composition space is still a daunting task, especially in the development of bulk metallic glasses that are typically based on three or more elements. In order to address this challenge, combinatorial approaches have been proposed. However, previous attempts have not successfully coupled the synthesis of combinatorial libraries with high-throughput characterization methods. The goal of my dissertation is to develop efficient high-throughput characterization methods, optimized to identify glass formers systematically. Here, two innovative approaches have been invented. One is to measure the nucleation temperature in parallel for up-to 800 compositions. The composition with the lowest nucleation temperature has a reasonable agreement with the best-known glass forming composition. In addition, the thermoplastic formability of a metallic glass forming system is determined through blow molding a compositional library. Our results reveal that the composition with the largest thermoplastic deformation correlates well with the best-known formability composition. I have demonstrated both methods as powerful tools to develop new bulk metallic glasses.

Foamed Bulk Metallic Glass (Foam) Investigation

NASA Technical Reports Server (NTRS)

2004-01-01

This soldering iron has an evacuated copper capsule at the tip that contains a pellet of Bulk Metallic Glass (BMG) aboard the International Space Station (ISS). Prior to flight, researchers sealed a pellet of bulk metallic glass mixed with microscopic gas-generating particles into the copper ampoule under vacuum. Once heated in space, such as in this photograph, the particles generated gas and the BMG becomes a viscous liquid. The released gas made the sample foam within the capsule where each microscopic particle formed a gas-filled pore within the foam. The inset image shows the oxidation of the sample after several minutes of applying heat. Although hidden within the brass sleeve, the sample retained the foam shape when cooled, because the viscosity increased during cooling until it was solid.

SEPARATION PROCESS FOR ZIRCONIUM AND COMPOUNDS THEREOF

DOEpatents

Crandall, H.W.; Thomas, J.R.

1959-06-30

The separation of zirconium from columbium, rare earths, yttrium and the alkaline earth metals, such mixtures of elements occurring in zirconium ores or neutron irradiated uranium is described. According to the invention a suitable separation of zirconium from a one normal acidic aqueous solution containing salts, nitrates for example, of tetravalent zirconium, pentavalent columbium, yttrium, rare earths in the trivalent state and alkaline earths can be obtained by contacting the aqueous solution with a fluorinated beta diketonc alone or in an organic solvent solution, such as benzene, to form a zirconium chelate compound. When the organic solvent is present the zirconium chelate compound is directly extracted; otherwise it is separated by filtration. The zirconium may be recovered from contacting the organic solvent solution containing the chelated compound by back extraction with either an aqueous hydrofluoric acid or an oxalic acid solution.

Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns

PubMed Central

Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko

2017-01-01

Background An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​ Aim: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Material and methods Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Results Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Conclusion Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding. PMID:28827846

Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns.

PubMed

Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko; Anić-Milošević, Sandra

2017-06-01

An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​: A im: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding.

A predictive structural model for bulk metallic glasses

PubMed Central

Laws, K. J.; Miracle, D. B.; Ferry, M.

2015-01-01

Great progress has been made in understanding the atomic structure of metallic glasses, but there is still no clear connection between atomic structure and glass-forming ability. Here we give new insights into perhaps the most important question in the field of amorphous metals: how can glass-forming ability be predicted from atomic structure? We give a new approach to modelling metallic glass atomic structures by solving three long-standing problems: we discover a new family of structural defects that discourage glass formation; we impose efficient local packing around all atoms simultaneously; and we enforce structural self-consistency. Fewer than a dozen binary structures satisfy these constraints, but extra degrees of freedom in structures with three or more different atom sizes significantly expand the number of relatively stable, ‘bulk' metallic glasses. The present work gives a new approach towards achieving the long-sought goal of a predictive capability for bulk metallic glasses. PMID:26370667

A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO 2 Adsorption and Chemical Fixation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jie; Usov, Pavel M.; Xu, Wenqian

Metal-organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr-6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintainsmore » the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO2 uptake capacity (up to similar to 9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO2 with epoxides, including sterically hindered epoxides. The MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.« less

The effect of high energy concentration source irradiation on structure and properties of Fe-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Pilarczyk, Wirginia

2016-06-01

Metallic glasses exhibit metastable structure and maintain this relatively stable amorphous state within certain temperature range. High intensity laser beam was used for the surface irradiation of Fe-Co-B-Si-Nb bulk metallic glasses. The variable parameter was laser beam pulse energy. For the analysis of structure and properties of bulk metallic glasses and their surface after laser remelting the X-ray analysis, microscopic observation and test of mechanical properties were carried out. Examination of the nanostructure of amorphous materials obtained by high pressure copper mold casting method and the irradiated with the use of TITAN 80-300 HRTEM was carried out. Nanohardness and reduced Young's modulus of particular amorphous and amorphous-crystalline material zone of the laser beam were examined with the use of Hysitron TI950 Triboindenter nanoindenter and with the use of Berkovich's indenter. The XRD and microscopic analysis showed that the test material is amorphous in its structure before irradiation. Microstructure observation with electron transmission microscopy gave information about alloy crystallization in the irradiated process. Identification of given crystal phases allows to determine the kind of crystal phases created in the first place and also further changes of phase composition of alloy. The main value of the nanohardness of the surface prepared by laser beam has the order of magnitude similar to bulk metallic glasses formed by casting process irrespective of the laser beam energy used. Research results analysis showed that the area between parent material and fusion zone is characterized by extraordinarily interesting structure which is and will be the subject of further analysis in the scope of bulk metallic glasses amorphous structure and high energy concentration source. The main goal of this work is the results' presentation of structure and chosen properties of the selected bulk metallic glasses after casting process and after irradiation

High-intensity low energy titanium ion implantation into zirconium alloy

NASA Astrophysics Data System (ADS)

Ryabchikov, A. I.; Kashkarov, E. B.; Pushilina, N. S.; Syrtanov, M. S.; Shevelev, A. E.; Korneva, O. S.; Sutygina, A. N.; Lider, A. M.

2018-05-01

This research describes the possibility of ultra-high dose deep titanium ion implantation for surface modification of zirconium alloy Zr-1Nb. The developed method based on repetitively pulsed high intensity low energy titanium ion implantation was used to modify the surface layer. The DC vacuum arc source was used to produce metal plasma. Plasma immersion titanium ions extraction and their ballistic focusing in equipotential space of biased electrode were used to produce high intensity titanium ion beam with the amplitude of 0.5 A at the ion current density 120 and 170 mA/cm2. The solar eclipse effect was used to prevent vacuum arc titanium macroparticles from appearing in the implantation area of Zr sample. Titanium low energy (mean ion energy E = 3 keV) ions were implanted into zirconium alloy with the dose in the range of (5.4-9.56) × 1020 ion/cm2. The effect of ion current density, implantation dose on the phase composition, microstructure and distribution of elements was studied by X-ray diffraction, scanning electron microscopy and glow-discharge optical emission spectroscopy, respectively. The results show the appearance of Zr-Ti intermetallic phases of different stoichiometry after Ti implantation. The intermetallic phases are transformed from both Zr0.7Ti0.3 and Zr0.5Ti0.5 to single Zr0.6Ti0.4 phase with the increase in the implantation dose. The changes in phase composition are attributed to Ti dissolution in zirconium lattice accompanied by the lattice distortions and appearance of macrostrains in intermetallic phases. The depth of Ti penetration into the bulk of Zr increases from 6 to 13 μm with the implantation dose. The hardness and wear resistance of the Ti-implanted zirconium alloy were increased by 1.5 and 1.4 times, respectively. The higher current density (170 mA/cm2) leads to the increase in the grain size and surface roughness negatively affecting the tribological properties of the alloy.

Thermoplastic deformation of ferromagnetic CoFe-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Wu, Chenguang; Hu, Renchao; Man, Qikui; Chang, Chuntao; Wang, Xinmin

2017-12-01

The superplastic deformation behavior of the ferromagnetic Co31Fe31Nb8B30 bulk metallic glass (BMG) in the supercooled liquid region was investigated. At a given temperature, the BMG exhibits a Newtonian behavior at low strain rates but a non-Newtonian behavior at high strain rates. The high thermal stability of this glassy alloy system offers an enough processing window to thermoplastic forming (TPF), and the strong processing ability was examined by simple micro-replication experiments. It is demonstrated that the TPF formability on length scales ranging down to nanometers can be achieved in the selected experimental condition. Based on the analysis of deformation behavior, the nearly full density sample (i.e. nearly 100%), was produced from water-atomized glassy powders and consolidated by the hot-pressing technique. The sample exhibits good soft-magnetic and mechanical properties, i.e., low coercive force of 0.43 Oe, high initial permeability of 4100 and high Vickers hardness 1398. These results suggest that the hot-pressing process opens up possibilities for the commercial exploitation of BMGs in engineering applications.

Bulk Fe-based metallic glass with extremely soft ferromagnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, T. D.; Harms, U. S.; Schwarz, R. B.

2001-01-01

The authors have investigated the DC and AC magnetic properties of a bulk glassy Fe{sub 65.5}Cr{sub 4}Mo{sub 4}Ga{sub 4}P{sub 12}B{sub 5.5}C{sub 5} alloy. In the annealed state the alloy has coercivity H{sub C} and maximum DC permeability {mu}{sub m} of approximately 0.4 A/m (5 mOe) and 2.8 x 10{sup 5}, comparable to those found in annealed zero-magnetostriction Co-based alloys. The low H{sub C} found in the bulk glassy alloy is attributed to the low ratio of surface-roughness to sample thickness, and low residual internal-stress. The total power loss in the annealed bulk glass is about one order of magnitude lowermore » than that of rapidly quenched Fe-based glassy ribbons. This is attributed to a low anomalous eddy-current loss.« less

Lithium assisted “dissolution–alloying” synthesis of nanoalloys from individual bulk metals

DOE PAGES

Barkholtz, Heather M.; Gallagher, James R.; Li, Tao; ...

2016-03-27

Here, we report new fundamental chemistry involved in the synthesis of bimetallic nanoalloys via dissolving the pure bulk transition metals in molten lithium. It is revealed at the atomic level that when two pure bulk transition metals such as Pd and Pt are placed in molten lithium (~200°C), they undergo a dissolution process in which the metal-metal bonds in pure bulk transition metals are completely ruptured, resulting in the existence of individual Pd and Pt atoms surrounded by lithium atoms, as is evident by synchrotron Xray adsorption techniques. Then, upon the conversion of metal lithium to LiOH in humid air,more » the Pd and Pt atoms undergo an alloying process, to aggregate into nanoalloys. This method was further expanded to include PdZn, which is notoriously difficult to prepare via traditional nanoalloy synthesis methods due to the easily oxidizable Zn component. The constantly reducing environment of metallic Li allowed for preparation of PdZn nanoalloys with minimal Zn oxidation via dissolution-alloying of individual bulk transition metals in molten lithium. Additionally, this lithium assisted “dissolutionalloying” method bypasses many complications intrinsic to conventional ion reductionbased nanoalloy synthesis including the necessity of ligated metal ions, the use of proper reducing agents and dispersing surfactants, and the presence of segregated phases due to different reduction potentials of the constituent metal ions.« less

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

DOE PAGES

Zheng, Tao; Yang, Zaixing; Gui, Daxiang; ...

2017-05-30

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest voidmore » volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.« less

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

PubMed Central

Zheng, Tao; Yang, Zaixing; Gui, Daxiang; Liu, Zhiyong; Wang, Xiangxiang; Dai, Xing; Liu, Shengtang; Zhang, Linjuan; Gao, Yang; Chen, Lanhua; Sheng, Daopeng; Wang, Yanlong; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

2017-01-01

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. Herein, we overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. These compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest void volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism. PMID:28555656

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Tao; Yang, Zaixing; Gui, Daxiang

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest voidmore » volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.« less

Modification in band gap of zirconium complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Mayank, E-mail: mayank30134@gmail.com; Singh, J.; Chouhan, S.

2016-05-06

The optical properties of zirconium complexes with amino acid based Schiff bases are reported here. The zirconium complexes show interesting stereo chemical features, which are applicable in organometallic and organic synthesis as well as in catalysis. The band gaps of both Schiff bases and zirconium complexes were obtained by UV-Visible spectroscopy. It was found that the band gap of zirconium complexes has been modified after adding zirconium compound to the Schiff bases.

The Relationship between Bulk and Mobile Forms of Heavy Metals in Soils of Kursk

NASA Astrophysics Data System (ADS)

Nevedrov, N. P.; Protsenko, E. P.; Glebova, I. V.

2018-01-01

The contamination of Kursk urboecotopes by heavy metals (Pb, Cd, Zn, Cu, Ni) is considered. The relationships between the contents of bulk and mobile forms of heavy metal ions have been examined. The results of monitoring studies attest to a tendency for the accumulation of both bulk and mobile forms of heavy metals in the humus-accumulative horizon, except for bulk cadmium and mobile nickel. Linear and nonlinear regression models of the bulk contents of Pb, Cd, Zn, and Ni as dependent on the contents of their mobile forms have been developed. These models allow us to calculate the bulk content of heavy metal ions in the soils of urboecotopes using simpler methods of the extraction and laboratory determination of their mobile forms.

A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

NASA Technical Reports Server (NTRS)

Dupraw, W. A.

1972-01-01

A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

Electrochemical response of carbon paste electrode modified with mixture of titanium dioxide/zirconium dioxide in the detection of heavy metals: lead and cadmium.

PubMed

Nguyen, Phuong Khanh Quoc; Lunsford, Suzanne K

2012-11-15

A novel carbon modified electrode was developed by incorporating titanium dioxide/zirconium dioxide into the graphite carbon paste electrode to detect heavy metals-cadmium and lead. In this work, the development of the novel titanium dioxide/zirconium dioxide modified carbon paste electrode was studied to determine the optimum synthesis conditions related to the temperature, heating duration, amount and ratio of titanium dioxide/zirconium dioxide, and amount of surfactant, to create the most reproducible results. Using cyclic voltammetric (CV) analysis, this study has proven that the novel titanium dioxide/zirconium dioxide can be utilized to detect heavy metals-lead and cadmium, at relatively low concentrations (7.6×10(-6) M and 1.1×10(-5) M for Pb and Cd, respectively) at optimum pH value (pH=3). From analyzing CV data the optimal electrodes surface area was estimated to be 0.028 (±0.003) cm(2). Also, under the specific experimental conditions, electron transfer coefficients were estimated to be 0.44 and 0.33 along with the heterogeneous electron transfer rate constants of 5.64×10(-3) and 2.42×10(-3) (cm/s) for Pb and Cd, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

METHOD OF FABRICATING A URANIUM-ZIRCONIUM HYDRIDE REACTOR CORE

DOEpatents

Weeks, I.F.; Goeddel, W.V.

1960-03-22

A method is described of evenly dispersing uranlum metal in a zirconium hydride moderator to produce a fuel element for nuclear reactors. According to the invention enriched uranium hydride and zirconium hydride powders of 200 mesh particle size are thoroughly admixed to form a mixture containing 0.1 to 3% by weight of U/sup 235/ hydride. The mixed powders are placed in a die and pressed at 100 tons per square inch at room temperature. The resultant compacts are heated in a vacuum to 300 deg C, whereby the uranium hydride deoomposes into uranium metal and hydrogen gas. The escaping hydrogen gas forms a porous matrix of zirconium hydride, with uramum metal evenly dispersed therethrough. The advantage of the invention is that the porosity and uranium distribution of the final fuel element can be more closely determined and controlled than was possible using prior methods of producing such fuel ele- ments.

METHOD OF IMPROVING CORROSION RESISTANCE OF ZIRCONIUM

DOEpatents

Shannon, D.W.

1961-03-28

An improved intermediate rinse for zirconium counteracts an anomalous deposit that often results in crevices and outof-the-way places when ordinary water is used to rinse away a strong fluoride etching solution designed to promote passivation of the metal. The intermediate rinse, which is used after the etching solution and before the water, is characterized by a complexing agent for fluoride ions such as aluminum or zirconium nitrates or chlorides.

On the evolution of morphology of zirconium sponge during reduction and distillation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kapoor, K.; Padmaprabu, C.; Nandi, D.

2008-03-15

High purity zirconium metal is produced by magnesio-thermic reduction of zirconium tetrachloride followed by vacuum distillation. The reduction process is carried out in a batch giving metal sponge and magnesium chloride in the reduced mass. The sponge is purified to using by vacuum distillation. The morphology of the sponge formed during the reduction and its influence on further processing has significant importance. In the present study, a detailed investigation involving evolution of the morphology of sponge particles and its implication during the vacuum distillation was carried out. The study of the microstructure was done using scanning electron microscopy and X-raymore » diffraction. It is observed that the nascent sponge formed is highly unstable which transforms to a needle-like morphology almost immediately, which further transforms to rounded and finally to a bulk shape. Faceting of the surface and needle-shape formation were observed in these particles, this is probably due to anisotropy in the surface energy. The morphology of the sponge formed during the reduction influences the distillation process. The fine needle-like shape sponge morphology leads to particle ejection, which is explained to be due to curvature effect. This is responsible for the formation of unwanted mass during distillation. XRD line broadening analysis indicates that the individual sponge particles are free from structural defects (dislocation) and are nearly single crystalline in nature.« less

Mechanical properties and structural features of novel Fe-based bulk metallic glasses with unprecedented plasticity

PubMed Central

Yang, Weiming; Liu, Haishun; Zhao, Yucheng; Inoue, Akihisa; Jiang, Kemin; Huo, Juntao; Ling, Haibo; Li, Qiang; Shen, Baolong

2014-01-01

Fe-based bulk metallic glasses (BMGs) have attracted great attention due to their unique magnetic and mechanical properties, but few applications have been materialized because of their brittleness at room temperature. Here we report a new Fe50Ni30P13C7 BMG which exhibits unprecedented compressive plasticity (>20%) at room temperature without final fracture. The mechanism of unprecedented plasticity for this new Fe-based BMG was also investigated. It was discovered that the ductile Fe50Ni30P13C7 BMG is composed of unique clusters mainly linked by less directional metal-metal bonds which are inclined to accommodate shear strain and absorbed energy in the front of crack tip. This conclusion was further verified by the X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy experiments of Fe80-xNixP13C7 (x = 0, 10, 20, 30) and Fe72-xNixB20Si4Nb4 (x = 0, 7.2, 14.4, 21.6, 28.8) glassy systems. The results also indicate a strong correlation between the p-d hybridization and plasticity, verifying that the transition from brittle to ductile induced by Ni addition is due to the change of bonding characteristics in atomic configurations. Thus, we can design the plasticity of Fe-based BMGs and open up a new possible pathway for manufacturing BMGs with high strength and plasticity. PMID:25167887

[The clinical application of zirconium-dioxide-ceramics. Case report].

PubMed

Somfai, Dóra; Zsigmond, Ágnes; Károlyházy, Katalin; Kispély, Barbara; Hermann, Péter

2015-12-01

Due to its outstanding physical, mechanical and esthetic properties, zirconium-dioxide is one of the most popular non-metal denture, capable of surpassing PFM in most cases. The recent advances of CAD/CAM technology makes it a good alternitve. Here we show the usefulness of zirconium-dioxide in everyday dental practice through three case reports.

Bioactivity and biocompatibility of hydroxyapatite-based bioceramic coatings on zirconium by plasma electrolytic oxidation.

PubMed

Aktuğ, Salim Levent; Durdu, Salih; Yalçın, Emine; Çavuşoğlu, Kültigin; Usta, Metin

2017-02-01

In the present work, hydroxyapatite (HAP)-based plasma electrolytic oxide (PEO) coatings were produced on zirconium at different current densities in a solution containing calcium acetate and β-calcium glycerophosphate by a single step. The phase structure, surface morphology, functional groups, thickness and roughness of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), eddy current method and surface profilometer, respectively. The phases of cubic-zirconia, calcium zirconate and HAP were detected by XRD. The amount of HAP and calcium zirconate increased with increasing current density. The surface of the coatings was very porous and rough. Moreover, bioactivity and biocompatibility of the coatings were analyzed in vitro immersion simulated body fluid (SBF) and MTT (3-(4,5-dimethyl thiazol-2yl)-2,5-diphenyl tetrazolium bromide) assay, hemolysis assay and bacterial formation. The apatite-forming ability of the coatings was evaluated after immersion in SBF up to 28days. After immersion, the bioactivity of HAP-based coatings on zirconium was greater than the ones of uncoated zirconium and zirconium oxide-based surface. The bioactivity of PEO surface on zirconium was significantly improved under SBF conditions. The bacterial adhesion of the coatings decreased with increasing current density. The bacterial adhesion of the coating produced at 0.370A/cm 2 was minimum compared to uncoated zirconium coated at 0.260 and 0.292A/cm 2 . The hemocompatibility of HAP-based surfaces was improved by PEO. The cell attachment and proliferation of the PEO coatings were better than the one of uncoated zirconium according to MTT assay results. Copyright © 2016 Elsevier B.V. All rights reserved.

A theoretical model of grain boundary self-diffusion in metals with phase transitions (case study into titanium and zirconium)

NASA Astrophysics Data System (ADS)

Semenycheva, Alexandra V.; Chuvil'deev, Vladimir N.; Nokhrin, Aleksey V.

2018-05-01

The paper offers a model describing the process of grain boundary self-diffusion in metals with phase transitions in the solid state. The model is based on ideas and approaches found in the theory of non-equilibrium grain boundaries. The range of application of basic relations contained in this theory is shown to expand, as they can be used to calculate the parameters of grain boundary self-diffusion in high-temperature and low-temperature phases of metals with a phase transition. The model constructed is used to calculate grain boundary self-diffusion activation energy in titanium and zirconium and an explanation is provided as to their abnormally low values in the low-temperature phase. The values of grain boundary self-diffusion activation energy are in good agreement with the experiment.

Superior Tensile Ductility in Bulk Metallic Glass with Gradient Amorphous Structure

PubMed Central

Wang, Q.; Yang, Y.; Jiang, H.; Liu, C. T.; Ruan, H. H.; Lu, J.

2014-01-01

Over centuries, structural glasses have been deemed as a strong yet inherently ‘brittle’ material due to their lack of tensile ductility. However, here we report bulk metallic glasses exhibiting both a high strength of ~2 GPa and an unprecedented tensile elongation of 2–4% at room temperature. Our experiments have demonstrated that intense structural evolution can be triggered in theses glasses by the carefully controlled surface mechanical attrition treatment, leading to the formation of gradient amorphous microstructures across the sample thickness. As a result, the engineered amorphous microstructures effectively promote multiple shear banding while delay cavitation in the bulk metallic glass, thus resulting in superior tensile ductility. The outcome of our research uncovers an unusual work-hardening mechanism in monolithic bulk metallic glasses and demonstrates a promising yet low-cost strategy suitable for producing large-sized, ultra-strong and stretchable structural glasses. PMID:24755683

STUDY OF THE OXIDATION OF NON-ALLOYED ZIRCONIUM AND OF OXYGEN DIFFUSION IN THE OXIDE FILM AND IN THE METAL (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Debuigne, J.; Lehr, P.

1963-12-01

The oxidation processes of zirconium at 600-850 deg C were studied. A micrographic and radiocrystallographic analysis of the oxide layers formed at the surface of the metal was carried out. The kinetic results, weight gains as function nf time, were completed by the study of oxygen diffusion through the oxide layer formed and in the underlying metal. (auth)

Concept Feasibility Report for Electroplating Zirconium onto Uranium Foil - Year 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coffey, Greg W.; Meinhardt, Kerry D.; Joshi, Vineet V.

2015-03-01

The Fuel Fabrication Capability within the U.S. High Performance Research Reactor Conversion Program is funded through the National Nuclear Security Administration (NNSA) NA-26 (Office of Material Management and Minimization). An investigation was commissioned to determine the feasibility of using electroplating techniques to apply a coating of zirconium onto depleted uranium/molybdenum alloy (U-10Mo). Electroplating would provide an alternative method to the existing process of hot roll-bonding zirconium foil onto the U-10Mo fuel foil during the fabrication of fuel elements for high-performance research reactors. The objective of this research was to develop a reproducible and scalable plating process that will produce amore » uniform, 25 μm thick zirconium metal coating on U-10Mo foil. In previous work, Pacific Northwest National Laboratory (PNNL) established a molten salt electroplating apparatus and protocol to plate zirconium metal onto molybdenum foil (Coffey 2015). During this second year of the research, PNNL furthered this work by moving to the U-10Mo alloy system (90 percent uranium:10 percent molybdenum). The original plating apparatus was disassembled and re-assembled in a laboratory capable of handling low-level radioactive materials. Initially, the work followed the previous year’s approach, and the salt bath composition was targeted at the eutectic composition (LiF:NaF:ZrF4 = 26:37:37 mol%). Early results indicated that the formation of uranium fluoride compounds would be problematic. Other salt bath compositions were investigated in order to eliminate the uranium fluoride production (LiF:NaF = 61:39 mol% and LiF:NaF:KF = 46.5:11.5:42 mol% ). Zirconium metal was used as the crucible for the molten salt. Three plating methods were used—isopotential, galvano static, and pulsed plating. The molten salt method for zirconium metal application provided high-quality plating on molybdenum in PNNL’s previous work. A key advantage of this approach is

Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts

DOEpatents

Choi, Jae Soon; Armstrong, Beth L; Schwartz, Viviane

2015-04-21

A method for synthesizing catalyst beads of bulk transmission metal carbides, nitrides and phosphides is provided. The method includes providing an aqueous suspension of transition metal oxide particles in a gel forming base, dropping the suspension into an aqueous solution to form a gel bead matrix, heating the bead to remove the binder, and carburizing, nitriding or phosphiding the bead to form a transition metal carbide, nitride, or phosphide catalyst bead. The method can be tuned for control of porosity, mechanical strength, and dopant content of the beads. The produced catalyst beads are catalytically active, mechanically robust, and suitable for packed-bed reactor applications. The produced catalyst beads are suitable for biomass conversion, petrochemistry, petroleum refining, electrocatalysis, and other applications.

Ignition and combustion of bulk metals at normal, elevated and reduced gravity

NASA Technical Reports Server (NTRS)

Branch, Melvyn C.; Daily, John W.; Abbud-Madrid, Angel

1995-01-01

Knowledge of the oxidation, ignition, and combustion of bulk metals is important for fire safety in the production, management, and utilization of liquid and gaseous oxygen for ground based and space applications. This proposal outlines studies in continuation of research initiated earlier under NASA support to investigate the ignition and combustion characteristics of bulk metals under varying gravity conditions. Metal ignition and combustion have not been studied previously under these conditions and the results are important not only for improved fire safety but also to increase knowledge of basic ignition and combustion mechanisms. The studies completed to date have led to the development of a clean and reproducible ignition source and diagnostic techniques for combustion measurements and have provided normal, elevated, and reduced gravity combustion data on a variety of different pure metals. The research conducted under this grant will use the apparatus and techniques developed earlier to continue the elevated and low gravity experiments, and to develop the overall modeling of the ignition and combustion process. Metal specimens are to be ignited using a xenon short-arc lamp and measurements are to be made of the ignition energy, surface temperature history, burning rates, spectroscopy of surface and gas products, and surface morphology and chemistry. Elevated gravity will be provided by the University of Colorado Geotechnical Centrifuge and microgravity will be obtained in NASA's DC-9 Reduced Gravity aircraft.

Surface characterization of anodized zirconium for biomedical applications

NASA Astrophysics Data System (ADS)

Sanchez, A. Gomez; Schreiner, W.; Duffó, G.; Ceré, S.

2011-05-01

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process. Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry. In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques. It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.

Mechanically durable underwater superoleophobic surfaces based on hydrophilic bulk metals for oil/water separation

NASA Astrophysics Data System (ADS)

Yu, Huadong; Lian, Zhongxu; Xu, Jinkai; Wan, Yanling; Wang, Zuobin; Li, Yiquan; Yu, Zhanjiang; Weng, Zhankun

2018-04-01

Despite the success of previous methods for fabricating underwater superoleophobic surfaces, most of the surfaces based on soft materials are prone to collapse and deformation due to their mechanically fragile nature, and they fail to perform their designed functions after the surface materials are damaged in water. In this work, the nanosecond laser-induced oxide coatings on hydrophilic bulk metals are reported which overcomes the limitation and shows the robust underwater superoleophobicity to a mechanical challenge encountered by surfaces deployed in water environment. The results show that the surface materials have the advantage that the underwater superoleophobicity is still preserved after the surfaces are scratched by knife or sandpaper and even completely destroyed because of the hydrophilic property of damaged materials in water. It is important that the results provide a guide for the design of durable underwater superoleophobic surfaces, and the development of superoleophobic materials in many potential applications such as the oil-repellent and the oil/water separation. Additionally, the nanosecond laser technology is simple, cost-effective and suitable for the large-area and mass fabrication of mechanically durable underwater superoleophobic metal materials.

A study of ignition phenomena of bulk metals by radiant heating

NASA Technical Reports Server (NTRS)

Branch, Melvin C.; Abbud-Madrid, A.; Feiereisen, T. J.; Daily, J. W.

1993-01-01

Early research on combustion of metals was motivated by the knowledge of the large heat release and corresponding high temperatures associated with metal-oxygen reactions. The advent of space flight brought about an increased interest in the ignition and combustion of metallic particles as additives in solid rocket propellants. More recently, attention has been given to the flammability properties of bulk, structural metals due to the number of accidental explosions of metal components in high-pressure oxygen systems. The following work represents a preliminary study that is part of a broader research effort aimed at providing further insight into the phenomena of bulk metal combustion by looking at the effects of gravity on the ignition behavior of metals. The scope of this preliminary experimental study includes the use of a non-coherent, continuous radiation ignition source, the measurement of temperature profiles of a variety of metals and a qualitative observation of the ignition phenomena at normal gravity. The specific objectives of the investigation include: (1) a feasibility study of the use of a continuous radiation source for metal ignition; (2) testing and characterization of the ignition behavior of a variety of metals; and (3) building a preliminary experimental database on ignition of metals under normal gravity conditions.

Nanoindentation hardness and atomic force microscope imaging studies of pressure-quenched zirconium metal

NASA Astrophysics Data System (ADS)

Catledge, Shane A.; Spencer, Philemon T.; Vohra, Yogesh K.

2000-11-01

We have carried out mechanical property measurements on zirconium metal compressed in a diamond anvil cell to 19 GPa at room temperature with subsequent quenching to room pressure. The irreversible transformation from the ambient hexagonal-close-packed phase to the simple hexagonal ω phase (AlB2 structure) is confirmed by synchrotron energy dispersive x-ray diffraction followed by nanoindentation of the pressure-quenched sample. We document an 80% increase in hardness as a consequence of the pressure-induced transformation to the ω phase at room temperature. This is a large increase for a metallic phase transformation and can be attributed to the presence of sp2-hybrid bonds forming graphite-like nets in the (0001) plane of the AlB2 structure. Atomic force microscopy of the indents shows that a plastic deformation of 2 μm in depth was achieved with a force of 200 mN.

Mechanical improvement of metal reinforcement rings for a finite ring-shaped superconducting bulk

NASA Astrophysics Data System (ADS)

Huang, Chen-Guang; Zhou, You-He

2018-03-01

As a key technique, reinforcement of type-II superconducting bulks with metal rings can efficiently improve their mechanical properties to enhance the maximum trapped field. In this paper, we study the magnetostrictive and fracture behaviors of a finite superconducting ring bulk reinforced by three typical reinforcing structures composed of metal rings during the magnetizing process by means of the minimization of magnetic energy and the finite element method. After a field-dependent critical current density is adopted, the magnetostriction, pinning-induced stress, and crack tip stress intensity factor are calculated considering the demagnetization effects. The results show that the mechanical properties of the ring bulk are strongly dependent on the reinforcing structure and the material and geometrical parameters of the metal rings. Introducing the metal ring can significantly reduce the hoop stress, and the reduction effect by internal reinforcement is much improved relative to external reinforcement. By comparison, bilateral reinforcement seems to be the best candidate structure. Only when the metal rings have particular Young's modulus and radial thickness will they contribute to improve the mechanical properties the most. In addition, if an edge crack is pre-existing in the ring bulk, the presence of metal rings can effectively avoid crack propagation since it reduces the crack tip stress intensity factor by nearly one order of magnitude.

About structural phase state of coating based on zirconium oxide formed by microplasma oxidation method

NASA Astrophysics Data System (ADS)

Gubaidulina, Tatiana A.; Sergeev, Viktor P.; Kuzmin, Oleg S.; Fedorischeva, Marina V.; Kalashnikov, Mark P.

2017-12-01

The oxide-ceramic coating based of zirconium oxide is formed by the method of microplasma oxidation. The producing modes of the oxide layers on E110 zirconium alloy are under testing. It was found that using microplasma treatment of E110 zirconium in aluminosilicate electrolyte makes possible the formation of porous oxide-ceramic coatings based on zirconium alloyed by aluminum and niobium. The study is focused on the modes how to form heat-shielding coatings with controlled porosity and minimal amount of microcracks. The structural-phase state of the coating is studied by X-ray diffraction analysis and scanning electron microscopy (SEM). It was found that the ratio of the monoclinic and tetragonal phases changes with the change occurring in the coating formation modes.

Structural rejuvenation in bulk metallic glasses

DOE PAGES

Tong, Yang; Iwashita, T.; Dmowski, Wojciech; ...

2015-01-05

Using high-energy X-ray diffraction we study structural changes in bulk metallic glasses after uniaxial compressive homogeneous deformation at temperatures slightly below the glass transition. We observe that deformation results in structural disordering corresponding to an increase in the fictive, or effective, temperature. However, the structural disordering saturates after yielding. Lastly, examination of the experimental structure and molecular dynamics simulation suggests that local changes in the atomic connectivity network are the main driving force of the structural rejuvenation.

Structural rejuvenation in bulk metallic glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong, Yang; Iwashita, T.; Dmowski, Wojciech

Using high-energy X-ray diffraction we study structural changes in bulk metallic glasses after uniaxial compressive homogeneous deformation at temperatures slightly below the glass transition. We observe that deformation results in structural disordering corresponding to an increase in the fictive, or effective, temperature. However, the structural disordering saturates after yielding. Lastly, examination of the experimental structure and molecular dynamics simulation suggests that local changes in the atomic connectivity network are the main driving force of the structural rejuvenation.

High-rate squeezing process of bulk metallic glasses

PubMed Central

Fan, Jitang

2017-01-01

High-rate squeezing process of bulk metallic glasses from a cylinder into an intact sheet achieved by impact loading is investigated. Such a large deformation is caused by plastic flow, accompanied with geometrical confinement, shear banding/slipping, thermo softening, melting and joining. Temperature rise during the high-rate squeezing process makes a main effect. The inherent mechanisms are illustrated. Like high-pressure torsion (HPT), equal channel angular pressing (ECAP) and surface mechanical attrition treatments (SMAT) for refining grain of metals, High-Rate Squeezing (HRS), as a multiple-functions technique, not only creates a new road of processing metallic glasses and other metallic alloys for developing advanced materials, but also directs a novel technology of processing, grain refining, coating, welding and so on for treating materials. PMID:28338092

High-rate squeezing process of bulk metallic glasses

NASA Astrophysics Data System (ADS)

Fan, Jitang

2017-03-01

High-rate squeezing process of bulk metallic glasses from a cylinder into an intact sheet achieved by impact loading is investigated. Such a large deformation is caused by plastic flow, accompanied with geometrical confinement, shear banding/slipping, thermo softening, melting and joining. Temperature rise during the high-rate squeezing process makes a main effect. The inherent mechanisms are illustrated. Like high-pressure torsion (HPT), equal channel angular pressing (ECAP) and surface mechanical attrition treatments (SMAT) for refining grain of metals, High-Rate Squeezing (HRS), as a multiple-functions technique, not only creates a new road of processing metallic glasses and other metallic alloys for developing advanced materials, but also directs a novel technology of processing, grain refining, coating, welding and so on for treating materials.

High-rate squeezing process of bulk metallic glasses.

PubMed

Fan, Jitang

2017-03-24

High-rate squeezing process of bulk metallic glasses from a cylinder into an intact sheet achieved by impact loading is investigated. Such a large deformation is caused by plastic flow, accompanied with geometrical confinement, shear banding/slipping, thermo softening, melting and joining. Temperature rise during the high-rate squeezing process makes a main effect. The inherent mechanisms are illustrated. Like high-pressure torsion (HPT), equal channel angular pressing (ECAP) and surface mechanical attrition treatments (SMAT) for refining grain of metals, High-Rate Squeezing (HRS), as a multiple-functions technique, not only creates a new road of processing metallic glasses and other metallic alloys for developing advanced materials, but also directs a novel technology of processing, grain refining, coating, welding and so on for treating materials.

Rapid Relaxation and Embrittlement of Zr-based Bulk Metallic Glasses by Electropulsing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yiu, P; Chen, Y. C.; Chu, J. P.

2013-01-01

Mechanical relaxation and embrittlement of Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glasses were achieved rapidly by the direct current electropulsing treatment. The temperature profile was recorded by an infrared camera and it was found to be non-uniform in the treated specimen. Specifically, temperatures below the glass transition temperature, near and above the crystallization temperature could be ach- ieved, respectively, at different locations in the same treated specimen. Two sets of nanoindentation were conducted. While the first set investigated the mechanical properties of three individually elec- tropulsed specimens with different conditions, the second set indented a single treated specimen along its temperature gradient. Bothmore » sets of indentation revealed that by Joule heating to different tempera- tures, relaxation, embrittlement, and crystallization were significantly accelerated by electrical pulses. Results suggest that electropulsing provides an opportunity to simultaneously achieve plastic forming and mechanical property control of metallic glasses.« less

Bulk metal concentrations versus total suspended solids in rivers: Time-invariant & catchment-specific relationships.

PubMed

Nasrabadi, Touraj; Ruegner, Hermann; Schwientek, Marc; Bennett, Jeremy; Fazel Valipour, Shahin; Grathwohl, Peter

2018-01-01

Suspended particles in rivers can act as carriers of potentially bioavailable metal species and are thus an emerging area of interest in river system monitoring. The delineation of bulk metals concentrations in river water into dissolved and particulate components is also important for risk assessment. Linear relationships between bulk metal concentrations in water (CW,tot) and total suspended solids (TSS) in water can be used to easily evaluate dissolved (CW, intercept) and particle-bound metal fluxes (CSUS, slope) in streams (CW,tot = CW + CSUS TSS). In this study, we apply this principle to catchments in Iran (Haraz) and Germany (Ammer, Goldersbach, and Steinlach) that show differences in geology, geochemistry, land use and hydrological characteristics. For each catchment, particle-bound and dissolved concentrations for a suite of metals in water were calculated based on linear regressions of total suspended solids and total metal concentrations. Results were replicable across sampling campaigns in different years and seasons (between 2013 and 2016) and could be reproduced in a laboratory sedimentation experiment. CSUS values generally showed little variability in different catchments and agree well with soil background values for some metals (e.g. lead and nickel) while other metals (e.g. copper) indicate anthropogenic influences. CW was elevated in the Haraz (Iran) catchment, indicating higher bioavailability and potential human and ecological health concerns (where higher values of CSUS/CW are considered as a risk indicator).

Trace metals in bulk precipitation and throughfall in a suburban area of Japan

NASA Astrophysics Data System (ADS)

Hou, H.; Takamatsu, T.; Koshikawa, M. K.; Hosomi, M.

Throughfall and bulk precipitation samples were collected monthly for 1.5 years over bare land and under canopies of Japanese cedar ( Cryptomeria japonica), Japanese red pine ( Pinus densiflora), Japanese cypress ( Chamaecyparis obtusa), and bamboo-leafed oak ( Quercus myrsinaefolia) in a suburban area of Japan. Samples were analyzed for dissolved Al, Mn, Fe, Cu, Zn, Ag, In, Sn, Sb and Bi by ICP-AES and ICP-MS. The metal concentrations were higher in throughfall, especially that of C. japonica, than bulk precipitation. Enrichment ratios (ERs: ratios of metal concentrations in throughfall to those in bulk precipitation) ranged from 2.5 (Zn) to 5.3 (Ag) (3.9 on average), and ERs for slightly soluble metals were generally higher than those for easily soluble metals. Concentrations of Mn, Fe, Cu, and Zn accounted for 99% of the total concentration of heavy metals in rainwater, whereas those of rare metals such as Ag, In, Sn, and Bi totaled <0.23%. Average concentrations of rare metals were 0.002 and 0.010 μg l -1 for Ag, 0.001 and 0.005 μg l -1 for In, 0.062 and 0.21 μg l -1 for Sn, and 0.006 and 0.023 μg l -1 for Bi in bulk precipitation and throughfall, respectively. The metal concentrations in rainwater were negatively correlated to the volume of rainwater, indicating that washout is the main mechanism that incorporates metals into rainwater. From the enrichment factors, that is, (X/Al) rain/(X/Al) crust, metals other than Fe were shown to be more enriched in rainwater than in the Earth's crust, including those present as a result of leaching from soil dust (Mn) and from anthropogenic sources (Cu, Zn, Ag, In, Sn, Sb, and Bi).

Superior removal of arsenic from water with zirconium metal-organic framework UiO-66.

PubMed

Wang, Chenghong; Liu, Xinlei; Chen, J Paul; Li, Kang

2015-11-12

In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5-280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds.

Superior removal of arsenic from water with zirconium metal-organic framework UiO-66

PubMed Central

Wang, Chenghong; Liu, Xinlei; Chen, J. Paul; Li, Kang

2015-01-01

In this study, water stable zirconium metal-organic framework (UiO-66) has been synthesized and for the first time applied as an adsorbent to remove aquatic arsenic contamination. The as-synthesized UiO-66 adsorbent functions excellently across a broad pH range of 1 to 10, and achieves a remarkable arsenate uptake capacity of 303 mg/g at the optimal pH, i.e., pH = 2. To the best of our knowledge, this is the highest arsenate As(V) adsorption capacity ever reported, much higher than that of currently available adsorbents (5–280 mg/g, generally less than 100 mg/g). The superior arsenic uptake performance of UiO-66 adsorbent could be attributed to the highly porous crystalline structure containing zirconium oxide clusters, which provides a large contact area and plenty of active sites in unit space. Two binding sites within the adsorbent framework are proposed for arsenic species, i.e., hydroxyl group and benzenedicarboxylate ligand. At equilibrium, seven equivalent arsenic species can be captured by one Zr6 cluster through the formation of Zr-O-As coordination bonds. PMID:26559001

A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO 2 Adsorption and Chemical Fixation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jie; Usov, Pavel M.; Xu, Wenqian

Metal–organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr 6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions andmore » maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO 2 uptake capacity (up to ~9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO 2 with epoxides, including sterically hindered epoxides. Thus, the MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.« less

A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO 2 Adsorption and Chemical Fixation

DOE PAGES

Zhu, Jie; Usov, Pavel M.; Xu, Wenqian; ...

2017-12-22

Metal–organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr 6 clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions andmore » maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO 2 uptake capacity (up to ~9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO 2 with epoxides, including sterically hindered epoxides. Thus, the MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.« less

Preparation of lead-zirconium-titanium film and powder by electrodeposition

DOEpatents

Bhattacharya, Raghu N.; Ginley, David S.

1995-01-01

A process for the preparation of lead-zirconium-titanium (PZT) film and powder compositions. The process comprises the steps of providing an electrodeposition bath, providing soluble salts of lead, zirconium and titanium metals to this bath, electrically energizing the bath to thereby direct ions of each respective metal to a substrate electrode and cause formation of metallic particles as a recoverable film of PZT powder on the electrode, and also recovering the resultant film as a powder. Recovery of the PZT powder can be accomplished by continually energizing the bath to thereby cause powder initially deposited on the substrate-electrode to drop therefrom into the bath from which it is subsequently removed. A second recovery alternative comprises energizing the bath for a period of time sufficient to cause PZT powder deposition on the substrate-electrode only, from which it is subsequently recovered. PZT film and powder so produced can be employed directly in electronic applications, or the film and powder can be subsequently oxidized as by an annealing process to thereby produce lead-zirconium-titanium oxide for use in electronic applications.

Continuum-Scale Modeling of Shear Banding in Bulk Metallic Glass-Matrix Composites

NASA Astrophysics Data System (ADS)

Gibbons, Michael

Metallic glasses represent a relatively new class of materials that have demonstrated enormous potential for functional and structural applications due to the unique set of properties attributed to them as a result of the disordered isotropic structure with metallically bonded elements. Amorphous metals benefit from the strong nature of the metallic bonds, but lack the crystallographic structure and polycrystalline nature of traditional metals which unsurprisingly has huge implications on the material properties, as all deformation mechanisms associated with a lattice are suppressed. This results in excellent strength, a high elastic strain limit, exceptional hardness, and improved corrosion and wear resistance. "Bulk" metallic glasses (BMG) represent the amorphous metals which can be produced at the cm length-scale, thus greatly expanding their applicability for structural applications. However, due to the catastrophic nature of the failure produced upon yielding, monolithic metallic glasses are seldomly used for structural applications. Bulk metallic glass-matrix composites (BMGMCs), however, are able to combine the excellent strength, hardness, and elastic strain limit of amorphous metallic glass with a ductile crystalline phase to achieve extraordinary toughness with minimal degradation in strength. In order to explore the mechanical interactions between the amorphous and crystalline phases, a full-field micromechanical model which couples the free-volume based constitutive behavior for the matrix phase with standard rate-dependent crystal plasticity for the dendrites, and its implementation via an elastic-viscoplastic Fast-Fourier Transform (FFT) solver. The model is calibrated to macroscale stress-strain data for Ti-Zr-V-Cu-Be BMGMCs with varying composition and furthermore by comparing the deformation behavior associated with the shear bands predicted by the model, to the artifacts observed from characterization microscopy analysis on the same failed BMGMC

Oxide film on metal substrate reduced to form metal-oxide-metal layer structure

NASA Technical Reports Server (NTRS)

Youngdahl, C. A.

1967-01-01

Electrically conductive layer of zirconium on a zirconium-oxide film residing on a zirconium substrate is formed by reducing the oxide in a sodium-calcium solution. The reduced metal remains on the oxide surface as an adherent layer and seems to form a barrier that inhibits further reaction.

Pair distribution function study and mechanical behavior of as-cast and structurally relaxed Zr-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Fan, Cang; Liaw, P. K.; Wilson, T. W.; Choo, H.; Gao, Y. F.; Liu, C. T.; Proffen, Th.; Richardson, J. W.

2006-12-01

Contrary to reported results on structural relaxation inducing brittleness in amorphous alloys, the authors found that structural relaxation actually caused an increase in the strength of Zr55Cu35Al10 bulk metallic glass (BMG) without changing the plasticity. Three dimensional models were rebuilt for the as-cast and structurally relaxed BMGs by reverse Monte Carlo (RMC) simulations based on the pair distribution function (PDF) measured by neutron scattering. Only a small portion of the atom pairs was found to change to more dense packing. The concept of free volume was defined based on the PDF and RMC studies, and the mechanism of mechanical behavior was discussed.

Development of Co-based bulk metallic glasses as potential biomaterials.

PubMed

Zhou, Zeyan; Wei, Qin; Li, Qiang; Jiang, Bingliang; Chen, You; Sun, Yanfei

2016-12-01

A new series of Co80-x-yCrxMoyP14B6 (x=5 y=5; x=5 y=10; x=10 y=10, all values in at.%) bulk metallic glasses (BMGs) with a maximum diameter of 1.5mm has been developed for using them as potential bio-implant materials by a combination of fluxing treatment and J-quenching technique. The performance of the present Co-based BMGs in biomedical implant applications was investigated as compared to the CoCrMo biomedical alloy (ASTM F75) and 316L stainless steel (316L SS). The corrosion behavior of the samples was investigated in both Hank's solution (pH=7.4) and artificial saliva solution (pH=6.3) at 37°C employing electrochemical measurements. The results indicate that the Co-based BMGs exhibit much higher corrosion resistance in the simulated body solutions than that of 316L SS. Compared with the corrosion resistance of ASTM F75, that of Co70Cr5Mo5P14B6 and Co65Cr5Mo10P14B6 BMGs is found to be lower and that of Co60Cr10Mo10P14B6 BMG is higher. The concentrations of Co, Cr, and Mo ions released into the simulated body solutions from our Co-based BMGs after potentiodynamic polarization are significantly lower than that released from ASTM F75. The biocompatibility of the specimens was evaluated using an in vitro test of NIH3T3 cell culture in the specimen extraction media for 1, 3, 5, and 7days, revealing the non-cytotoxicity of the Co-based BMGs towards NIH3T3 cells. Moreover, examinations on the cell adhesion and growth on the surface of the specimens indicate that the Co-based BMGs exhibit better cell viability compared to ASTM F75 and 316L SS biomedical alloys. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemical Study of Corrosion Phenomena in Zirconium Alloys

DTIC Science & Technology

2005-06-01

required reaction rates [1.1]. Based predominantly on this fact, zirconium alloys were chosen to sheath, or clad, the fuel. With the increasing demand...cathode or anode. As the oxidation and reduction reactions occur, a galvanic cell is developed. The electrons on the anode are released from the metallic...matrix as the ions are released into the aqueous solution in the initial half-cell reaction . The second half-cell reaction , taking place on the

Fracture behaviors under pure shear loading in bulk metallic glasses.

PubMed

Chen, Cen; Gao, Meng; Wang, Chao; Wang, Wei-Hua; Wang, Tzu-Chiang

2016-12-23

Pure shear fracture test, as a special mechanical means, had been carried out extensively to obtain the critical information for traditional metallic crystalline materials and rocks, such as the intrinsic deformation behavior and fracture mechanism. However, for bulk metallic glasses (BMGs), the pure shear fracture behaviors have not been investigated systematically due to the lack of a suitable test method. Here, we specially introduce a unique antisymmetrical four-point bend shear test method to realize a uniform pure shear stress field and study the pure shear fracture behaviors of two kinds of BMGs, Zr-based and La-based BMGs. All kinds of fracture behaviors, the pure shear fracture strength, fracture angle and fracture surface morphology, are systematically analyzed and compared with those of the conventional compressive and tensile fracture. Our results indicate that both the Zr-based and La-based BMGs follow the same fracture mechanism under pure shear loading, which is significantly different from the situation of some previous research results. Our results might offer new enlightenment on the intrinsic deformation and fracture mechanism of BMGs and other amorphous materials.

Fracture behaviors under pure shear loading in bulk metallic glasses

NASA Astrophysics Data System (ADS)

Chen, Cen; Gao, Meng; Wang, Chao; Wang, Wei-Hua; Wang, Tzu-Chiang

2016-12-01

Pure shear fracture test, as a special mechanical means, had been carried out extensively to obtain the critical information for traditional metallic crystalline materials and rocks, such as the intrinsic deformation behavior and fracture mechanism. However, for bulk metallic glasses (BMGs), the pure shear fracture behaviors have not been investigated systematically due to the lack of a suitable test method. Here, we specially introduce a unique antisymmetrical four-point bend shear test method to realize a uniform pure shear stress field and study the pure shear fracture behaviors of two kinds of BMGs, Zr-based and La-based BMGs. All kinds of fracture behaviors, the pure shear fracture strength, fracture angle and fracture surface morphology, are systematically analyzed and compared with those of the conventional compressive and tensile fracture. Our results indicate that both the Zr-based and La-based BMGs follow the same fracture mechanism under pure shear loading, which is significantly different from the situation of some previous research results. Our results might offer new enlightenment on the intrinsic deformation and fracture mechanism of BMGs and other amorphous materials.

Tribological studies of a Zr-based bulk metallic glass with different states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Feng; Qu, Jun; Fan, Guojiang

The tribological characteristics of a bulk-metallic glass (BMG) Zr52.5Cu17.9Ni14.6Al10.0Ti5.0 (Vit 105) with different states have been studied. Friction and wear tests were conducted using a ball-on-flat reciprocating sliding apparatus against AISI E52100 bearing steel under dry condition. The observed wear resistance in an ascending order is deformed, crept, relaxed, and as-cast. Results suggested that the wear process of BMG alloys involved abrasion, adhesion, and oxidation. The differences in hardness, free volume, and embrittlement at different states significantly affected the friction and wear behaviors of the BMG alloys.

Geologic structure of Gofitsky deposit of titanium and zirconium and perspectives of the reserve base of titanium and zirconium in Russia

NASA Astrophysics Data System (ADS)

Kukhmazov, Iskander

2016-04-01

With the fall of the Soviet Union, all the mining deposits of titanium and zirconium appeared outside of Russian Federation. Therefore the studying of deposits of titanium and zirconium in Russia is very important nowadays. There is a paradoxical situation in the country: in spite of possible existence of national mineral resource base of Ti-Zr material, which can cover needs of the country, Russia is the one of the largest buyers of imported Ti-Zr material in the world. Many deposits are not mined, and those which are in the process of mining have poor reserves. Demand for this raw material is very great not only for Russia, but also for the world in general. Today there is a scarcity of zircon around the world and it will only increase through time. Therefore prices of products of titanium and zirconium also increase. Consequently Russian deposits of titanium and zirconium with higher content than foreign may become competitive. Russia is forced to buy raw materials (zirconium and titanium production) from former Soviet Union countries at prices higher than the world's and thus incur huge losses, including customs charges. Russia should create its own mineral resource base of Ti-Zr. Studied titanium-zirconium deposits of Stavropol region may become the basis for the south part of Russia. At first, Beshpagirsky deposit should be pointed out. It has large reserves of ore sands with high content of Ti-Zr. A combination of favorable geographical position of the area with developed industrial infrastructure makes it very beneficial as an object for high priority development. Gofitsky deposit should be pointed out as well. Its sands have a wide areal distribution and a high content of titanium and zirconium. Chokrak, Karagan-Konksk and Sarmatian sediments of the Miocene of Gofitsky deposit are productive for titanium and zirconium placers within Stavropol region of Russia. Gofitsky deposit was evaluated from financial and economic point of view and the following data

Isomerization of Cyclooctadiene to Cyclooctyne with a Zinc/Zirconium Heterobimetallic Complex

PubMed Central

Butler, Michael J.; White, Andrew J. P.

2016-01-01

Abstract Reaction of a zinc/zirconium heterobimetallic complex with 1,5‐cyclooctadiene (1,5‐COD) results in slow isomerization to 1,3‐cyclooctadiene (1,3‐COD), along with the formation of a new complex that includes a cyclooctyne ligand bridging two metal centers. While analogous magnesium/zirconium and aluminum/zirconium heterobimetallic complexes are competent for the catalytic isomerization of 1,5‐COD to 1,3‐COD, only in the case of the zinc species is the cyclooctyne adduct observed. PMID:27071992

Mechanical rejuvenation in bulk metallic glass induced by thermo-mechanical creep

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tong, Yang; Dmowski, W.; Bei, Hongbin

Using high energy X-ray diffraction we studied the temperature, stress, and time effect on structural changes in a Zr-based bulk metallic glass induced by thermo-mechanical creep. Pair distribution functions obtained from two-dimensional diffraction patterns show that thermo-mechanical creep induces structural disordering, but only when the stress beyond a threshold is applied. A similar threshold behavior was observed for anelastic strain. We conclude that anelastic creep strain induces rejuvenation, whereas plastic strain does not.

Mechanical rejuvenation in bulk metallic glass induced by thermo-mechanical creep

DOE PAGES

Tong, Yang; Dmowski, W.; Bei, Hongbin; ...

2018-02-16

Using high energy X-ray diffraction we studied the temperature, stress, and time effect on structural changes in a Zr-based bulk metallic glass induced by thermo-mechanical creep. Pair distribution functions obtained from two-dimensional diffraction patterns show that thermo-mechanical creep induces structural disordering, but only when the stress beyond a threshold is applied. A similar threshold behavior was observed for anelastic strain. We conclude that anelastic creep strain induces rejuvenation, whereas plastic strain does not.

Bulk metal concentrations versus total suspended solids in rivers: Time-invariant & catchment-specific relationships

PubMed Central

Ruegner, Hermann; Schwientek, Marc; Bennett, Jeremy; Fazel Valipour, Shahin; Grathwohl, Peter

2018-01-01

Suspended particles in rivers can act as carriers of potentially bioavailable metal species and are thus an emerging area of interest in river system monitoring. The delineation of bulk metals concentrations in river water into dissolved and particulate components is also important for risk assessment. Linear relationships between bulk metal concentrations in water (CW,tot) and total suspended solids (TSS) in water can be used to easily evaluate dissolved (CW, intercept) and particle-bound metal fluxes (CSUS, slope) in streams (CW,tot = CW + CSUS TSS). In this study, we apply this principle to catchments in Iran (Haraz) and Germany (Ammer, Goldersbach, and Steinlach) that show differences in geology, geochemistry, land use and hydrological characteristics. For each catchment, particle-bound and dissolved concentrations for a suite of metals in water were calculated based on linear regressions of total suspended solids and total metal concentrations. Results were replicable across sampling campaigns in different years and seasons (between 2013 and 2016) and could be reproduced in a laboratory sedimentation experiment. CSUS values generally showed little variability in different catchments and agree well with soil background values for some metals (e.g. lead and nickel) while other metals (e.g. copper) indicate anthropogenic influences. CW was elevated in the Haraz (Iran) catchment, indicating higher bioavailability and potential human and ecological health concerns (where higher values of CSUS/CW are considered as a risk indicator). PMID:29342204

Ductilizing bulk metallic glass composite by tailoring stacking fault energy.

PubMed

Wu, Y; Zhou, D Q; Song, W L; Wang, H; Zhang, Z Y; Ma, D; Wang, X L; Lu, Z P

2012-12-14

Martensitic transformation was successfully introduced to bulk metallic glasses as the reinforcement micromechanism. In this Letter, it was found that the twinning property of the reinforcing crystals can be dramatically improved by reducing the stacking fault energy through microalloying, which effectively alters the electron charge density redistribution on the slipping plane. The enhanced twinning propensity promotes the martensitic transformation of the reinforcing austenite and, consequently, improves plastic stability and the macroscopic tensile ductility. In addition, a general rule to identify effective microalloying elements based on their electronegativity and atomic size was proposed.

Fabrication and Mechanical Behavior of Ex Situ Mg-Based Bulk Metallic Glass Matrix Composite Reinforced with Electroless Cu-Coated SiC Particles.

PubMed

Wang, Xin; Zhao, Lichen; Hu, Ximei; Cheng, Yongjian; Liu, Shuiqing; Chen, Peng; Cui, Chunxiang

2017-11-30

Magnesium-based bulk metallic glass matrix composites (BMGMCs) have better plasticity than the corresponding bulk metallic glasses (BMGs); however, their strength and density are often compromised due to the fact that the effective reinforcement phase is mostly plastic heavy metal. For lightweight SiC-particle reinforced BMGMCs, interface wettability and the sharpness of the particles often reduce the strengthening effect. In this work, SiC particles were coated with a thin Cu coating by electroless plating, and added to Mg 54 Cu 26.5 Ag 8.5 Gd 11 melt in an amount of 5 wt % to prepare a BMGMC. The microstructure of the interface, mechanical behavior and fracture morphology of the BMGMC were studied by scanning electron microscopy and quasi-static compression testing. The results showed that the Cu coating improved the wettability between SiC and the matrix alloy without obvious interfacial reactions, leading to the dispersion of SiC particles in the matrix. The addition of Cu-coated SiC particles improved the plastic deformation ability of Mg 54 Cu 26.5 Ag 8.5 Gd 11 BMG, proving that electroless plating was an effective method for controlling the interface microstructure and mechanical behavior of BMGMCs.

Isomerization of Cyclooctadiene to Cyclooctyne with a Zinc/Zirconium Heterobimetallic Complex.

PubMed

Butler, Michael J; White, Andrew J P; Crimmin, Mark R

2016-06-06

Reaction of a zinc/zirconium heterobimetallic complex with 1,5-cyclooctadiene (1,5-COD) results in slow isomerization to 1,3-cyclooctadiene (1,3-COD), along with the formation of a new complex that includes a cyclooctyne ligand bridging two metal centers. While analogous magnesium/zirconium and aluminum/zirconium heterobimetallic complexes are competent for the catalytic isomerization of 1,5-COD to 1,3-COD, only in the case of the zinc species is the cyclooctyne adduct observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of lead-zirconium-titanium film and powder by electrodeposition

DOEpatents

Bhattacharya, R.N.; Ginley, D.S.

1995-10-31

A process is disclosed for the preparation of lead-zirconium-titanium (PZT) film and powder compositions. The process comprises the steps of providing an electrodeposition bath, providing soluble salts of lead, zirconium and titanium metals to this bath, electrically energizing the bath to thereby direct ions of each respective metal to a substrate electrode and cause formation of metallic particles as a recoverable film of PZT powder on the electrode, and also recovering the resultant film as a powder. Recovery of the PZT powder can be accomplished by continually energizing the bath to thereby cause powder initially deposited on the substrate-electrode to drop therefrom into the bath from which it is subsequently removed. A second recovery alternative comprises energizing the bath for a period of time sufficient to cause PZT powder deposition on the substrate-electrode only, from which it is subsequently recovered. PZT film and powder so produced can be employed directly in electronic applications, or the film and powder can be subsequently oxidized as by an annealing process to thereby produce lead-zirconium-titanium oxide for use in electronic applications. 4 figs.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Feasibility of using bulk metallic glass for self-expandable stent applications.

PubMed

Praveen Kumar, Gideon; Jafary-Zadeh, Mehdi; Tavakoli, Rouhollah; Cui, Fangsen

2017-10-01

Self-expandable stents are widely used to restore blood flow in a diseased artery segment by keeping the artery open after angioplasty. Despite the prevalent use of conventional crystalline metallic alloys, for example, nitinol, to construct self-expandable stents, new biomaterials such as bulk metallic glasses (BMGs) are being actively pursued to improve stent performance. Here, we conducted a series of analyses including finite element analysis and molecular dynamics simulations to investigate the feasibility of using a prototypical Zr-based BMG for self-expandable stent applications. We model stent crimping of several designs for different percutaneous applications. Our results indicate that BMG-based stents with diamond-shaped crowns suffer from severe localization of plastic deformation and abrupt failure during crimping. As a possible solution, we further illustrate that such abrupt failure could be avoided in BMG-based stents without diamond shape crowns. This work would open a new horizon for a quest toward exploiting superior mechanical and functional properties of metallic glasses to design future stents. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1874-1882, 2017. © 2016 Wiley Periodicals, Inc.

In-situ surface science studies of the interaction between sulfur dioxide and two-dimensional palladium loaded-cerium/zirconium mixed metal oxide model catalysts

NASA Astrophysics Data System (ADS)

Romano, Esteban Javier

2005-07-01

Cerium and zirconium oxides are important materials in industrial catalysis. Particularly, the great advances attained in the past 30 years in controlling levels of gaseous pollutants released from internal combustion engines can be attributed to the development of catalysts employing these materials. Unfortunately, oxides of sulfur are known threats to the longevity of many catalytic systems by irreversibly interacting with catalytic materials. In this work, polycrystalline cerium-zirconium mixed-metal-oxide (MMO) solid solutions were synthesized. High resolution x-ray photoelectron spectroscopy (XPS) spectral data was collected and examined for revelation of the surface species that form on these metal oxides after in-situ exposures to sulfur dioxide. The model catalysts were exposed to sulfur dioxide using a custom modified in-situ reaction cell and platen heater. The results of this study demonstrate the formation of sulfate and sulfite surface sulfur species. Temperature and compositional dependencies were displayed, with higher temperatures and ceria molar ratios displaying a larger propensity for forming surface sulfur species. In addition to analysis of sulfur photoemission, the photoemission regions of oxygen, zirconium, and cerium were examined for the materials used in this study before and after the aforementioned treatments with sulfur dioxide. The presence of surface hydroxyl groups was observed and metal oxidation state changes were probed to further enhance the understanding of sulfur dioxide adsorption on the synthesized materials. Palladium loaded mixed-metal oxides were synthesized using a unique solid-state methodology to probe the effect of palladium addition on sulfur dioxide adsorption. The addition of palladium to this model system is shown to have a strong effect on the magnitude of adsorption for sulfur dioxide on some material/exposure condition combinations. Ceria/zirconia sulfite and sulfate species are identified on the palladium

PROCESS FOR DISSOLVING BINARY URANIUM-ZIRCONIUM OR ZIRCONIUM-BASE ALLOYS

DOEpatents

Jonke, A.A.; Barghusen, J.J.; Levitz, N.M.

1962-08-14

A process of dissolving uranium-- zirconium and zircaloy alloys, e.g. jackets of fuel elements, with an anhydrous hydrogen fluoride containing from 10 to 32% by weight of hydrogen chloride at between 400 and 450 deg C., preferably while in contact with a fluidized inert powder, such as calcium fluoride is described. (AEC)

NEUTRON REACTOR FUEL ELEMENT UTILIZING ZIRCONIUM-BASE ALLOYS

DOEpatents

Saller, H.A.; Keeler, J.R.; Szumachowski, E.R.

1957-11-12

This patent relates to clad fuel elements for use in neutronic reactors and is drawn to such a fuel element which consists of a core of fissionable material, comprised of an alloy of zirconium and U/sup 235/ enriched uranium, encased in a jacket of a binary zirconium-tin alloy in which the tin content ranges between 1 and 15% by weight.

Criticality in Bulk Metallic Glass Constituent Elements

NASA Astrophysics Data System (ADS)

Mota, Rodrigo Miguel Ojeda; Graedel, T. E.; Pekarskaya, Evgenia; Schroers, Jan

2017-11-01

Bulk metallic glasses (BMGs), which readily form amorphous phases during solidification, are increasingly being used in first applications of watch components, electronic casings, and sporting goods. The compositions of BMGs typically include four to six elements. Various political and geological factors have recently led to supply disruptions for several metals, including some present in BMG compositions. In this work, we assess the "criticality" of 22 technologically interesting BMG compositions, compare the results with those for three common engineering alloy groups, and derive recommendations for BMG composition choices from a criticality perspective. The criticality of BMGs is found to be generally much higher compared with those for the established engineering alloys. Therefore, criticality concerns should also be considered in the choice between existing and developing novel BMGs.

Cavitation instability in bulk metallic glasses

NASA Astrophysics Data System (ADS)

Dai, L. H.; Huang, X.; Ling, Z.

2015-09-01

Recent experiments have shown that fracture surfaces of bulk metallic glasses (BMGs) usually exhibit an intriguing nanoscale corrugation like fractographic feature mediated by nanoscale void formation. We attribute the onset of this nanoscale corrugation to TTZs (tension transformation zones) mediated cavitation. In our recent study, the spall experiments of Zr-based BMG using a single-stage light gas gun were performed. To uncover the mechanisms of the spallation damage nucleation and evolution, the samples were designed to be subjected to dynamic tensile loadings of identical amplitude but with different durations by making use of the multi-stress pulse and the double-flyer techniques. It is clearly revealed that the macroscopic spall fracture in BMGs originates from the nucleation, growth and coalescence of micro-voids. Then, a microvoid nucleation model of BMGs based on free volume theory is proposed, which indicates that the nucleation of microvoids at the early stage of spallation in BMGs is resulted from diffusion and coalescence of free volume. Furthermore, a theoretical model of void growth in BMGs undergoing remote dynamic hydrostatic tension is developed. The critical condition of cavitation instability is obtained. It is found that dynamic void growth in BMGs can be well controlled by a dimensionless inertial number characterizing the competition between intrinsic and extrinsic time scales. To unveil the atomic-level mechanism of cavitation, a systematic molecular dynamics (MD) simulation of spallation behaviour of a binary metallic glass with different impact velocities was performed. It is found that micro-void nucleation is determined TTZs while the growth is controlled by shear transformation zones (STZs) at atomic scale.

Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

PubMed Central

Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

2016-01-01

The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated. PMID:26754315

ZIRCONIUM-TITANIUM-BERYLLIUM BRAZING ALLOY

DOEpatents

Gilliland, R.G.; Patriarca, P.; Slaughter, G.M.; Williams, L.C.

1962-06-12

A new and improved ternary alloy is described which is of particular utility in braze-bonding parts made of a refractory metal selected from Group IV, V, and VI of the periodic table and alloys containing said metal as a predominating alloying ingredient. The brazing alloy contains, by weight, 40 to 50 per cent zirconium, 40 to 50 per cent titanium, and the balance beryllium in amounts ranging from 1 to 20 per cent, said alloy having a melting point in the range 950 to 1400 deg C. (AEC)

Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

DOE PAGES

Ma, Wen; Senanayake, Sanjaya D.; Herbert, F. William; ...

2015-03-11

The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+, Zr 2+, and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. As a result, themore » presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.« less

METHOD AND ALLOY FOR BONDING TO ZIRCONIUM

DOEpatents

McCuaig, F.D.; Misch, R.D.

1960-04-19

A brazing alloy can be used for bonding zirconium and its alloys to other metals, ceramics, and cermets, and consists of 6 to 9 wt.% Ni, 6 to 9 wn~.% Cr, Mo, or W, 0 to 7.5 wt.% Fe, and the balance Zr.

In situ ceramic layer growth on coated fuel particles dispersed in a zirconium metal matrix

DOE Office of Scientific and Technical Information (OSTI.GOV)

Terrani, Kurt A; Silva, G W Chinthaka M; Kiggans, Jim

2013-01-01

The extent and nature of the chemical interaction between the outermost coating layer of coated fuel particles embedded in zirconium metal during fabrication of metal matrix microencapsulated fuels was examined. Various particles with outermost coating layers of pyrocarbon, SiC, and ZrC have been investigated in this study. ZrC-Zr interaction was least substantial while PyC-Zr reaction can be exploited to produce a ZrC layer at the interface in an in situ manner. The thickness of the ZrC layer in the latter case can be controlled by adjusting the time and temperature during processing. The kinetics of ZrC layer growth is significantlymore » faster from what is predicted using literature carbon diffusivity data in ZrC. SiC-Zr interaction is more complex and results in formation of various chemical phases in a layered aggregate morphology at the interface.« less

THE ANALYSIS OF URANIUM-ZIRCONIUM ALLOYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milner, G.W.C.; Skewies, A.F.

1953-03-01

A satisfactory procedure is described for the analysis of uranium-zirconium alloys containing up to 25% zirconium. It is based on the separation of the zirconium from the uranium by dissolving the cupferron complex of the former element into chloroform. After the evaporation of the solvent from the combined organic extracts, the residue is ignited to zirconium oxide. The latter is then re-dissolved and zirconium is separated from other elements co-extracted in the solvent extraction procedure by precipitation with mandelic acid. The zirconium mandelate is finally ignited to oxide at 960 deg C. The uranium is separated from the aqueous solutionmore » remaining from the cupferron extraction by precipitating with tannin at a pH of 8; the precipitate being removed by filtration and then ignited a t 800 deg C. The residue is dissolved in nitric acid and the uranium is finally determined by precipitating as ammonium diuranate and then igniting to U{sub 3}O{sub 8}. (auth)« less

Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

DOEpatents

Hu, Michael Z.

2006-05-23

Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.

In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

DOEpatents

Kim, Choong Paul; Hays, Charles C.; Johnson, William L.

2004-03-23

A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

In-situ ductile metal/bulk metallic glass matrix composites formed by chemical partitioning

DOEpatents

Kim, Choong Paul [Northridge, CA; Hays, Charles C [Pasadena, CA; Johnson, William L [Pasadena, CA

2007-07-17

A composite metal object comprises ductile crystalline metal particles in an amorphous metal matrix. An alloy is heated above its liquidus temperature. Upon cooling from the high temperature melt, the alloy chemically partitions, forming dendrites in the melt. Upon cooling the remaining liquid below the glass transition temperature it freezes to the amorphous state, producing a two-phase microstructure containing crystalline particles in an amorphous metal matrix. The ductile metal particles have a size in the range of from 0.1 to 15 micrometers and spacing in the range of from 0.1 to 20 micrometers. Preferably, the particle size is in the range of from 0.5 to 8 micrometers and spacing is in the range of from 1 to 10 micrometers. The volume proportion of particles is in the range of from 5 to 50% and preferably 15 to 35%. Differential cooling can produce oriented dendrites of ductile metal phase in an amorphous matrix. Examples are given in the Zr--Ti--Cu--Ni--Be alloy bulk glass forming system with added niobium.

Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release.

PubMed

Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

2016-08-01

Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future.

Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release

PubMed Central

Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

2016-01-01

Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future. PMID:27493996

Joining of Zirconium Diboride-Based Ceramic Composites to Metallic Systems for High-Temperature Applications

NASA Technical Reports Server (NTRS)

Asthana, R.; Singh, M.

2008-01-01

Three types of hot-pressed zirconium diboride (ZrB2)-based ultra-high-temperature ceramic composites (UHTCC), ZrB2-SiC (ZS), ZrB2-SiC-C (ZSC), and ZrB2-SCS9-SiC (ZSS), were joined to Cu-clad-Mo using two Ag-Cu brazes (Cusil-ABA and Ticusil, T(sub L) approx.1073-1173 K) and two Pd-base brazes (Palco and Palni, T(sub L) approx.1493-1513 K). Scanning Electron Microscopy (SEM) coupled with energy-dispersive spectroscopy (EDS) revealed greater chemical interaction in joints made using Pd-base brazes than in joints made using Ag-Cu based active brazes. The degree of densification achieved in hot pressed composites influenced the Knoop hardness of the UHTCC and the hardness distribution across the braze interlayer. The braze region in Pd-base system displayed higher hardness in joints made using fully-dense ZS composites than in joints made using partially-dense ZSS composites and the carbon-containing ZSC composites. Calculations indicate a small negative elastic strain energy and an increase in the UHTCC's fracture stress up to a critical clad layer thickness . Above this critical thickness, strain energy in the UHTCC is positive, and it increases with increasing clad layer thickness. Empirical projections show a reduction in the effective thermal resistance of the joints and highlight the potential benefits of joining the UHTCC to Cu-clad-Mo.

Spallation behaviour of a Zr-bulk metallic glass

NASA Astrophysics Data System (ADS)

Ling, Z.; Huang, X.; Shen, L. T.; Dai, L. H.

2012-08-01

Plate impact experiments have been conducted on a Zr-based bulk metal glass (BMG) using a single stage light gas gun. To understand the spallation process of the material, samples were subjected to dynamic tensile loadings of the same amplitude but different durations. Fractographs of spallation surface and fracture features were characterized and the fracture mechanism of different regions of the spallation surface was discussed. Morphology of the spallation surface in the Zr-BMG exhibited a typical equiaxial cellular pattern and porous microstructure. These experiments revealed that, subjected to hydro-tensile stresses, the microdamage of the spallation occurred in the Zr-BMG is microvoids; the spallation in the Zr-BMG is resulted from nucleation, growth and coalescence of microvoids; and the time needed for these microvoids nucleation is less than 100 ns with a stress amplitude of 3.18 GPa.

Dynamic fracture instability of tough bulk metallic glass

NASA Astrophysics Data System (ADS)

Meng, J. X.; Ling, Z.; Jiang, M. Q.; Zhang, H. S.; Dai, L. H.

2008-04-01

We report the observations of a clear fractographic evolution from vein pattern, dimple structure, and then to periodic corrugation structure, followed by microbranching pattern, along the crack propagation direction in the dynamic fracture of a tough Zr41.2Ti13.8Cu12.5Ni10Be22.5 (Vit.1) bulk metallic glass (BMGs) under high-velocity plate impact. A model based on fracture surface energy dissipation and void growth is proposed to characterize this fracture pattern transition. We find that once the dynamic crack propagation velocity reaches a critical fraction of Rayleigh wave speed, the crack instability occurs; hence, crack microbranching goes ahead. Furthermore, the correlation between the critical velocity of amorphous materials and their intrinsic strength such as Young's modulus is uncovered. The results may shed new insight into dynamic fracture instability for BMGs.

Liquid-solid joining of bulk metallic glasses

NASA Astrophysics Data System (ADS)

Huang, Yongjiang; Xue, Peng; Guo, Shu; Wu, Yang; Cheng, Xiang; Fan, Hongbo; Ning, Zhiliang; Cao, Fuyang; Xing, Dawei; Sun, Jianfei; Liaw, Peter K.

2016-07-01

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr51Ti5Ni10Cu25Al9 and Zr50.7Cu28Ni9Al12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. The liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components.

Liquid-solid joining of bulk metallic glasses

PubMed Central

Huang, Yongjiang; Xue, Peng; Guo, Shu; Wu, Yang; Cheng, Xiang; Fan, Hongbo; Ning, Zhiliang; Cao, Fuyang; Xing, Dawei; Sun, Jianfei; Liaw, Peter K.

2016-01-01

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr51Ti5Ni10Cu25Al9 and Zr50.7Cu28Ni9Al12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. The liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components. PMID:27471073

Liquid-solid joining of bulk metallic glasses.

PubMed

Huang, Yongjiang; Xue, Peng; Guo, Shu; Wu, Yang; Cheng, Xiang; Fan, Hongbo; Ning, Zhiliang; Cao, Fuyang; Xing, Dawei; Sun, Jianfei; Liaw, Peter K

2016-07-29

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr51Ti5Ni10Cu25Al9 and Zr50.7Cu28Ni9Al12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. The liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components.

Liquid-solid joining of bulk metallic glasses

DOE PAGES

Huang, Yongjiang; Xue, Peng; Guo, Shu; ...

2016-07-29

Here, we successfully welded two bulk metallic glass (BMG) materials, Zr 51Ti 5Ni 10Cu 25Al 9 and Zr 50.7Cu 28Ni 9Al 12.3 (at. %), using a liquid-solid joining process. An atomic-scale metallurgical bonding between two BMGs can be achieved. The interface has a transition layer of ~50 μm thick. In conclusion, the liquid-solid joining of BMGs can shed more insights on overcoming their size limitation resulting from their limited glass-forming ability and then promoting their applications in structural components.

Towards the Better: Intrinsic Property Amelioration in Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Sarac, Baran; Zhang, Long; Kosiba, Konrad; Pauly, Simon; Stoica, Mihai; Eckert, Jürgen

2016-06-01

Tailoring the intrinsic length-scale effects in bulk metallic glasses (BMGs) via post-heat treatment necessitates a systematic analyzing strategy. Although various achievements were made in the past years to structurally enhance the properties of different BMG alloys, the influence of short-term sub-glass transition annealing on the relaxation kinetics is still not fully covered. Here, we aim for unraveling the connection between the physical, (thermo)mechanical and structural changes as a function of selected pre-annealing temperatures and time scales with an in-house developed Cu46Zr44Al8Hf2 based BMG alloy. The controlled formation of nanocrystals below 50 nm with homogenous distribution inside the matrix phase via thermal treatment increase the material’s resistance to strain softening by almost an order of magnitude. The present work determines the design aspects of metallic glasses with enhanced mechanical properties via nanostructural modifications, while postulating a counter-argument to the intrinsic property degradation accounted for long-term annealing.

High pressure phase-transformation induced texture evolution and strengthening in zirconium metal: Experiment and modeling

DOE PAGES

Yu, Xiaohui; Zhang, Ruifeng; Weldon, David; ...

2015-07-28

We studied the phase-transition induced texture changes and strengthening mechanism for zirconium metal under quasi-hydrostatic compression and uni-axial deformation under confined high pressure using the deformation-DIA (D-DIA) apparatus. It is shown that the experimentally obtained texture for ω-phase Zr can be qualitatively described by combining a subset of orientation variants previously proposed in two different models. The determined flow stress for the high-pressure ω-phase is 0.5–1.2 GPa, more than three times higher than that of the α-phase. Using first-principles calculations, we investigated the mechanical and electronic properties of the two Zr polymorphs. We find that the observed strengthening can bemore » attributed to the relatively strong directional bonding in the ω phase, which significantly increases its shear plastic resistance over the α-phase Zr. The present findings provide an alternate route for Zr metal strengthening by high-pressure phase transformation.« less

Evaluation of metal biouptake from the analysis of bulk metal depletion kinetics at various cell concentrations: theory and application.

PubMed

Rotureau, Elise; Billard, Patrick; Duval, Jérôme F L

2015-01-20

Bioavailability of trace metals is a key parameter for assessment of toxicity on living organisms. Proper evaluation of metal bioavailability requires monitoring the various interfacial processes that control metal partitioning dynamics at the biointerface, which includes metal transport from solution to cell membrane, adsorption at the biosurface, internalization, and possible excretion. In this work, a methodology is proposed to quantitatively describe the dynamics of Cd(II) uptake by Pseudomonas putida. The analysis is based on the kinetic measurement of Cd(II) depletion from bulk solution at various initial cell concentrations using electroanalytical probes. On the basis of a recent formalism on the dynamics of metal uptake by complex biointerphases, the cell concentration-dependent depletion time scales and plateau values reached by metal concentrations at long exposure times (>3 h) are successfully rationalized in terms of limiting metal uptake flux, rate of excretion, and metal affinity to internalization sites. The analysis shows the limits of approximate depletion models valid in the extremes of high and weak metal affinities. The contribution of conductive diffusion transfer of metals from the solution to the cell membrane in governing the rate of Cd(II) uptake is further discussed on the basis of estimated resistances for metal membrane transfer and extracellular mass transport.

Pulsed Laser Beam Welding of Pd43Cu27Ni10P20 Bulk Metallic Glass.

PubMed

Shao, Ling; Datye, Amit; Huang, Jiankang; Ketkaew, Jittisa; Woo Sohn, Sung; Zhao, Shaofan; Wu, Sujun; Zhang, Yuming; Schwarz, Udo D; Schroers, Jan

2017-08-11

We used pulsed laser beam welding method to join Pd 43 Cu 27 Ni 10 P 20 (at.%) bulk metallic glass and characterized the properties of the joint. Fusion zone and heat-affected zone in the weld joint can be maintained completely amorphous as confirmed by X-ray diffraction and differential scanning calorimetry. No visible defects were observed in the weld joint. Nanoindentation and bend tests were carried out to determine the mechanical properties of the weld joint. Fusion zone and heat-affected zone exhibit very similar elastic moduli and hardness when compared to the base material, and the weld joint shows high ductility in bending which is accomplished through the operation of multiple shear bands. Our results reveal that pulsed laser beam welding under appropriate processing parameters provides a practical viable method to join bulk metallic glasses.

Origin of anomalous inverse notch effect in bulk metallic glasses

NASA Astrophysics Data System (ADS)

Pan, J.; Zhou, H. F.; Wang, Z. T.; Li, Y.; Gao, H. J.

2015-11-01

Understanding notch-related failure is crucial for the design of reliable engineering structures. However, substantial controversies exist in the literature on the notch effect in bulk metallic glasses (BMGs), and the underlying physical mechanism responsible for the apparent confusion is still poorly understood. Here we investigate the physical origin of an inverse notch effect in a Zr-based metallic glass, where the tensile strength of the material is dramatically enhanced, rather than decreased (as expected from the stress concentration point of view), by introduction of a notch. Our experiments and molecular dynamics simulations show that the seemingly anomalous inverse notch effect is in fact caused by a transition in failure mechanism from shear banding at the notch tip to cavitation and void coalescence. Based on our theoretical analysis, the transition occurs as the stress triaxiality in the notched sample exceeds a material-dependent threshold value. Our results fill the gap in the current understanding of BMG strength and failure mechanism by resolving the conflicts on notch effects and may inspire re-interpretation of previous reports on BMG fracture toughness where pre-existing notches were routinely adopted.

Zirconium-based metal organic frameworks loaded on polyurethane foam membrane for simultaneous removal of dyes with different charges.

PubMed

Li, Juan; Gong, Ji-Lai; Zeng, Guang-Ming; Zhang, Peng; Song, Biao; Cao, Wei-Cheng; Liu, Hong-Yu; Huan, Shuang-Yan

2018-10-01

Treating dye wastewater by membrane filtration technology has received much attention from researchers all over the world, however, current studies mainly focused on the removal of singly charged dyes but actual wastewater usually contains dyes with different charges. In this study, the removal of neutral, cationic and anionic dyes in binary or ternary systems was conducted by using zirconium-based metal organic frameworks loaded on polyurethane foam (Zr-MOFs-PUF) membrane. The Zr-MOFs-PUF membrane was fabricated by an in-situ hydrothermal synthesis approach and a hot-pressing process. Neutrally charged Rhodamine B (RB), positively charged Methylene blue (MB), and negatively charged Congo red (CR) were chosen as model pollutants for investigating filtration performance of the membrane. The results of filtration experiments showed that the Zr-MOFs-PUF membrane could simultaneously remove RB, MB, and CR not only from their binary system including RB/MB, RB/CR, and MB/CR mixtures, but also from RB/MB/CR ternary system. The removal of dyes by Zr-MOFs-PUF membrane was mainly attributed to the electrostatic interactions, hydrogen bond interaction, and Lewis acid-base interactions between the membrane and dye molecules. The maximum removal efficiencies by Zr-MOFs-PUF membrane were 98.80% for RB at pH ≈ 7, 97.57% for MB at pH ≈ 9, and 87.39% for CR at pH ≈ 3. Additionally, when the NaCl concentration reached 0.5 mol/L in single dye solutions, the removal efficiencies of RB, MB, and CR by Zr-MOFs-PUF membrane were 93.08%, 79.52%, and 97.82%, respectively. All the results suggested that the as-prepared Zr-MOFs-PUF membrane has great potential in practical treatment of dye wastewater. Copyright © 2018 Elsevier Inc. All rights reserved.

Thermal activation in Au-based bulk metallic glass characterized by high-temperature nanoindentation

NASA Astrophysics Data System (ADS)

Yang, Bing; Wadsworth, Jeffrey; Nieh, Tai-Gang

2007-02-01

High-temperature nanoindentation experiments have been conducted on a Au49Ag5.5Pd2.3Cu26.9Si16.3 bulk metallic glass from 30to140°C, utilizing loading rates ranging from 0.1to100mN/s. Generally, the hardness decreased with increasing temperature. An inhomogeneous-to-homogeneous flow transition was clearly observed when the test temperature approached the glass transition temperature. Analyses of the pop-in pattern and hardness variation showed that the inhomogeneous-to-homogeneous transition temperature was loading-rate dependent. Using a free-volume model, the authors deduced the size of the basic flow units and the activation energy for the homogeneous flow. In addition, the strain rate dependency of the transition temperature was predicted.

Guided evolution of bulk metallic glass nanostructures: A platform for designing three-dimensional electrocatalytic surfaces

DOE PAGES

Doubek, Gustavo; Sekol, Ryan C.; Li, Jinyang; ...

2015-12-22

Precise control over catalyst surface composition and structure is necessary to improve the function of electrochemical systems. To that end, bulk metallic glass (BMG) alloys with atomically dispersed elements provide a highly processable, nanoscale platform for electrocatalysis and surface modification. Here we report on nanostructures of Pt-based BMGs that are modified with various subtractive and additive processes to improve their electrochemical performance.

International strategic minerals inventory summary report; zirconium

USGS Publications Warehouse

Towner, R.R.

1992-01-01

Zircon, a zirconium silicate, is currently the most important commercial zirconium-bearing mineral. Baddeleyite, a natural form of zirconia, is less important but has some specific end uses. Both zircon and baddeleyite occur in hard-rock and placer deposits, but at present all zircon production is from placer deposits. Most baddeleyite production is from hard-rock deposits, principally as a byproduct of copper and phosphate-rock mining. World zirconium resources in identified, economically exploitable deposits are about 46 times current production rates. Of these resources, some 71 percent are in South Africa, Australia, and the United States. The principal end uses of zirconium minerals are in ceramic applications and as refractories, abrasives, and mold linings in foundries. A minor amount, mainly of zircon, is used for the production of hafnium-free zirconium metal, which is used principally for sheathing fuel elements in nuclear reactors and in the chemical-processing industry, aerospace engineering, and electronics. Australia and South Africa are the largest zircon producers and account for more than 70 percent of world output; the United States and the Soviet Union account for another 20 percent. South Africa accounts for almost all the world's production of baddeleyite, which is about 2 percent of world production of contained zirconia. Australia and South Africa are the largest exporters of zircon. Unless major new deposits are developed in countries that have not traditionally produced zircon, the pattern of world production is unlikely to change by 2020. The proportions, however, of production that come from existing producing countries may change somewhat.

Mineral resource of the month: zirconium and hafnium

USGS Publications Warehouse

Gambogi, Joseph

2007-01-01

Zirconium and hafnium are corrosion-resistant metals that are grouped in the same family as titanium on the periodic table. The two elements commonly occur in oxide and silicate minerals and have significant economic importance in everything from ink, ceramics and golf shoes to nuclear fuel rods.

Metal/ceramic composites with high hydrogen permeability

DOEpatents

Dorris, Stephen E.; Lee, Tae H.; Balachandran, Uthamalingam

2003-05-27

A membrane for separating hydrogen from fluids is provided comprising a sintered homogenous mixture of a ceramic composition and a metal. The metal may be palladium, niobium, tantalum, vanadium, or zirconium or a binary mixture of palladium with another metal such as niobium, silver, tantalum, vanadium, or zirconium.

Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

PubMed

Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

2016-02-01

Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

Imprinting bulk amorphous alloy at room temperature

DOE PAGES

Kim, Song-Yi; Park, Eun-Soo; Ott, Ryan T.; ...

2015-11-13

We present investigations on the plastic deformation behavior of a brittle bulk amorphous alloy by simple uniaxial compressive loading at room temperature. A patterning is possible by cold-plastic forming of the typically brittle Hf-based bulk amorphous alloy through controlling homogenous flow without the need for thermal energy or shaping at elevated temperatures. The experimental evidence suggests that there is an inconsistency between macroscopic plasticity and deformability of an amorphous alloy. Moreover, imprinting of specific geometrical features on Cu foil and Zr-based metallic glass is represented by using the patterned bulk amorphous alloy as a die. These results demonstrate the abilitymore » of amorphous alloys or metallic glasses to precisely replicate patterning features onto both conventional metals and the other amorphous alloys. In conclusion, our work presents an avenue for avoiding the embrittlement of amorphous alloys associated with thermoplastic forming and yields new insight the forming application of bulk amorphous alloys at room temperature without using heat treatment.« less

Effect of MoSi2 Content on Dry Sliding Tribological Properties of Zr-Based Bulk Metallic Glass Composites

NASA Astrophysics Data System (ADS)

Liu, Longfei; Yang, Jun

2017-12-01

Zr55Cu30Al10Ni5 bulk metallic glass and its composites were prepared by suction casting into a copper mold. The effect of MoSi2 content on the tribological behavior of Zr55Cu30Al10Ni5 BMG was studied by using a high-speed reciprocating friction and wear tester. The results indicate that the friction coefficient and wear resistance of the BMGs can be improved by a certain amount of crystalline phase induced by MoSi2 content from 1 to 3% and deteriorated with MoSi2 content of 4%. The wear mechanism of both the metallic glass and its composite is abrasive wear. The mechanism of crystalline phase-dependent tribological properties of the composite was discussed based on the wear track and mechanical properties in the present work. The wear behavior of Zr55Cu30Al10Ni5 BMG and its composite indicates that a good combination of the toughness and the hardness can make the composite be well wear resistant.

Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Banerjee, Debasis; Xu, Wenqian; Nie, Zimin

2016-09-06

Efficient removal of pertechnetate (TcO4-) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4- anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium basedmore » metal-organic framework can adsorb perrhenate (ReO4-) anions, a non-radioactive sur-rogate for TcO4-, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4- (surrogate for TcO4-) molecule within the framework.« less

Nanoindentation study on the characteristic of shear transformation zone in a Pd-based bulk metallic glass during serrated flow

NASA Astrophysics Data System (ADS)

Liao, G. K.; Long, Z. L.; Zhao, M. S. Z.; Peng, L.; Chai, W.; Ping, Z. H.

2018-04-01

This paper presents the research on the evolution of shear transformation zone (STZ) in a Pd-based bulk metallic glass (BMG) during serrated flow under nanoindentation. A novel method of estimating the STZ volume through statistical analysis of the serrated flow behavior was proposed for the first time. Based on the proposed method, the STZ volume of the studied BMG at various peak loads have been systematically investigated. The results indicate that the measured STZ volumes are in good agreement with that documented in literature, and the STZ size exhibits an increasing trend during indentation. Moreover, the correlation between the serrated flow dynamics and the STZ activation has also been evaluated. It is found that the STZ activation can promote the formation of self-organized critical (SOC) state during serrated flow.

Electron-band theory inspired design of magnesium-precious metal bulk metallic glasses with high thermal stability and extended ductility.

PubMed

Laws, Kevin J; Shamlaye, Karl F; Granata, Davide; Koloadin, Leah S; Löffler, Jörg F

2017-06-13

Magnesium-based bulk metallic glasses (BMGs) exhibit high specific strengths and excellent glass-forming ability compared to other metallic systems, making them suitable candidates for next-generation materials. However, current Mg-based BMGs tend to exhibit low thermal stability and are prone to structural relaxation and brittle failure. This study presents a range of new magnesium-precious metal-based BMGs from the ternary Mg-Ag-Ca, Mg-Ag-Yb, Mg-Pd-Ca and Mg-Pd-Yb alloy systems with Mg content greater than 67 at.%. These alloys were designed for high ductility by utilising atomic bond-band theory and a topological efficient atomic packing model. BMGs from the Mg-Pd-Ca alloy system exhibit high glass-forming ability with critical casting sizes of up to 3 mm in diameter, the highest glass transition temperatures (>200 °C) of any reported Mg-based BMG to date, and sustained compressive ductility. Alloys from the Mg-Pd-Yb family exhibit critical casting sizes of up to 4 mm in diameter, and the highest compressive plastic (1.59%) and total (3.78%) strain to failure of any so far reported Mg-based glass. The methods and theoretical approaches presented here demonstrate a significant step forward in the ongoing development of this extraordinary class of materials.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, R.J.; Cecchi, J.L.

1991-08-20

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen. 4 figures.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1991-01-01

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1990-01-01

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

The Effect of Luting Cement and Titanium Base on the Final Color of Zirconium Oxide Core Material.

PubMed

Capa, Nuray; Tuncel, Ilkin; Tak, Onjen; Usumez, Aslihan

2017-02-01

To evaluate the effects of different types of luting cements and different colors of zirconium cores on the final color of the restoration that simulates implant-supported fixed partial dentures (FPDs) by using a titanium base on the bottom. One hundred and twenty zirconium oxide core plates (Zr-Zahn; 10 mm in width, 5 mm in length, 0.5 mm in height) were prepared in different shades (n = 20; noncolored, A2, A3, B1, C2, D2). The specimens were subdivided into two subgroups for the two types of luting cements (n = 10). The initial color measurements were made on zirconium oxide core plates using a spectrometer. To create the cement thicknesses, stretch strips with holes in the middle (5 mm in diameter, 70 μm in height) were used. The second measurement was done on the zirconium oxide core plates after the application of the resin cement (U-200, A2 Shade) or polycarboxylate cement (Lumicon). The final measurement was done after placing the titanium discs (5 mm in diameter, 3 mm in height) in the bottom. The data were analyzed with two-way ANOVA and Tukey's honestly significant differences (HSD) tests (α = 0.05). The ∆E* ab value was higher in the resin cement-applied group than in the polycarboxylate cement-applied group (p < 0.001). The highest ∆E* ab value was recorded for the zirconium oxide core-resin cement-titanium base, and the lowest was recorded for the polycarboxylate cement-zirconium oxide core (p < 0.001). The luting cement, the presence of titanium, and the color of zirconium are all important factors that determine the final shade of zirconia cores in implant-supported FPDs. © 2015 by the American College of Prosthodontists.

Zirconium Phosphate Supported MOF Nanoplatelets.

PubMed

Kan, Yuwei; Clearfield, Abraham

2016-06-06

We report a rare example of the preparation of HKUST-1 metal-organic framework nanoplatelets through a step-by-step seeding procedure. Sodium ion exchanged zirconium phosphate, NaZrP, nanoplatelets were judiciously selected as support for layer-by-layer (LBL) assembly of Cu(II) and benzene-1,3,5-tricarboxylic acid (H3BTC) linkers. The first layer of Cu(II) is attached to the surface of zirconium phosphate through covalent interaction. The successive LBL growth of HKUST-1 film is then realized by soaking the NaZrP nanoplatelets in ethanolic solutions of cupric acetate and H3BTC, respectively. The amount of assembled HKUST-1 can be readily controlled by varying the number of growth cycles, which was characterized by powder X-ray diffraction and gas adsorption analyses. The successful construction of HKUST-1 on NaZrP was also supported by its catalytic performance for the oxidation of cyclohexene.

Temperature rise and flow of Zr-based bulk metallic glasses under high shearing stress

NASA Astrophysics Data System (ADS)

Zhang, Weiguo; Ma, Mingzhen; Song, Aijun; Liang, Shunxing; Hao, Qiuhong; Tan, Chunlin; Jing, Qin; Liu, Riping

2011-11-01

Deformation of the bulk metallic glasses (BMGs) and the creation and propagation of the shear bands are closely interconnected. Shearing force was loaded on Zr41.2Ti13.8Cu12.5Ni10.0Be22.5(Vit.1) BMGs by cutting during the turning of the BMG rod. The temperature rise of alloy on the shear bands was calculated and the result showed that it could reach the temperature of the super-cooled liquid zone or exceed the melting point. The temperature rise caused viscous fluid flow and brought about the deformation of BMGs. This suggested that the deformation of BMGs was derived, at least to some extent, from the adiabatic shear temperature rise.

First-principles design of nanostructured hybrid photovoltaics based on layered transition metal phosphates

DOE PAGES

Lentz, Levi C.; Kolpak, Alexie M.

2017-04-28

The performance of bulk organic and hybrid organic-inorganic heterojunction photovoltaics is often limited by high carrier recombination arising from strongly bound excitons and low carrier mobility. Structuring materials to minimize the length scales required for exciton separation and carrier collection is therefore a promising approach for improving efficiency. In this work, first-principles computations are employed to design and characterize a new class of photovoltaic materials composed of layered transition metal phosphates (TMPs) covalently bound to organic absorber molecules to form nanostructured superlattices. Using a combination of transition metal substitution and organic functionalization, the electronic structure of these materials is systematicallymore » tuned to design a new hybrid photovoltaic material predicted to exhibit very low recombination due to the presence of a local electric field and spatially isolated, high mobility, two-dimensional electron and hole conducting channels. Furthermore, this material is predicted to have a large open-circuit voltage of 1.7 V. Here, this work suggests that hybrid TMPs constitute an interesting class of materials for further investigation in the search for achieving high efficiency, high power, and low cost photo Zirconium phosphate was chosen, in part, due to previous experiment voltaics.« less

First-principles design of nanostructured hybrid photovoltaics based on layered transition metal phosphates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lentz, Levi C.; Kolpak, Alexie M.

The performance of bulk organic and hybrid organic-inorganic heterojunction photovoltaics is often limited by high carrier recombination arising from strongly bound excitons and low carrier mobility. Structuring materials to minimize the length scales required for exciton separation and carrier collection is therefore a promising approach for improving efficiency. In this work, first-principles computations are employed to design and characterize a new class of photovoltaic materials composed of layered transition metal phosphates (TMPs) covalently bound to organic absorber molecules to form nanostructured superlattices. Using a combination of transition metal substitution and organic functionalization, the electronic structure of these materials is systematicallymore » tuned to design a new hybrid photovoltaic material predicted to exhibit very low recombination due to the presence of a local electric field and spatially isolated, high mobility, two-dimensional electron and hole conducting channels. Furthermore, this material is predicted to have a large open-circuit voltage of 1.7 V. Here, this work suggests that hybrid TMPs constitute an interesting class of materials for further investigation in the search for achieving high efficiency, high power, and low cost photo Zirconium phosphate was chosen, in part, due to previous experiment voltaics.« less

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

NASA Technical Reports Server (NTRS)

Spaepen, F.

1985-01-01

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Deficiency of the bulk spin Hall effect model for spin-orbit torques in magnetic-insulator/heavy-metal heterostructures

NASA Astrophysics Data System (ADS)

Li, Junxue; Yu, Guoqiang; Tang, Chi; Liu, Yizhou; Shi, Zhong; Liu, Yawen; Navabi, Aryan; Aldosary, Mohammed; Shao, Qiming; Wang, Kang L.; Lake, Roger; Shi, Jing

2017-06-01

Electrical currents in a magnetic-insulator/heavy-metal heterostructure can induce two simultaneous effects, namely, spin Hall magnetoresistance (SMR) on the heavy-metal side and spin-orbit torques (SOTs) on the magnetic-insulator side. Within the framework of a pure spin current model based on the bulk spin Hall effect (SHE), the ratio of the spin Hall-induced anomalous Hall effect (SH-AHE) to SMR should be equal to the ratio of the fieldlike torque (FLT) to the dampinglike torque (DLT). We perform a quantitative study of SMR, SH-AHE, and SOTs in a series of thulium iron garnet/platinum or T m3F e5O12/Pt heterostructures with different T m3F e5O12 thicknesses, where T m3F e5O12 is a ferrimagnetic insulator with perpendicular magnetic anisotropy. We find the ratio between the measured effective fields of FLT and DLT is at least two times larger than the ratio of the SH-AHE to SMR. In addition, the bulk SHE model grossly underestimates the spin-torque efficiency of FLT. Our results reveal deficiencies of the bulk SHE model and also address the importance of interfacial effects such as the Rashba and magnetic proximity effects in magnetic-insulator/heavy-metal heterostructures.

The effect of zirconium-based surface treatment on the cathodic disbonding resistance of epoxy coated mild steel

NASA Astrophysics Data System (ADS)

Ghanbari, A.; Attar, M. M.

2014-10-01

The effect of zirconium-based surface treatment on the cathodic disbonding resistance and adhesion performance of an epoxy coated mild steel substrate was investigated. The obtained data from pull-off, cathodic disbonding test and electrochemical impedance spectroscopy (EIS) indicated that the zirconium conversion layer significantly improved the adhesion strength and cathodic disbonding resistance of the epoxy coating. This may be attributed to formation of some polar zirconium compounds on the surface and increment of surface roughness, that were evident in the results of field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM), respectively.

Bulk and surface half-metallicity: The case of D0{sub 3}-type Mn{sub 3}Ge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Hao; Gao, G. Y., E-mail: guoying-gao@mail.hust.edu.cn; Hu, Lei

2014-01-21

Motivated by the experimental realization of D0{sub 22}-type Mn{sub 3}Ge (001) films [Kurt et al. Appl. Phys. Lett. 101, 132410 (2012)] and the structural stability of D0{sub 3}-type Heusler alloy Mn{sub 3}Ge [Zhang et al. J. Phys.: Condens. Matter 25, 206006 (2013)], we use the first-principles calculations based on the full potential linearized augmented plane-wave method to investigate the electronic and magnetic properties of D0{sub 3}-type Heusler alloy Mn{sub 3}Ge and its (001) surface. We show that bulk D0{sub 3}-Mn{sub 3}Ge is a half-metallic ferromagnet with the minority-spin energy gap of 0.52 eV and the magnetic moment of 1.00 μ{sub B} permore » formula unit. The bulk half-metallicity is preserved at the pure Mn-terminated (001) surface due to the large exchange split, but the MnGe-terminated (001) surface destroys the bulk half-metallicity. We also reveal that the surface stabilities are comparable between the D0{sub 3}-Mn{sub 3}Ge (001) and the experimental D0{sub 22}-Mn{sub 3}Ge (001), which indicates the feasibility to grow the Mn{sub 3}Ge (001) films with D0{sub 3} phase other than D0{sub 22} one. The surface half-metallicity and stability make D0{sub 3}-Mn{sub 3}Ge a promising candidate for spintronic applications.« less

Anomalous shear band characteristics and extra-deep shock-affected zone in Zr-based bulk metallic glass treated with nanosecond laser peening.

PubMed

Wei, Yanpeng; Xu, Guangyue; Zhang, Kun; Yang, Zhe; Guo, Yacong; Huang, Chenguang; Wei, Bingchen

2017-03-07

The effects of nanosecond laser peening on Zr 41 Ti 14 Cu 12.5 Ni 10 Be 22.5 metallic glass were investigated in this study. The peening treatment produced an extra-deep shock-affected zone compared to crystal metal. As opposed to the conventional shear bands, numerous arc shear bands appeared and aggregated in the vertical direction of the laser beam, forming basic units for accommodating plastic deformation. The arc shear bands exhibited short and discrete features near the surface of the material, then grew longer and fewer at deeper peened layer depths, which was closely related to the laser shock wave attenuation. An energy dissipation model was established based on Hugoniot Elastic Limit and shear band characteristics to represent the formation of an extra-deep shock-affected zone. The results presented here suggest that the bulk modification of metallic glass with a considerable affected depth is feasible. Further, they reveal that nanosecond laser peening is promising as an effective approach to tuning shear bands for improved MGs ductility.

Highly effective removal of heavy metals by polymer-based zirconium phosphate: a case study of lead ion.

PubMed

Pan, B C; Zhang, Q R; Zhang, W M; Pan, B J; Du, W; Lv, L; Zhang, Q J; Xu, Z W; Zhang, Q X

2007-06-01

Zirconium phosphate (ZrP) has recently been demonstrated as an excellent sorbent for heavy metals due to its high selectivity, high thermal stability, and absolute insolubility in water. However, it cannot be readily adopted in fixed beds or any other flowthrough system due to the excessive pressure drop and poor mechanical strength resulting from its fine submicrometer particle sizes. In the present study a hybrid sorbent, i.e., polymer-supported ZrP, was prepared by dispersing ZrP within a strongly acidic cation exchanger D-001 and used for enhanced lead removal from contaminated waters. D-001 was selected as a host material for sorbent preparation mainly because of the Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid group on the exchanger surface, which would enhance permeation of the targeted metal ions. The hybrid sorbent (hereafter denoted ZrP-001) was characterized using a nitrogen adsorption technique, scanning electron microscope (SEM), and X-ray diffraction (XRD). Lead sorption onto ZrP-001 was found to be pH dependent due to the ion-exchange mechanism, and its sorption kinetics onto ZrP-001 followed the pseudo-first-order model. Compared to D-001, ZrP-001 exhibited more favorable lead sorption particularly in terms of high selectivity, as indicated by its substantially larger distribution coefficients when other competing cations Na(+), Ca(2+), and Mg(2+) coexisted at a high level in solution. Fixed-bed column runs showed that lead sorption on ZrP-001 resulted in a conspicuous decrease of this toxic metal from 40 mg/L to below 0.05 mg/L. By comparison with D-001 and ZrP-CP (ZrP dispersion within a neutrally charged polymer CP), enhanced removal efficiency of ZrP-001 resulted from the Donnan membrane effect of the host material D-001. Moreover, its feasible regeneration by diluted acid solution and negligible ZrP loss during operation also helps ZrP-001 to be a potential candidate for lead removal from water. Thus

Manufacturing process to reduce large grain growth in zirconium alloys

DOEpatents

Rosecrans, P.M.

1984-08-01

It is an object of the present invention to provide a procedure for desensitizing zirconium-based alloys to large grain growth (LGG) during thermal treatment above the recrystallization temperature of the alloy. It is a further object of the present invention to provide a method for treating zirconium-based alloys which have been cold-worked in the range of 2 to 8% strain to reduce large grain growth. It is another object of the present invention to provide a method for fabricating a zirconium alloy clad nuclear fuel element wherein the zirconium clad is resistant to large grain growth.

PLUTONIUM-ZIRCONIUM ALLOYS

DOEpatents

Schonfeld, F.W.; Waber, J.T.

1960-08-30

A series of nuclear reactor fuel alloys consisting of from about 5 to about 50 at.% zirconium (or higher zirconium alloys such as Zircaloy), balance plutonium, and having the structural composition of a plutonium are described. Zirconium is a satisfactory diluent because it alloys readily with plutonium and has desirable nuclear properties. Additional advantages are corrosion resistance, excellent fabrication propenties, an isotropie structure, and initial softness.

METHOD FOR ANNEALING AND ROLLING ZIRCONIUM-BASE ALLOYS

DOEpatents

Picklesimer, M.L.

1959-07-14

A fabrication procedure is presented for alpha-stabilized zirconium-base alloys, and in particular Zircaloy-2. The alloy is initially worked at a temperature outside the alpha-plus-beta range (810 to 970 deg ), held at a temperature above 970 deg C for 30 minutes and cooled rapidly. The alloy is then cold-worked to reduce the size at least 20% and annealed at a temperature from 700 to 810 deg C. This procedure serves both to prevent the formation of stringers and to provide a randomly oriented crystal structure.

Viscous flow of the Pd43Ni10Cu27P20 bulk metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Fan, G. J.; Fecht, H.-J.; Lavernia, E. J.

2004-01-01

The equilibrium viscosity of the Pd43Ni10Cu27P20 bulk metallic glass-forming liquid was measured over a wide temperature range from the equilibrium supercooled liquid state to the glass transition region using parallel-plate rheometry and three-point beam bending. Based on the measured viscosity data, the fragility of this liquid was quantitatively determined. The Pd43Ni10Cu27P20 alloy, despite exhibiting the best glass-forming ability reported thus far, is relatively fragile compared with other bulk glass-forming liquids, such as Vit 1 and Vit 4.

Evolution of the Valley Position in Bulk Transition-Metal Chalcogenides and Their Monolayer Limit

DOE PAGES

Yuan, Hongtao; Liu, Zhongkai; Xu, Gang; ...

2016-07-12

Valley physics based on layered transition metal chalcogenides have recently sparked much interest due to their potential spintronics and valleytronics applications. However, most current understanding of the electronic structure near band valleys in momentum space is based on either theoretical investigations or optical measurements, leaving the detailed band structure elusive. For example, the exact position of the conduction band valley of bulk MoS 2 remains controversial. Here, using angle-resolved photoemission spectroscopy with sub-micron spatial resolution (micro- ARPES), we systematically imaged the conduction/valence band structure evolution across representative chalcogenides MoS 2, WS 2 and WSe 2, as well as the thicknessmore » dependent electronic structure from bulk to the monolayer limit. These results establish a solid basis to understand the underlying valley physics of these materials, and also provide a link between chalcogenide electronic band structure and their physical properties for potential valleytronics applications.« less

ZIRCONIUM-CLADDING OF THORIUM

DOEpatents

Beaver, R.J.

1961-11-21

A method of cladding thorium with zirconium is described. The quality of the bond achieved between thorium and zirconium by hot-rolling is improved by inserting and melting a thorium-zirconium alloy foil between the two materials prior to rolling. (AEC)

Coincidence of collective relaxation anomaly and specific heat peak in a bulk metallic glass-forming liquid

DOE PAGES

Jaiswal, Abhishek; Podlesynak, Andrey; Ehlers, Georg; ...

2015-07-21

The study of multicomponent metallic liquids' relaxational behavior is still the key to understanding and improving the glass-forming abilities of bulk metallic glasses. Here, we report measurements of the collective relaxation times in a melted bulk metallic glass (LM601Zr 51Cu 36Ni 4Al 9) in the kinetic regime (Q: 1.5–4.0Å –1) using quasielastic neutron scattering. The results reveal an unusual slope change in the Angell plots of this metallic liquid's collective relaxation time around 950°C, beyond the material's melting point. Measurement of specific heat capacity also reveals a peak around the same temperature. Adams-Gibbs theory is used to rationalize the coincidence,more » which motivates more careful experimental and computational studies of the metallic liquids in the future.« less

Laser Shock Peening on Zr-based Bulk Metallic Glass and Its Effect on Plasticity: Experiment and Modeling

NASA Astrophysics Data System (ADS)

Cao, Yunfeng; Xie, Xie; Antonaglia, James; Winiarski, Bartlomiej; Wang, Gongyao; Shin, Yung C.; Withers, Philip J.; Dahmen, Karin A.; Liaw, Peter K.

2015-05-01

The Zr-based bulk metallic glasses (BMGs) are a new family of attractive materials with good glass-forming ability and excellent mechanical properties, such as high strength and good wear resistance, which make them candidates for structural and biomedical materials. Although the mechanical behavior of BMGs has been widely investigated, their deformation mechanisms are still poorly understood. In particular, their poor ductility significantly impedes their industrial application. In the present work, we show that the ductility of Zr-based BMGs with nearly zero plasticity is improved by a laser shock peening technique. Moreover, we map the distribution of laser-induced residual stresses via the micro-slot cutting method, and then predict them using a three-dimensional finite-element method coupled with a confined plasma model. Reasonable agreement is achieved between the experimental and modeling results. The analyses of serrated flows reveal plentiful and useful information of the underlying deformation process. Our work provides an easy and effective way to extend the ductility of intrinsically-brittle BMGs, opening up wider applications of these materials.

Laser shock peening on Zr-based bulk metallic glass and its effect on plasticity: Experiment and modeling

DOE PAGES

Cao, Yunfeng; Xie, Xie; Antonaglia, James; ...

2015-05-20

The Zr-based bulk metallic glasses (BMGs) are a new family of attractive materials with good glass-forming ability and excellent mechanical properties, such as high strength and excellent wear resistance, which make them candidates for structural and biomedical materials. Although the mechanical behavior of BMGs has been widely investigated, their deformation mechanisms are still poorly understood. In particular, their poor ductility significantly impedes their industrial application. In the present work, we show that the ductility of Zr-based BMGs with nearly zero plasticity is improved by a laser shock peening technique. Moreover, we map the distribution of laser-induced residual stresses via themore » micro-slot cutting method, and then predict them using a three dimensional finite-element method coupled with a confined plasma model. Reasonable agreement is achieved between the experimental and modeling results. The analysis of serrated flow reveals plentiful and useful information of the underlying deformation process. As a result, our work provides an easy and effective way to extend the ductility of intrinsically-brittle BMGs, opening up wider applications of these materials.« less

Materials properties of hafnium and zirconium silicates: Metal interdiffusion and dopant penetration studies

NASA Astrophysics Data System (ADS)

Quevedo Lopez, Manuel Angel

Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050°C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixO y are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford Backscattering Spectroscopy (RBS), Heavy Ion RBS (HI-RBS), X-ray Photoelectron Spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM), and Time of Flight and Dynamic Secondary Ion Mass Spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixO y films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSi xOyNz films.

The influence of Sc addition on the welding microstructure of Zr-based bulk metallic glass: The stability of the amorphous phase

NASA Astrophysics Data System (ADS)

Wang, Shing Hoa; Kuo, Pei Hung; Tsang, Hsiao Tsung; Jeng, Rong Ruey; Lin, Yu Lon

2007-10-01

Pulsed direct current autogeneous tungsten inert gas arc welding was conducted on rods of bulk metallic glasses (BMGs) Zr55Cu30Ni5Al10 and (Zr55Cu30Ni5Al10)99.98Sc0.02 under two different cooling conditions. The crystalline precipitates in the fusion zone of BMG Zr55Cu30Ni5Al10 were confirmed by microfocused x-ray diffraction pattern analysis as Zr2Ni and Zr2(Cu,Al) intermetallic compounds. In contrast, BMG with Sc addition (Zr55Cu30Ni5Al10)99.98Sc0.02 shows an excellent stable glass forming ability. The fusion zone of BMG (Zr55Cu30Ni5Al10)99.98Sc0.02 remains in the same amorphous state as that of the amorphous base metal when the weld is cooled with accelerated cooling.

ELECTROLYTIC CLADDING OF ZIRCONIUM ON URANIUM

DOEpatents

Wick, J.J.

1959-09-22

A method is presented for coating uranium with zircoalum by rendering the uranium surface smooth and oxidefree, immersing it in a molten electrolytic bath in NaCI, K/sub 2/ZrF/sub 6/, KF, and ZrO/sub 2/, and before the article reaches temperature equilibrium with the bath, applying an electrolyzing current of 60 amperes per square dectmeter at approximately 3 volts to form a layer of zirconium metal on the uranium.

Effect of hydrogenation conditions on the microstructure and mechanical properties of zirconium hydride

NASA Astrophysics Data System (ADS)

Muta, Hiroaki; Nishikane, Ryoji; Ando, Yusuke; Matsunaga, Junji; Sakamoto, Kan; Harjo, Stefanus; Kawasaki, Takuro; Ohishi, Yuji; Kurosaki, Ken; Yamanaka, Shinsuke

2018-03-01

Precipitation of brittle zirconium hydrides deteriorate the fracture toughness of the fuel cladding tubes of light water reactor. Although the hydride embrittlement has been studied extensively, little is known about physical properties of the hydride due to the experimental difficulties. In the present study, to elucidate relationship between mechanical properties and microstructure, two δ-phase zirconium hydrides and one ε-phase zirconium hydride were carefully fabricated considering volume changes at the metal-to-hydride transformation. The δ-hydride that was fabricated from α-zirconium exhibits numerous inner cracks due to the large volume change. Analyses of the neutron diffraction pattern and electron backscatter diffraction (EBSD) data show that the sample displays significant stacking faults in the {111} plane and in the pseudo-layered microstructure. On the other hand, the δ-hydride sample fabricated from β-zirconium at a higher temperature displays equiaxed grains and no cracks. The strong crystal orientation dependence of mechanical properties were confirmed by indentation test and EBSD observation. The δ-hydride hydrogenated from α-zirconium displays a lower Young's modulus than that prepared from β-zirconium. The difference is attributed to stacking faults within the {111} plane, for which the Young's modulus exhibits the highest value in the perpendicular direction. The strong influence of the crystal orientation and dislocation density on the mechanical properties should be considered when evaluating hydride precipitates in nuclear fuel cladding.

Low temperature reduction of free-standing graphene oxide papers with metal iodides for ultrahigh bulk conductivity.

PubMed

Liu, Chenyang; Hao, Feng; Zhao, Xiaochong; Zhao, Qiancheng; Luo, Songping; Lin, Hong

2014-02-05

Here we report a green and facile route for highly efficient reduction of free-standing graphene oxide (GO) papers with metal iodide aqueous solutions at low cost. The metal iodides (MgI2, AlI3, ZnI2, FeI2) were synthesized directly from metal and iodine powder with water as a catalyzer. An extremely high bulk conductivity of 55088 S/m for reduced graphene oxide (rGO) papers were obtained with FeI2 solution of which pH = 0 at 95°C for 6 hours. The catalytic effect of strong Lewis acid for the promotion of the nucleophilic substitution reaction is responsible for the greatly improved bulk conductivity. Furthermore, it was found that the layer-to-layer distance (dL) and the crystallinity of the rGO papers are regarded as two main factors affecting the bulk conductivity rather than C/O ratio and defect concentration.

Clinical efficacy of veneered zirconium dioxide-based posterior partial fixed dental prostheses: five-year results.

PubMed

Raigrodski, Ariel J; Yu, Alika; Chiche, Gerard J; Hochstedler, J L; Mancl, Lloyd A; Mohamed, Shawky E

2012-10-01

In recent years, zirconium dioxide-based partial fixed dental prostheses (FDP) have been suggested as an alternative treatment to traditional metal ceramic FDPs. However, clinical studies evaluating their longevity and related complications are limited. The purpose of this cohort clinical study was to assess the efficacy of zirconium dioxide-based posterior 3-unit FDPs. Twenty 3-unit posterior FDPs (Lava) were placed in 16 participants missing a second premolar or a first molar. All participants met specific inclusion and exclusion criteria and provided informed consent. All teeth were prepared in a standardized manner: occlusal reduction of 1.5 to 2 mm; axial reduction of 1 to 1.5 mm; a 1.0 mm 360-degree rounded shoulder placed 0.5 mm subgingivally on the facial aspect and supragingivally on the lingual aspect on sound tooth structure; and rounded internal line angles. Definitive impressions were made with vinyl polysiloxane impression material. Frameworks were fabricated by using computer-aided design and computer-aided manufacturing (CAD/CAM) technology with a uniform retainer thickness of 0.6 mm and a minimal connector surface area of 9 mm(2). Restorations were luted with resin-modified glass ionomer cement (Rely-X Luting). Participants were recalled at 2 weeks, 6 months, and 12 months, and thereafter, annually for up to 60 months. Clinical fracture measurements, marginal discoloration, marginal adaptation, radiographic proximal recurrent caries, and periapical pathoses were assessed over time by using modified Ryge criteria. The probability distributions of these variables were calculated for the baseline data and for the recall data. An analysis of survival was made by using the Kaplan-Meier method. Eighteen FDPs were clinically evaluated at 5 years and 1 at 48 months. Fifteen were rated Alpha for fracture measurements, and 2 were rated Bravo (minor chipping of veneering porcelain and not requiring restoration replacement). Two were rated Charlie (major

Three-dimensional microstructural characterization of bulk plutonium and uranium metals using focused ion beam technique

NASA Astrophysics Data System (ADS)

Chung, Brandon W.; Erler, Robert G.; Teslich, Nick E.

2016-05-01

Nuclear forensics requires accurate quantification of discriminating microstructural characteristics of the bulk nuclear material to identify its process history and provenance. Conventional metallographic preparation techniques for bulk plutonium (Pu) and uranium (U) metals are limited to providing information in two-dimension (2D) and do not allow for obtaining depth profile of the material. In this contribution, use of dual-beam focused ion-beam/scanning electron microscopy (FIB-SEM) to investigate the internal microstructure of bulk Pu and U metals is demonstrated. Our results demonstrate that the dual-beam methodology optimally elucidate microstructural features without preparation artifacts, and the three-dimensional (3D) characterization of inner microstructures can reveal salient microstructural features that cannot be observed from conventional metallographic techniques. Examples are shown to demonstrate the benefit of FIB-SEM in improving microstructural characterization of microscopic inclusions, particularly with respect to nuclear forensics.

Predicting Novel Bulk Metallic Glasses via High- Throughput Calculations

NASA Astrophysics Data System (ADS)

Perim, E.; Lee, D.; Liu, Y.; Toher, C.; Gong, P.; Li, Y.; Simmons, W. N.; Levy, O.; Vlassak, J.; Schroers, J.; Curtarolo, S.

Bulk metallic glasses (BMGs) are materials which may combine key properties from crystalline metals, such as high hardness, with others typically presented by plastics, such as easy processability. However, the cost of the known BMGs poses a significant obstacle for the development of applications, which has lead to a long search for novel, economically viable, BMGs. The emergence of high-throughput DFT calculations, such as the library provided by the AFLOWLIB consortium, has provided new tools for materials discovery. We have used this data to develop a new glass forming descriptor combining structural factors with thermodynamics in order to quickly screen through a large number of alloy systems in the AFLOWLIB database, identifying the most promising systems and the optimal compositions for glass formation. National Science Foundation (DMR-1436151, DMR-1435820, DMR-1436268).

Tuned critical avalanche scaling in bulk metallic glasses

DOE PAGES

Antonaglia, James; Xie, Xie; Schwarz, Gregory; ...

2014-03-17

In this study, ingots of the bulk metallic glass (BMG), Zr 64.13Cu 15.75Ni 10.12Al 10 in atomic percent (at. %), are compressed at slow strain rates. The deformation behavior is characterized by discrete, jerky stress-drop bursts (serrations). Here we present a quantitative theory for the serration behavior of BMGs, which is a critical issue for the understanding of the deformation characteristics of BMGs. The mean-field interaction model predicts the scaling behavior of the distribution, D(S), of avalanche sizes, S, in the experiments. D(S) follows a power law multiplied by an exponentially-decaying scaling function. The size of the largest observed avalanchemore » depends on experimental tuning-parameters, such as either imposed strain rate or stress. Similar to crystalline materials, the plasticity of BMGs reflects tuned criticality showing remarkable quantitative agreement with the slip statistics of slowly-compressed nanocrystals. The results imply that material-evaluation methods based on slip statistics apply to both crystalline and BMG materials.« less

A Zr-based bulk metallic glass for future stent applications: Materials properties, finite element modeling, and in vitro human vascular cell response.

PubMed

Huang, Lu; Pu, Chao; Fisher, Richard K; Mountain, Deidra J H; Gao, Yanfei; Liaw, Peter K; Zhang, Wei; He, Wei

2015-10-01

Despite the prevalent use of crystalline alloys in current vascular stent technology, new biomaterials are being actively sought after to improve stent performance. In this study, we demonstrated the potential of a Zr-Al-Fe-Cu bulk metallic glass (BMG) to serve as a candidate stent material. The mechanical properties of the Zr-based BMG, determined under both static and cyclic loadings, were characterized by high strength, which would allow for the design of thinner stent struts to improve stent biocompatibility. Finite element analysis further complemented the experimental results and revealed that a stent made of the Zr-based BMG was more compliant with the beats of a blood vessel, compared with medical 316L stainless steel. The Zr-based BMG was found to be corrosion resistant in a simulated body environment, owing to the presence of a highly stable ZrO2-rich surface passive film. Application-specific biocompatibility studies were conducted using human aortic endothelial cells and smooth muscle cells. The Zr-Al-Fe-Cu BMG was found to support stronger adhesion and faster coverage of endothelial cells and slower growth of smooth muscle cells than 316L stainless steel. These results suggest that the Zr-based BMG could promote re-endothelialization and potentially lower the risk of restenosis, which are critical to improve vascular stent implantation integration. In general, findings in this study raised the curtain for the potential application of BMGs as future candidates for stent applications. Vascular stents are medical devices typically used to restore the lumen of narrowed or clogged blood vessel. Despite the clinical success of metallic materials in stent-assisted angioplasty, post-surgery complications persist due to the mechanical failures, corrosion, and in-stent restenosis of current stents. To overcome these hurdles, strategies including new designs and surface functionalization have been exercised. In addition, the development of new materials with

Experimental Calcium Silicate-Based Cement with and without Zirconium Oxide Modulates Fibroblasts Viability.

PubMed

Slompo, Camila; Peres-Buzalaf, Camila; Gasque, Kellen Cristina da Silva; Damante, Carla Andreotti; Ordinola-Zapata, Ronald; Duarte, Marco Antonio Hungaro; de Oliveira, Rodrigo Cardoso

2015-01-01

The aim of this study was to verify whether the use of zirconium oxide as a radiopacifier of an experimental calcium silicate-based cement (WPCZO) leads to cytotoxicity. Fibroblasts were treated with different concentrations (10 mg/mL, 1 mg/mL, and 0.1 mg/mL) of the cements diluted in Dulbecco's modified Eagle's medium (DMEM) for periods of 12, 24, and 48 h. Groups tested were white Portland cement (WPC), white Portland cement with zirconium oxide (WPCZO), and white mineral trioxide aggregate Angelus (MTA). Control group cells were not treated. The cytotoxicity was evaluated through mitochondrial-activity (MTT) and cell-density (crystal violet) assays. All cements showed low cytotoxicity. In general, at the concentration of 10 mg/mL there was an increase in viability of those groups treated with WPC and WPCZO when compared to the control group (p<0.05). A similar profile for the absorbance values was noted among the groups: 10 mg/mL presented an increase in viability compared to the control group. On the other hand, smaller concentrations presented a similar or lower viability compared to the control group, in general. A new dental material composed of calcium silicate-based cement with 20% zirconium oxide as the radiopacifier showed low cytotoxicity as a promising material to be exploited for root-end filling.

Influence of thin-film metallic glass coating on fatigue behavior of bulk metallic glass: Experiments and finite element modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Chia-Chi; Chu, Jinn P.; Jia, Haoling

In this paper, a coating of the Zr-based thin-film metallic glass (TFMG) was deposited on the Zr 50Cu 30Al 10Ni 10 bulk metallic glass (BMG) to investigate shear-band evolution under four-point-bend fatigue testing. The fatigue endurance-limit of the TFMG-coated samples is ~ 33% higher than that of the BMG. The results of finite-element modeling (FEM) revealed a delay in the shear-band nucleation and propagation in TFMG-coated samples under applied cyclic-loading. The FEM study of spherical indentation showed that the redistribution of stress by the TFMG coating prevents localized shear-banding in the BMG substrate. Finally, the enhanced fatigue characteristics of themore » BMG substrates can be attributed to the TFMG coatings retarding shear-band initiation at defects on the surface of the BMG.« less

Influence of thin-film metallic glass coating on fatigue behavior of bulk metallic glass: Experiments and finite element modeling

DOE PAGES

Yu, Chia-Chi; Chu, Jinn P.; Jia, Haoling; ...

2017-03-21

In this paper, a coating of the Zr-based thin-film metallic glass (TFMG) was deposited on the Zr 50Cu 30Al 10Ni 10 bulk metallic glass (BMG) to investigate shear-band evolution under four-point-bend fatigue testing. The fatigue endurance-limit of the TFMG-coated samples is ~ 33% higher than that of the BMG. The results of finite-element modeling (FEM) revealed a delay in the shear-band nucleation and propagation in TFMG-coated samples under applied cyclic-loading. The FEM study of spherical indentation showed that the redistribution of stress by the TFMG coating prevents localized shear-banding in the BMG substrate. Finally, the enhanced fatigue characteristics of themore » BMG substrates can be attributed to the TFMG coatings retarding shear-band initiation at defects on the surface of the BMG.« less

Do oxidized zirconium femoral heads reduce polyethylene wear in cemented THAs? A blinded randomized clinical trial.

PubMed

Zaoui, Amine; Hage, Samer El; Langlois, Jean; Scemama, Caroline; Courpied, Jean Pierre; Hamadouche, Moussa

2015-12-01

Charnley low-friction torque total hip arthroplasty (THA) remains the gold standard in THA. The main cause for failure is wear of the socket. Highly crosslinked polyethylene (HXLPE) has been associated with reduced wear rates. Also, oxidized zirconium has shown in vitro reduced wear rates. However, to our knowledge, there are no data comparing oxidized zirconium femoral heads with metal heads against HXLPE or ultrahigh-molecular-weight polyethylene (UHMWPE) when 22.25-mm bearings were used, which was the same size that performed so well in Charnley-type THAs. We hypothesized that after a minimal 4-year followup (1) use of HXLPE would result in lower radiographic wear than UHMWPE when articulating with a stainless steel head or with an oxidized zirconium head; (2) use of oxidized zirconium would result in lower radiographic wear than stainless steel when articulating with UHMWPE and HXLPE; and (3) there would be no difference in terms of Merle d'Aubigné scores between the bearing couple combinations. One hundred patients were randomized to receive cemented THA with either oxidized zirconium or a stainless steel femoral head. UHMWPE was used in the first 50 patients, whereas HXLPE was used in the next 50 patients. There were 25 patients in each of the four bearing couple combinations. All other parameters were identical in both groups. Complete followup was available in 86 of these patients. Femoral head penetration was measured using a validated computer-assisted method dedicated to all-polyethylene sockets. Clinical results were compared between the groups using the Merle d'Aubigné score. In the UHMWPE series, the median steady-state penetration rate from 1 year onward was 0.03 mm/year (range, 0.003-0.25 mm/year) in the oxidized zirconium group versus 0.11 mm/year (range, 0.03-0.29 mm/year) in the metal group (difference of medians 0.08, p < 0.001). In the HXLPE series, the median steady-state penetration rate from 1 year onward was 0.02 mm/year (range, -0.32 to

A comparative study of zirconium and titanium implants in rat: osseointegration and bone material quality.

PubMed

Hoerth, Rebecca M; Katunar, María R; Gomez Sanchez, Andrea; Orellano, Juan C; Ceré, Silvia M; Wagermaier, Wolfgang; Ballarre, Josefina

2014-02-01

Permanent metal implants are widely used in human medical treatments and orthopedics, for example as hip joint replacements. They are commonly made of titanium alloys and beyond the optimization of this established material, it is also essential to explore alternative implant materials in view of improved osseointegration. The aim of our study was to characterize the implant performance of zirconium in comparison to titanium implants. Zirconium implants have been characterized in a previous study concerning material properties and surface characteristics in vitro, such as oxide layer thickness and surface roughness. In the present study, we compare bone material quality around zirconium and titanium implants in terms of osseointegration and therefore characterized bone material properties in a rat model using a multi-method approach. We used light and electron microscopy, micro Raman spectroscopy, micro X-ray fluorescence and X-ray scattering techniques to investigate the osseointegration in terms of compositional and structural properties of the newly formed bone. Regarding the mineralization level, the mineral composition, and the alignment and order of the mineral particles, our results show that the maturity of the newly formed bone after 8 weeks of implantation is already very high. In conclusion, the bone material quality obtained for zirconium implants is at least as good as for titanium. It seems that the zirconium implants can be a good candidate for using as permanent metal prosthesis for orthopedic treatments.

Role of Alloying Additions in Glass Formation and Properties of Bulk Metallic Glasses

PubMed Central

Chen, Na; Martin, Laura; Luzguine-Luzgin, Dmitri V.; Inoue, Akihisa

2010-01-01

Alloying addition, as a means of improving mechanical properties and saving on costs of materials, has been applied to a broad range of uses and products in the metallurgical fields. In the field of bulk metallic glasses (BMGs), alloying additions have also proven to play effective and important roles in promoting glass formation, enhancing thermal stability and improving plasticity of the materials. Here, we review the work on the role of alloying additions in glass formation and performance improvement of BMGs, with focus on our recent results of alloying additions in Pd-based BMGs. PMID:28883386

Three-dimensional microstructural characterization of bulk plutonium and uranium metals using focused ion beam technique

DOE PAGES

Chung, Brandon W.; Erler, Robert G.; Teslich, Nick E.

2016-03-03

Nuclear forensics requires accurate quantification of discriminating microstructural characteristics of the bulk nuclear material to identify its process history and provenance. Conventional metallographic preparation techniques for bulk plutonium (Pu) and uranium (U) metals are limited to providing information in two-dimension (2D) and do not allow for obtaining depth profile of the material. In this contribution, use of dual-beam focused ion-beam/scanning electron microscopy (FIB-SEM) to investigate the internal microstructure of bulk Pu and U metals is demonstrated. Our results demonstrate that the dual-beam methodology optimally elucidate microstructural features without preparation artifacts, and the three-dimensional (3D) characterization of inner microstructures can revealmore » salient microstructural features that cannot be observed from conventional metallographic techniques. As a result, examples are shown to demonstrate the benefit of FIB-SEM in improving microstructural characterization of microscopic inclusions, particularly with respect to nuclear forensics.« less

Effect of cooling rates on the structure, density and micro-indentation behavior of the Fe, Co-based bulk metallic glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lesz, Sabina, E-mail: sabina.lesz@polsl.pl

The experiments demonstrate that ductility of the samples of bulk metallic glass (BMG) with the same chemical composition increased with decreasing sample size. It is shown that microhardness and density increases with decreasing the cooling rate. The fracture morphology of rods after compressive fracture were different on the cross section. Two characteristic features of the compressive fracture morphologies of metallic glasses (MGs) were observed in samples: smooth region and the vein pattern. Many parallel shear bands were observed on the deformed specimen with ϕ = 2 mm in diameter. The results provide more understanding on the relationship among the coolingmore » rate, structure and micro-indentation behavior of the Fe-Co-based BMGs. - Highlights: •Fracture morphology and micro-indentation behavior is studied. •The smaller BMG sample exhibits the larger plasticity. •Microhardness and density increase with decreasing the cooling rate. •Formation of shear bands has been reported in deformed specimens. •Structure and mechanical properties of BMGs can be controlled by the cooling rate.« less

Effect of size on bulk and surface cohesion energy of metallic nano-particles

NASA Astrophysics Data System (ADS)

Yaghmaee, M. S.; Shokri, B.

2007-04-01

The knowledge of nano-material properties not only helps us to understand the extreme behaviour of small-scale materials better (expected to be different from what we observe from their bulk value) but also helps us to analyse and design new advanced functionalized materials through different nano technologies. Among these fundamental properties, the cohesion (binding) energy mainly describes most behaviours of materials in different environments. In this work, we discuss this fundamental property through a nano-thermodynamical approach using two algorithms, where in the first approach the size dependence of the inner (bulk) cohesion energy is studied, and in the second approach the surface cohesion energy is considered too. The results, which are presented through a computational demonstration (for four different metals: Al, Ga, W and Ag), can be compared with some experimental values for W metallic nano-particles.

The 5-year Results of an Oxidized Zirconium Femoral Component for TKA

PubMed Central

Innocenti, Massimo; Carulli, Christian; Matassi, Fabrizio; Villano, Marco

2009-01-01

Osteolysis secondary to polyethylene wear is one of the major factors limiting long-term performance of TKA. Oxidized zirconium is a new material that combines the strength of a metal with the wear properties of a ceramic. It remains unknown whether implants with a zirconium femoral component can be used safely in TKA. To answer that question, we reviewed, at a minimum of 5 years, the clinical outcome and survivorship of a ceramic-surfaced oxidized zirconium femoral component implanted during 98 primary TKAs between April 2001 and December 2003. Survivorship was 98.7% at 7 years postoperatively. No revision was necessary and only one component failed because of aseptic loosening. Mean Knee Society score improved from 36 to 89. No adverse events were observed clinically or radiologically. These results justify pursuing the use of oxidized zirconium as an alternative bearing surface for a femoral component in TKA. Level of Evidence: Level IV, therapeutic study. See Guidelines for Authors for a complete description of levels of evidence. PMID:19798541

Artefacts in multimodal imaging of titanium, zirconium and binary titanium–zirconium alloy dental implants: an in vitro study

PubMed Central

Schöllchen, Maximilian; Aarabi, Ghazal; Assaf, Alexandre T; Rendenbach, Carsten; Beck-Broichsitter, Benedicta; Semmusch, Jan; Sedlacik, Jan; Heiland, Max; Fiehler, Jens; Siemonsen, Susanne

2017-01-01

Objectives: To analyze and evaluate imaging artefacts induced by zirconium, titanium and titanium–zirconium alloy dental implants. Methods: Zirconium, titanium and titanium–zirconium alloy implants were embedded in gelatin and MRI, CT and CBCT were performed. Standard protocols were used for each modality. For MRI, line–distance profiles were plotted to quantify the accuracy of size determination. For CT and CBCT, six shells surrounding the implant were defined every 0.5 cm from the implant surface and histogram parameters were determined for each shell. Results: While titanium and titanium–zirconium alloy induced extensive signal voids in MRI owing to strong susceptibility, zirconium implants were clearly definable with only minor distortion artefacts. For titanium and titanium–zirconium alloy, the MR signal was attenuated up to 14.1 mm from the implant. In CT, titanium and titanium–zirconium alloy resulted in less streak artefacts in comparison with zirconium. In CBCT, titanium–zirconium alloy induced more severe artefacts than zirconium and titanium. Conclusions: MRI allows for an excellent image contrast and limited artefacts in patients with zirconium implants. CT and CBCT examinations are less affected by artefacts from titanium and titanium–zirconium alloy implants compared with MRI. The knowledge about differences of artefacts through different implant materials and image modalities might help support clinical decisions for the choice of implant material or imaging device in the clinical setting. PMID:27910719

Artefacts in multimodal imaging of titanium, zirconium and binary titanium-zirconium alloy dental implants: an in vitro study.

PubMed

Smeets, Ralf; Schöllchen, Maximilian; Gauer, Tobias; Aarabi, Ghazal; Assaf, Alexandre T; Rendenbach, Carsten; Beck-Broichsitter, Benedicta; Semmusch, Jan; Sedlacik, Jan; Heiland, Max; Fiehler, Jens; Siemonsen, Susanne

2017-02-01

To analyze and evaluate imaging artefacts induced by zirconium, titanium and titanium-zirconium alloy dental implants. Zirconium, titanium and titanium-zirconium alloy implants were embedded in gelatin and MRI, CT and CBCT were performed. Standard protocols were used for each modality. For MRI, line-distance profiles were plotted to quantify the accuracy of size determination. For CT and CBCT, six shells surrounding the implant were defined every 0.5 cm from the implant surface and histogram parameters were determined for each shell. While titanium and titanium-zirconium alloy induced extensive signal voids in MRI owing to strong susceptibility, zirconium implants were clearly definable with only minor distortion artefacts. For titanium and titanium-zirconium alloy, the MR signal was attenuated up to 14.1 mm from the implant. In CT, titanium and titanium-zirconium alloy resulted in less streak artefacts in comparison with zirconium. In CBCT, titanium-zirconium alloy induced more severe artefacts than zirconium and titanium. MRI allows for an excellent image contrast and limited artefacts in patients with zirconium implants. CT and CBCT examinations are less affected by artefacts from titanium and titanium-zirconium alloy implants compared with MRI. The knowledge about differences of artefacts through different implant materials and image modalities might help support clinical decisions for the choice of implant material or imaging device in the clinical setting.

Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan

The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VIImore » of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.« less

Evolution of the Valley Position in Bulk Transition-Metal Chalcogenides and Their Monolayer Limit.

PubMed

Yuan, Hongtao; Liu, Zhongkai; Xu, Gang; Zhou, Bo; Wu, Sanfeng; Dumcenco, Dumitru; Yan, Kai; Zhang, Yi; Mo, Sung-Kwan; Dudin, Pavel; Kandyba, Victor; Yablonskikh, Mikhail; Barinov, Alexei; Shen, Zhixun; Zhang, Shoucheng; Huang, Yingsheng; Xu, Xiaodong; Hussain, Zahid; Hwang, Harold Y; Cui, Yi; Chen, Yulin

2016-08-10

Layered transition metal chalcogenides with large spin orbit coupling have recently sparked much interest due to their potential applications for electronic, optoelectronic, spintronics, and valleytronics. However, most current understanding of the electronic structure near band valleys in momentum space is based on either theoretical investigations or optical measurements, leaving the detailed band structure elusive. For example, the exact position of the conduction band valley of bulk MoS2 remains controversial. Here, using angle-resolved photoemission spectroscopy with submicron spatial resolution (micro-ARPES), we systematically imaged the conduction/valence band structure evolution across representative chalcogenides MoS2, WS2, and WSe2, as well as the thickness dependent electronic structure from bulk to the monolayer limit. These results establish a solid basis to understand the underlying valley physics of these materials, and also provide a link between chalcogenide electronic band structure and their physical properties for potential valleytronics applications.

Flexible transparent conductors based on metal nanowire networks

DOE PAGES

Guo, Chuan Fei; Ren, Zhifeng

2015-04-01

Few conductors are transparent and flexible. Metals have the best electrical conductivity, but they are opaque and stiff in bulk form. However, metals can be transparent and flexible when they are very thin or properly arranged on the nanoscale. This review focuses on the flexible transparent conductors based on percolating networks of metal. Specifically, we discuss the fabrication, the means to improve the electrical conductivity, the large stretchability and its mechanism, and the applications of these metal networks. We also suggest some criteria for evaluating flexible transparent conductors and propose some new research directions in this emerging field.

Zirconium as a Structural Material for Naval Systems

DTIC Science & Technology

1985-03-29

case with the technologically critical chemical elements chromium and cobalt, for example, from a military perspective. The case, therefore, for...By adding small amounts of tin, iron, nickel, and chromium , the impurities were effectively bound or coalesced within the metal and the corrosion...and nitrogen from the atmosphere, embrittling the weld. The techniques used for zirconium welding are gas tungsten arc welding ( GTAW ), tungsten inert

NMR signature of evolution of ductile-to-brittle transition in bulk metallic glasses.

PubMed

Yuan, C C; Xiang, J F; Xi, X K; Wang, W H

2011-12-02

The mechanical properties of monolithic metallic glasses depend on the structures at atomic or subnanometer scales, while a clear correlation between mechanical behavior and structures has not been well established in such amorphous materials. In this work, we find a clear correlation of (27)Al NMR isotropic shifts with a microalloying induced ductile-to-brittle transition at ambient temperature in bulk metallic glasses, which indicates that the (27)Al NMR isotropic shift can be regarded as a structural signature to characterize plasticity for this metallic glass system. The study provides a compelling approach for investigating and understanding the mechanical properties of metallic glasses from the point of view of electronic structure. © 2011 American Physical Society

Atomistic modeling of high temperature uranium-zirconium alloy structure and thermodynamics

NASA Astrophysics Data System (ADS)

Moore, A. P.; Beeler, B.; Deo, C.; Baskes, M. I.; Okuniewski, M. A.

2015-12-01

A semi-empirical Modified Embedded Atom Method (MEAM) potential is developed for application to the high temperature body-centered-cubic uranium-zirconium alloy (γ-U-Zr) phase and employed with molecular dynamics (MD) simulations to investigate the high temperature thermo-physical properties of U-Zr alloys. Uranium-rich U-Zr alloys (e.g. U-10Zr) have been tested and qualified for use as metallic nuclear fuel in U.S. fast reactors such as the Integral Fast Reactor and the Experimental Breeder Reactors, and are a common sub-system of ternary metallic alloys like U-Pu-Zr and U-Zr-Nb. The potential was constructed to ensure that basic properties (e.g., elastic constants, bulk modulus, and formation energies) were in agreement with first principles calculations and experimental results. After which, slight adjustments were made to the potential to fit the known thermal properties and thermodynamics of the system. The potentials successfully reproduce the experimental melting point, enthalpy of fusion, volume change upon melting, thermal expansion, and the heat capacity of pure U and Zr. Simulations of the U-Zr system are found to be in good agreement with experimental thermal expansion values, Vegard's law for the lattice constants, and the experimental enthalpy of mixing. This is the first simulation to reproduce the experimental thermodynamics of the high temperature γ-U-Zr metallic alloy system. The MEAM potential is then used to explore thermodynamics properties of the high temperature U-Zr system including the constant volume heat capacity, isothermal compressibility, adiabatic index, and the Grüneisen parameters.

Braze material for joining ceramic to metal and ceramic to ceramic surfaces and joined ceramic to metal and ceramic to ceramic article

DOEpatents

Hunt, T.K.; Novak, R.F.

1991-05-07

An improved active metal braze filler material is provided in which the coefficient of thermal expansion of the braze filler is more closely matched with that of the ceramic and metal, or two ceramics, to provide ceramic to metal, or ceramic to ceramic, sealed joints and articles which can withstand both high temperatures and repeated thermal cycling without failing. The braze filler material comprises a mixture of a material, preferably in the form of a powder, selected from the group consisting of molybdenum, tungsten, silicon carbide and mixtures thereof, and an active metal filler material selected from the group consisting of alloys or mixtures of nickel and titanium, alloys or mixtures of nickel and zirconium, alloys or mixtures of nickel, titanium, and copper, alloys or mixtures of nickel, titanium, and zirconium, alloys or mixtures of niobium and nickel, alloys or mixtures of niobium and zirconium, alloys or mixtures of niobium and titanium, alloys or mixtures of niobium, titanium, and nickel, alloys or mixtures of niobium, zirconium, and nickel, and alloys or mixtures of niobium, titanium, zirconium, and nickel. The powder component is selected such that its coefficient of thermal expansion will effect the overall coefficient of thermal expansion of the braze material so that it more closely matches the coefficients of thermal expansion of the ceramic and metal parts to be joined. 3 figures.

Braze material for joining ceramic to metal and ceramic to ceramic surfaces and joined ceramic to metal and ceramic to ceramic article

DOEpatents

Hunt, Thomas K.; Novak, Robert F.

1991-01-01

An improved active metal braze filler material is provided in which the coefficient of thermal expansion of the braze filler is more closely matched with that of the ceramic and metal, or two ceramics, to provide ceramic to metal, or ceramic to ceramic, sealed joints and articles which can withstand both high temperatures and repeated thermal cycling without failing. The braze filler material comprises a mixture of a material, preferably in the form of a powder, selected from the group consisting of molybdenum, tungsten, silicon carbide and mixtures thereof, and an active metal filler material selected from the group consisting of alloys or mixtures of nickel and titanium, alloys or mixtures of nickel and zirconium, alloys or mixtures of nickel, titanium, and copper, alloys or mixtures of nickel, titanium, and zirconium, alloys or mixtures of niobium and nickel, alloys or mixtures of niobium and zirconium, alloys or mixtures of niobium and titanium, alloys or mixtures of niobium, titanium, and nickel, alloys or mixtures of niobium, zirconium, and nickel, and alloys or mixtures of niobium, titanium, zirconium, and nickel. The powder component is selected such that its coefficient of thermal expansion will effect the overall coefficient of thermal expansion of the braze material so that it more closely matches the coefficients of thermal expansion of the ceramic and metal parts to be joined.

Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions

PubMed Central

Nayak, Nadiya B.; Nayak, Bibhuti B.

2016-01-01

Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution. PMID:26980545

Influence of tool speeds on dissimilar friction stir spot welding characteristics of bulk metallic glass/Mg alloy

NASA Astrophysics Data System (ADS)

Shin, Hyung-Seop; Jung, Yoon-Chul; Lee, Jin-Kyu

2012-08-01

A small-scale joining technique of dissimilar friction stir spot welding (FSSW) between bulk metallic glass and Mg alloy sheet has been tried using an apparatus which was devised with a CNC milling machine to give a precise control of tool speeds. The influence of tool speeds on the joining characteristics during FSSW was investigated. As a result, it was found that the rotation speed and plunge speed of a tool during FSSW significantly influenced the welding performance of dissimilar FSSW between bulk metallic glasses and Mg alloy.

Gel-based morphological design of zirconium metal-organic frameworks.

PubMed

Bueken, Bart; Van Velthoven, Niels; Willhammar, Tom; Stassin, Timothée; Stassen, Ivo; Keen, David A; Baron, Gino V; Denayer, Joeri F M; Ameloot, Rob; Bals, Sara; De Vos, Dirk; Bennett, Thomas D

2017-05-01

The ability of metal-organic frameworks (MOFs) to gelate under specific synthetic conditions opens up new opportunities in the preparation and shaping of hierarchically porous MOF monoliths, which could be directly implemented for catalytic and adsorptive applications. In this work, we present the first examples of xero- or aerogel monoliths consisting solely of nanoparticles of several prototypical Zr 4+ -based MOFs: UiO-66-X (X = H, NH 2 , NO 2 , (OH) 2 ), UiO-67, MOF-801, MOF-808 and NU-1000. High reactant and water concentrations during synthesis were observed to induce the formation of gels, which were converted to monolithic materials by drying in air or supercritical CO 2 . Electron microscopy, combined with N 2 physisorption experiments, was used to show that irregular nanoparticle packing leads to pure MOF monoliths with hierarchical pore systems, featuring both intraparticle micropores and interparticle mesopores. Finally, UiO-66 gels were shaped into monolithic spheres of 600 μm diameter using an oil-drop method, creating promising candidates for packed-bed catalytic or adsorptive applications, where hierarchical pore systems can greatly mitigate mass transfer limitations.

Photophysical properties of [Ru(2,2‧-bipyridine)3]2+ encapsulated within the Uio-66 zirconium based metal organic framework

NASA Astrophysics Data System (ADS)

Larsen, Randy W.; Wojtas, Lukasz

2017-03-01

The ability to encapsulate photo-active guest molecules within the pores of metal organic frameworks (MOFs) affords the opportunity to develop robust photocatalysts as well as solar energy conversion systems. An important criteria for such systems is stability of the new materials towards moisture, high temperatures, etc which preclude the use of many MOF frameworks. Here, the ability to encapsulate [Ru(II)(2,2‧-bipyridine)3]2+([Ru(bpy)3]2+) into the cavities of the zirconium based MOF Uio-66 as well as the photophysical properties of the complex are reported. The X-ray powder diffraction data of the orange Uio-66 powder are consistent with the formation of Uio-66 in the presence of [Ru(bpy)3]2+. The steady state emission exhibits a significant bathochromic shift from 603 nm in ethanol to 610 nm in Uio-66. The corresponding emission decay of the encapsulated [Ru(bpy)3]2+ complex is biexponential with a fast component of 128 ns and a slower component of 1176 ns (20 deg C). The slow component is consistent with encapsulation of [Ru(bpy)3]2+ into cavities with restricted volume that prevents the population of a triplet ligand field transition that is anti-bonding with respect to the Ru-N bonds. The origin of the fast component is unclear but may involve interactions of the [Ru(bpy)3]2+ encapsulated within large cavities formed through missing ligand defect sites within the Uio-66 materials. Co-encapsulated quenchers contained within these larger cavities gives rise to the reduced lifetimes of the [Ru(bpy)3]2+ complexes.

The structural properties of Zr-based bulk metallic glasses subjected to high pressure torsion at different temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boltynjuk, E. V., E-mail: boltynjuk@gmail.com; Ubyivovk, E. V.; Kshumanev, A. M.

2016-06-17

The structural properties of a Zr{sub 62}Cu{sub 22}Al{sub 10}Fe{sub 5}Dy{sub 1} bulk metallic glasses were investigated. Cylindrical rods of the Zr{sub 62}Cu{sub 22}Al{sub 10}Fe{sub 5}Dy{sub 1} BMG were subjected to high pressure torsion at temperatures of 20°C and 150°C. X-ray diffraction, transmission electron microscopy were used to determine peculiarities of the modified structure. Analysis of fracture surfaces, nanohardness measurements were conducted to investigate the influence of structural changes on mechanical behavior of processed samples.

Microyielding of core-shell crystal dendrites in a bulk-metallic-glass matrix composite

DOE PAGES

Huang, E. -Wen; Qiao, Junwei; Winiarski, Bartlomiej; ...

2014-03-18

In-situ synchrotron x-ray experiments have been used to follow the evolution of the diffraction peaks for crystalline dendrites embedded in a bulk metallic glass matrix subjected to a compressive loading-unloading cycle. We observe irreversible diffraction-peak splitting even though the load does not go beyond half of the bulk yield strength. The chemical analysis coupled with the transmission electron microscopy mapping suggests that the observed peak splitting originates from the chemical heterogeneity between the core (major peak) and the stiffer shell (minor peak) of the dendrites. A molecular dynamics model has been developed to compare the hkl-dependent microyielding of the bulkmore » metallic-glass matrix composite. As a result, the complementary diffraction measurements and the simulation results suggest that the interfaces between the amorphous matrix and the (211) crystalline planes relax under prolonged load that causes a delay in the reload curve which ultimately catches up with the original path.« less

Improved Yttrium and Zirconium Abundances in Metal-Poor Stars

NASA Astrophysics Data System (ADS)

Violante, Renata; Biemont, E.; Cowan, J. J.; Sneden, C.

2012-01-01

Abstract We present new abundances of the lighter n-capture elements, Yttrium (Z=39) and Zirconium (Z=40) in the very metal poor, r-process rich stars BD+17 3248 and HD 221170. Very accurate abundances were obtained by use of the new transition probabilities for Y II published by Biémont et al. 2011, and Zr II by Malcheva et al. 2006, and by expanding the number of transitions employed for each element. For example, in BD+17 3248, we find log ɛπσιλον=-0.03 +/- 0.03 (σιγμα=0.15, from 23 lines) for Y II. As for Zr II, log ɛπσιλον = 0.65 +/- 0.03 (σɛγμα = 0.1, from 13 lines). The resulting abundance ratio is log ɛπσιλον [Y/Zr] = -0.68 +/- 0.05. The results for HD 221170 are in accord with those of BD+17 3248. The quantity of lines used to form the abundance means has increased significantly since the original studies of these stars, resulting in more trustworthy abundances. These observed abundance ratios are in agreement with an r-process-only value predicted from stellar models, but is under-abundant compared to an empirical model derived from direct analyses of meteoritic material. This ambiguity should stimulate further nucleosynthetic analysis to explain this abundance ratio. We would like to extend our gratitude to NSF grant AST-0908978 and the University of Texas Astronomy Department Rex G. Baker, Jr. Endowment for their financial support in this project.

Dynamic Pressure Induced Transformation Toughening and Strengthening in Bulk Metallic Glasses

DTIC Science & Technology

2013-11-01

involved impact of 303 stainless steel flyer-plate on 303 stainless steel sample holder containing two BMGMC samples, at varying velocities. The Hugoniot...Technology. An aluminum sabot was used as the projectile with 303 Stainless Steel (SS) flyer plate to impact the DV1 bulk metallic glass composite. As...crystallization; polyamorphism; shear banding; high- strain -rate deformation REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR

Refractory metal joining for first wall applications

NASA Astrophysics Data System (ADS)

Cadden, C. H.; Odegard, B. C.

2000-12-01

The potential use of high temperature coolant (e.g. 900°C He) in first wall structures would preclude the applicability of copper alloy heat sink materials and refractory metals would be potential replacements. Brazing trials were conducted in order to examine techniques to join tungsten armor to high tungsten (90-95 wt%) or molybdenum TZM heat sink materials. Palladium-, nickel- and zirconium-based filler metals were investigated using brazing temperatures ranging from 1000°C to 1275°C. Palladium-nickel and palladium-cobalt braze alloys were successful in producing generally sound metallurgical joints in tungsten alloy/tungsten couples, although there was an observed tendency for the pure tungsten armor material to exhibit grain boundary cracking after bonding. The zirconium- and nickel-based filler metals produced defect-containing joints, specifically cracking and porosity, respectively. The palladium-nickel braze alloy produced sound joints in the Mo TZM/tungsten couple. Substitution of a lanthanum oxide-containing, fine-grained tungsten material (for the pure tungsten) eliminated the observed tungsten grain boundary cracking.

METHOD OF FORMING A PROTECTIVE COATING ON FERROUS METAL SURFACES

DOEpatents

Schweitzer, D.G.; Weeks, J.R.; Kammerer, O.F.; Gurinsky, D.H.

1960-02-23

A method is described of protecting ferrous metal surfaces from corrosive attack by liquid metals, such as liquid bismuth or lead-bismuth alloys. The nitrogen content of the ferrous metal surface is first reduced by reacting the metal surface with a metal which forms a stable nitride. Thereafter, the surface is contacted with liquid metal containing at least 2 ppm zirconium at a temperature in the range of 550 to 1100 deg C to form an adherent zirconium carbide layer on the ferrous surface.

From chemistry to mechanics: bulk modulus evolution of Li-Si and Li-Sn alloys via the metallic electronegativity scale.

PubMed

Li, Keyan; Xie, Hui; Liu, Jun; Ma, Zengsheng; Zhou, Yichun; Xue, Dongfeng

2013-10-28

Toward engineering high performance anode alloys for Li-ion batteries, we proposed a useful method to quantitatively estimate the bulk modulus of binary alloys in terms of metallic electronegativity (EN), alloy composition and formula volume. On the basis of our proposed potential viewpoint, EN as a fundamental chemistry concept can be extended to be an important physical parameter to characterize the mechanical performance of Li-Si and Li-Sn alloys as anode materials for Li-ion batteries. The bulk modulus of binary alloys is linearly proportional to the combination of average metallic EN and atomic density of alloys. We calculated the bulk moduli of Li-Si and Li-Sn alloys with different Li concentrations, which can agree well with the reported data. The bulk modulus of Li-Si and Li-Sn alloys decreases with increasing Li concentration, leading to the elastic softening of the alloys, which is essentially caused by the decreased strength of constituent chemical bonds in alloys from the viewpoint of EN. This work provides a deep understanding of mechanical failure of Si and Sn anodes for Li-ion batteries, and permits the prediction of the composition dependent bulk modulus of various lithiated alloys on the basis of chemical formula, metallic EN and cell volume (or alloy density), with no structural details required.

The use of precious-metal-modified nickel-based superalloys for thin gage applications

NASA Astrophysics Data System (ADS)

Ballard, Donna L.; Pilchak, Adam L.

2010-10-01

Precious-metal-modified nickel-based superalloys are being investigated for use in thin gage applications, such as thermal protection systems or heat exchangers, due to their strength and inherent oxidation resistance at temperatures in excess of 1,050°C. This overview paper summarizes the Air Force Research Laboratory (AFRL) interest in experimental two-phase γ-Ni + γ'-Ni3Al superalloys. The AFRL is interested in alloys with a based composition of Ni-15Al-5Cr (at. %) with carbon, boron, and zirconium additions for grain-boundary refinement and strengthening. The alloys currently being evaluated also contain 4-5 at.% of platinum-group metals, in this case platinum and iridium. The feasibility of hot rolling these alloys to a final thickness of 0.12-0.25 mm and obtaining a nearly fully recrystallized microstructure was demonstrated.

Zirconium determination by cooling curve analysis during the pyroprocessing of used nuclear fuel

NASA Astrophysics Data System (ADS)

Westphal, B. R.; Price, J. C.; Bateman, K. J.; Marsden, K. C.

2015-02-01

An alternative method to sampling and chemical analyses has been developed to monitor the concentration of zirconium in real-time during the casting of uranium products from the pyroprocessing of used nuclear fuel. The method utilizes the solidification characteristics of the uranium products to determine zirconium levels based on standard cooling curve analyses and established binary phase diagram data. Numerous uranium products have been analyzed for their zirconium content and compared against measured zirconium data. From this data, the following equation was derived for the zirconium content of uranium products:

Zirconium-based highly porous metal-organic framework (MOF-545) as an efficient adsorbent for vortex assisted-solid phase extraction of lead from cereal, beverage and water samples.

PubMed

Tokalıoğlu, Şerife; Yavuz, Emre; Demir, Selçuk; Patat, Şaban

2017-12-15

In this study, zirconium-based highly porous metal-organic framework, MOF-545, was synthesized and characterized. The surface area of MOF-545 was found to be 2192m 2 /g. This adsorbent was used for the first time as an adsorbent for the vortex assisted-solid phase extraction of Pb(II) from cereal, beverage and water samples. Lead in solutions was determined by FAAS. The optimal experimental conditions were as follows: the amount of MOF-545, 10mg; pH of sample, 7; adsorption and elution time, 15min; and elution solvent, 2mL of 1molL -1 HCl. Under the optimal conditions of the method, the limit of detection, preconcentration factor and precision as RSD% were found to be 1.78μgL -1 , 125 and 2.6%, respectively. The adsorption capacity of the adsorbent for lead was found to be 73mgg -1 . The method was successfully verified by analyzing two certified reference materials (BCR-482 Lichen and SPS-WW1 Batch 114) and spiked chickpea, bean, wheat, lentil, cherry juice, mineral water, well water and wastewater samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Method of making crack-free zirconium hydride

DOEpatents

Sullivan, Richard W.

1980-01-01

Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

Optimal aluminum/zirconium: Protein interactions for predicting antiperspirant efficacy using zeta potential measurements.

PubMed

Yuan, Shaotang; Vaughn, John; Pappas, Iraklis; Fitzgerald, Michael; Masters, James G; Pan, Long

2015-01-01

The interactions between commercial antiperspirant (AP) salts [aluminum chlorohydrate (ACH), activated ACH, aluminum sesquichlorohydrate (ASCH), zirconium aluminum glycine (ZAG), activated ZAG), pure aluminum polyoxocations (Al13-mer, Al30-mer), and the zirconium(IV)-glycine complex Zr6 (O)4 (OH)4 (H2O)8 (Gly)8]12+(-) (CP-2 or ZG) with Bovine serum albumin (BSA) were studied using zeta potential and turbidity measurements. The maximal turbidity, which revealed the optimal interactions between protein and metal salts, for all protein-metal salt samples was observed at the isoelectric point (IEP), where the zeta potential of the solution was zero. Efficacy of AP salts was determined via three parameters: the amount of salt required to flocculate BSA to reach IEP, the turbidity of solution at the IEP, and the pH range over which the turbidity of the solution remains sufficiently high. By comparing active salt performance from this work to traditional prescreening methods, this methodology was able to provide a consistent efficacy assessment for metal actives in APs or in water treatment.

Ternary cobalt-molybdenum-zirconium coatings for alternative energies

NASA Astrophysics Data System (ADS)

Yar-Mukhamedova, Gulmira; Ved', Maryna; Sakhnenko, Nikolay; Koziar, Maryna

2017-11-01

Consistent patterns for electrodeposition of Co-Mo-Zr coatings from polyligand citrate-pyrophosphate bath were investigated. The effect of both current density amplitude and pulse on/off time on the quality, composition and surface morphology of the galvanic alloys were determined. It was established the coating Co-Mo-Zr enrichment by molybdenum with current density increasing up to 8 A dm-2 as well as the rising of pulse time and pause duration promotes the content of molybdenum because of subsequent chemical reduction of its intermediate oxides by hydrogen ad-atoms. It was found that the content of the alloying metals in the coating Co-Mo-Zr depends on the current density and on/off times extremely and maximum Mo and Zr content corresponds to the current density interval 4-6 A dm-2, on-/off-time 2-10 ms. Chemical resistance of binary and ternary coatings based on cobalt is caused by the increased tendency to passivity and high resistance to pitting corrosion in the presence of molybdenum and zirconium, as well as the acid nature of their oxides. Binary coating with molybdenum content not less than 20 at.% and ternary ones with zirconium content in terms of corrosion deep index are in a group ;very proof;. It was shown that Co-Mo-Zr alloys exhibits the greatest level of catalytic properties as cathode material for hydrogen electrolytic production from acidic media which is not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2-4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for red-ox processes activating by oxygen as well as electrode materials for red-ox batteries.

An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. I. Model and validation

NASA Astrophysics Data System (ADS)

Hegde, Ganesh; Povolotskyi, Michael; Kubis, Tillmann; Boykin, Timothy; Klimeck, Gerhard

2014-03-01

Semi-empirical Tight Binding (TB) is known to be a scalable and accurate atomistic representation for electron transport for realistically extended nano-scaled semiconductor devices that might contain millions of atoms. In this paper, an environment-aware and transferable TB model suitable for electronic structure and transport simulations in technologically relevant metals, metallic alloys, metal nanostructures, and metallic interface systems are described. Part I of this paper describes the development and validation of the new TB model. The new model incorporates intra-atomic diagonal and off-diagonal elements for implicit self-consistency and greater transferability across bonding environments. The dependence of the on-site energies on strain has been obtained by appealing to the Moments Theorem that links closed electron paths in the system to energy moments of angular momentum resolved local density of states obtained ab initio. The model matches self-consistent density functional theory electronic structure results for bulk face centered cubic metals with and without strain, metallic alloys, metallic interfaces, and metallic nanostructures with high accuracy and can be used in predictive electronic structure and transport problems in metallic systems at realistically extended length scales.

Ductile Damage and Fatigue Behavior of Semi-Finished Tailored Blanks for Sheet-Bulk Metal Forming Processes

NASA Astrophysics Data System (ADS)

Besserer, Hans-Bernward; Hildenbrand, Philipp; Gerstein, Gregory; Rodman, Dmytro; Nürnberger, Florian; Merklein, Marion; Maier, Hans Jürgen

2016-03-01

To produce parts from sheet metal with thickened functional elements, bulk forming operations can be employed. For this new process class, the term sheet-bulk metal forming has been established recently. Since sheet-bulk metal forming processes such as orbital forming generates triaxial stress and strain states, ductile damage is induced in the form of voids in the microstructure. Typical parts will experience cyclic loads during service, and thus, the influence of ductile damage on the fatigue life of parts manufactured by orbital forming is of interest. Both the formation and growth of voids were characterized following this forming process and then compared to the as-received condition of the ferritic deep drawing steel DC04 chosen for this study. Subsequent to the forming operation, the specimens were fatigued and the evolution of ductile damage and the rearrangement of the dislocation networks occurring during cyclic loading were determined. It was shown, that despite an increased ductile damage due to the forming process, the induced strain hardening has a positive effect on the fatigue life of the material. However, by analyzing the fatigued specimens a development of the ductile damage by an increasing number of voids and a change in the void shape were detected.

The Effect of Boron and Zirconium on the Structure and Tensile Properties of the Cast Nickel-Based Superalloy ATI 718Plus

NASA Astrophysics Data System (ADS)

Hosseini, Seyed Ali; Abbasi, Seyed Mehdi; Madar, Karim Zangeneh

2018-04-01

The effects of boron and zirconium on cast structure, hardness, and tensile properties of the nickel-based superalloy 718Plus were investigated. For this purpose, five alloys with different contents of boron and zirconium were cast via vacuum induction melting and then purified via vacuum arc remelting. Microstructural analysis by light-optical microscope and scanning electron microscope equipped with energy-dispersive x-ray spectroscopy and phase studies by x-ray diffraction analysis were performed. The results showed that boron and zirconium tend to significantly reduce dendritic arm spacing and increase the amount of Laves, Laves/gamma eutectic, and carbide phases. It was also found that boron led to the formation of B4C and (Cr, Fe, Mo, Ni, Ti)3B2 phases and zirconium led to the formation of intermetallic phases and ZrC carbide. In the presence of boron and zirconium, the hardness and its difference between dendritic branches and inter-dendritic spaces increased by concentrating such phases as Laves in the inter-dendritic spaces. These elements had a negative effect on tensile properties of the alloy, including ductility and strength, mainly because of the increase in the Laves phase. It should be noted that the largest degradation of the tensile properties occurred in the alloys containing the maximum amount of zirconium.

Corrosion-electrochemical behavior of zirconium in molten alkali metal carbonates

NASA Astrophysics Data System (ADS)

Nikitina, E. V.

2016-08-01

The corrosion and electrochemical characteristics of zirconium during its interaction with molten lithium, sodium, and potassium carbonates containing from 1 to 5 wt % additives to the salt phase are studied in a temperature range of 500-800°C using gravimetry, corrosion potential measurement, and anodic polarization. The substances decreasing the corrosion losses due to the strengthening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used as passivators. Sodium chloride, fluoride, and sulfate serve as corrosion stimulators (activators).

2D zirconium-based metal-organic framework nanosheets for highly sensitive detection of mucin 1: consistency between electrochemical and surface plasmon resonance methods

NASA Astrophysics Data System (ADS)

He, Linghao; Duan, Fenghe; Song, Yingpan; Guo, Chuanpan; Zhao, Hui; Tian, Jia-Yue; Zhang, Zhihong; Liu, Chun-Sen; Zhang, Xiaojing; Wang, Peiyuan; Du, Miao; Fang, Shao-Ming

2017-06-01

Two-dimensional (2D) zirconium-based metal-organic framework (denoted as 521-MOF) nanosheets with the thickness of 6.0-7.5 nm were prepared with the aid of polyvinyl pyrrolidone (PVP) under the mild conditions and low temperature (50 °C). Since 521-MOF nanosheets displayed good electrochemical activity, high surface area, and strong affinity interaction between the MOF and the oligonucleotides sequences, they can impel the immobilization of large amounts of aptamer strands when applied as a platform of biosensor. As a result, the developed aptasensor exhibited sensitive bio-recognition for the cancer determination marker protein, mucin 1 (MUC1). The combination of electrochemical techniques and surface plasmon resonance spectroscopy (SPR) was performed to probe the kinetic processes of the aptamer immobilization and the MUC1 detection. The consistency between different determination approaches was observed, in which the developed aptasensor based on 521-MOF nanosheets exhibits pretty high sensitivity for detecting MUC1 with a low detect limit of 0.12 and 0.65 pg·ml-1 deduced from electrochemical impedance spectroscopy and SPR, respectively, within the broad concentration range of MUC1 from 0.001 to 0.5 ng·ml-1. Simultaneously, a comparable affinity constant, K a, was derived from EIS and SPR, which also demonstrates that this new biosensing strategy has high selectivity, stability, reproducibility, and good applicability for the MUC1 detection in the human serum. The present finding indicates that the synthesized 521-MOF nanosheets can be employed in the fields of the biosensing or biomedical diagnosis and explored for different kinds of biosensors.

Ignition and Combustion of Bulk Metals in a Microgravity Environment

NASA Technical Reports Server (NTRS)

Branch, M. C.; Daily, J. W.; Abbud-Madrid, A.

1996-01-01

This annual report summarizes the latest results obtained in a NASA-supported project to investigate the effect of gravity on the ignition and combustion of bulk metals. The experimental arrangement used for this purpose consists of a 1000-W xenon lamp that irradiates the top surface of cylindrical titanium and magnesium specimens, 4 mm in diameter and 4 mm in height, in a quiescent, pure-oxygen environment at 1 atm. Reduced gravity is obtained from the NASA LeRC DC-9 aircraft flying parabolic trajectories. Values of critical and ignition temperatures are obtained from thermocouple records. Qualitative observations and propagation rates are extracted from high-speed cinematography. Emission spectra of gas-phase reactions are obtained with an imaging spectrograph/diode array system. It was found that high applied heating rates and large internal conduction losses generate critical and ignition temperatures that are several hundred degrees above the values obtained from isothermal experiments. Because of high conduction and radiation heat losses, no appreciable effect on ignition temperatures with reduced convection in low gravity is detected. Lower propagation rates of the molten interface on titanium and of ignition waves on magnesium are obtained at reduced gravity. These rates are compared to theoretical results from heat conduction analyses with a diffusion/convection controlled reaction. The close agreement found between experimental and theoretical values indicates the importance of the influence of natural convection-enhanced oxygen transport on combustion rates. Lower oxygen flux and lack of oxide product removal in the absence of convective currents appear to be responsible for longer burning times of magnesium diffusion flames at reduced gravity. The accumulation of condensed oxide particles in the flame front at low gravity produces a previously unreported unsteady explosion phenomenon in bulk magnesium flames. This spherically symmetric explosion

Induction detection of concealed bulk banknotes

NASA Astrophysics Data System (ADS)

Fuller, Christopher; Chen, Antao

2012-06-01

The smuggling of bulk cash across borders is a serious issue that has increased in recent years. In an effort to curb the illegal transport of large numbers of paper bills, a detection scheme has been developed, based on the magnetic characteristics of bank notes. The results show that volumes of paper currency can be detected through common concealing materials such as plastics, cardboard, and fabrics making it a possible potential addition to border security methods. The detection scheme holds the potential of also reducing or eliminating false positives caused by metallic materials found in the vicinity, by observing the stark difference in received signals caused by metal and currency. The detection scheme holds the potential to detect for both the presence and number of concealed bulk notes, while maintaining the ability to reduce false positives caused by metal objects.

High pressure die casting of Fe-based metallic glass.

PubMed

Ramasamy, Parthiban; Szabo, Attila; Borzel, Stefan; Eckert, Jürgen; Stoica, Mihai; Bárdos, András

2016-10-11

Soft ferromagnetic Fe-based bulk metallic glass key-shaped specimens with a maximum and minimum width of 25.4 and 5 mm, respectively, were successfully produced using a high pressure die casting (HPDC) method, The influence of die material, alloy temperature and flow rate on the microstructure, thermal stability and soft ferromagnetic properties has been studied. The results suggest that a steel die in which the molten metal flows at low rate and high temperature can be used to produce completely glassy samples. This can be attributed to the laminar filling of the mold and to a lower heat transfer coefficient, which avoids the skin effect in the steel mold. In addition, magnetic measurements reveal that the amorphous structure of the material is maintained throughout the key-shaped samples. Although it is difficult to control the flow and cooling rate of the molten metal in the corners of the key due to different cross sections, this can be overcome by proper tool geometry. The present results confirm that HPDC is a suitable method for the casting of Fe-based bulk glassy alloys even with complex geometries for a broad range of applications.

High pressure die casting of Fe-based metallic glass

NASA Astrophysics Data System (ADS)

Ramasamy, Parthiban; Szabo, Attila; Borzel, Stefan; Eckert, Jürgen; Stoica, Mihai; Bárdos, András

2016-10-01

Soft ferromagnetic Fe-based bulk metallic glass key-shaped specimens with a maximum and minimum width of 25.4 and 5 mm, respectively, were successfully produced using a high pressure die casting (HPDC) method, The influence of die material, alloy temperature and flow rate on the microstructure, thermal stability and soft ferromagnetic properties has been studied. The results suggest that a steel die in which the molten metal flows at low rate and high temperature can be used to produce completely glassy samples. This can be attributed to the laminar filling of the mold and to a lower heat transfer coefficient, which avoids the skin effect in the steel mold. In addition, magnetic measurements reveal that the amorphous structure of the material is maintained throughout the key-shaped samples. Although it is difficult to control the flow and cooling rate of the molten metal in the corners of the key due to different cross sections, this can be overcome by proper tool geometry. The present results confirm that HPDC is a suitable method for the casting of Fe-based bulk glassy alloys even with complex geometries for a broad range of applications.

High pressure die casting of Fe-based metallic glass

PubMed Central

Ramasamy, Parthiban; Szabo, Attila; Borzel, Stefan; Eckert, Jürgen; Stoica, Mihai; Bárdos, András

2016-01-01

Soft ferromagnetic Fe-based bulk metallic glass key-shaped specimens with a maximum and minimum width of 25.4 and 5 mm, respectively, were successfully produced using a high pressure die casting (HPDC) method, The influence of die material, alloy temperature and flow rate on the microstructure, thermal stability and soft ferromagnetic properties has been studied. The results suggest that a steel die in which the molten metal flows at low rate and high temperature can be used to produce completely glassy samples. This can be attributed to the laminar filling of the mold and to a lower heat transfer coefficient, which avoids the skin effect in the steel mold. In addition, magnetic measurements reveal that the amorphous structure of the material is maintained throughout the key-shaped samples. Although it is difficult to control the flow and cooling rate of the molten metal in the corners of the key due to different cross sections, this can be overcome by proper tool geometry. The present results confirm that HPDC is a suitable method for the casting of Fe-based bulk glassy alloys even with complex geometries for a broad range of applications. PMID:27725780

Ablation Resistant Zirconium and Hafnium Ceramics

NASA Technical Reports Server (NTRS)

Bull, Jeffrey (Inventor); White, Michael J. (Inventor); Kaufman, Larry (Inventor)

1998-01-01

High temperature ablation resistant ceramic composites have been made. These ceramics are composites of zirconium diboride and zirconium carbide with silicon carbide, hafnium diboride and hafnium carbide with silicon carbide and ceramic composites which contain mixed diborides and/or carbides of zirconium and hafnium. along with silicon carbide.

James C. McGroddy Prize Talk: Development and Applications of Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Inoue, Akihisa

2009-03-01

We realized, through detailed amorphous material investigations in the 1980's, that a number of metallic glassy alloys of multi-component La-, Mg- and Zr-based systems exhibit a large supercooled-liquid region prior to crystallization. The stabilization phenomenon of these supercooled liquid should enable us to fabricate, by slow cooling processes, bulk metallic glasses (BMGs) with critical diameters larger than several millimeters. Caltech's group also succeeded the fabrication of BMG in Zr-based alloy system in 1993. Since then, much attention has been paid to BMGs because of their novel characteristics in basic science and engineering aspects and new materials science and engineering fields have emerged for BMGs. Based on knowledge obtained thus far, we have successfully developed new BMGs with technologically-important transition metals, such as Zr-, Ti-, Fe-, Co-, Ni- and Cu-based alloys. Currently, the maximum diameter for glass formation reaches 30 mm for Zr- and Cu-based systems, 12 mm for Ti-based system, 18 mm for Fe-Co-based system and 20 mm for Ni-based system, even employing the copper mold casting technique. These large size BMGs possess nearly the same fundamental properties as those of the BMGs with smaller diameters. BMGs with diameters above 10 mm can be formed in Zr-Al-Ni-Cu system with Zr compositions higher than 65 at% and they exhibit excellent properties, such as high Poisson's ratio, high ductility, high fracture toughness, high fatigue strength and high stability of mechanical properties to annealing-induced embrittlement. The new Ti-based BMGs without allergic and toxic elements should exhibit good compatibility to bio-tissues. Applications of BMGs in Fe-, Co-, Ti- and Zr-based systems have advanced many devices including the following; choke coil, power inductor, electro magnetic shielding, magnetic and position sensors, micro-geared motor, pressure sensor, Coriolis flowmeter, surface coating layer, precise polishing medium, magnetic and

Method for preparing hydrous zirconium oxide gels and spherules

DOEpatents

Collins, Jack L.

2003-08-05

Methods for preparing hydrous zirconium oxide spherules, hydrous zirconium oxide gels such as gel slabs, films, capillary and electrophoresis gels, zirconium monohydrogen phosphate spherules, hydrous zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite sorbent, zirconium monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite, hydrous zirconium oxide fiber materials, zirconium oxide fiber materials, hydrous zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite and spherules of barium zirconate. The hydrous zirconium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process are useful as inorganic ion exchangers, catalysts, getters and ceramics.

Atomic layer deposition of zirconium silicate films using zirconium tetrachloride and tetra-n-butyl orthosilicate

NASA Astrophysics Data System (ADS)

Kim, Won-Kyu; Kang, Sang-Woo; Rhee, Shi-Woo; Lee, Nae-In; Lee, Jong-Ho; Kang, Ho-Kyu

2002-11-01

Atomic layer chemical vapor deposition of zirconium silicate films with a precursor combination of ZrCl4 and tetra-n-butyl orthosilicate (TBOS) was studied for high dielectric gate insulators. The effect of deposition conditions, such as deposition temperature, pulse time for purge and precursor injection on the deposition rate per cycle, and composition of the film were studied. At 400 °C, the growth rate saturated to 1.35 Å/cycle above 500 sccm of the argon purge flow rate. The growth rate, composition ratio ((Zr/Zr+Si)), and impurity contents (carbon and chlorine) saturated with the increase of the injection time of ZrCl4 and TBOS and decreased with the increased deposition temperature from 300 to 500 °C. The growth rate, composition ratio, carbon, and chlorine contents of the Zr silicate thin films deposited at 500 °C were 1.05 Å/cycle, 0.23, 1.1 at. %, and 2.1 at. %, respectively. It appeared that by using only zirconium chloride and silicon alkoxide sources, the content of carbon and chlorine impurities could not be lowered below 1%. It was also found that the incorporation rate of metal from halide source was lower than alkoxide source.

A combined arc-melting and tilt-casting furnace for the manufacture of high-purity bulk metallic glass materials.

PubMed

Soinila, E; Pihlajamäki, T; Bossuyt, S; Hänninen, H

2011-07-01

An arc-melting furnace which includes a tilt-casting facility was designed and built, for the purpose of producing bulk metallic glass specimens. Tilt-casting was chosen because reportedly, in combination with high-purity processing, it produces the best fatigue endurance in Zr-based bulk metallic glasses. Incorporating the alloying and casting facilities in a single piece of equipment reduces the amount of laboratory space and capital investment needed. Eliminating the sample transfer step from the production process also saves time and reduces sample contamination. This is important because the glass forming ability in many alloy systems, such as Zr-based glass-forming alloys, deteriorates rapidly with increasing oxygen content of the specimen. The challenge was to create a versatile instrument, in which high purity conditions can be maintained throughout the process, even when melting alloys with high affinity for oxygen. Therefore, the design provides a high-vacuum chamber to be filled with a low-oxygen inert atmosphere, and takes special care to keep the system hermetically sealed throughout the process. In particular, movements of the arc-melting electrode and sample manipulator arm are accommodated by deformable metal bellows, rather than sliding O-ring seals, and the whole furnace is tilted for tilt-casting. This performance of the furnace is demonstrated by alloying and casting Zr(55)Cu(30)Al(10)Ni(5) directly into rods up to ø 10 mm which are verified to be amorphous by x-ray diffraction and differential scanning calorimetry, and to exhibit locally ductile fracture at liquid nitrogen temperature.

Effect of shock pressure on the structure and superconducting properties of Y-Ba-Cu-O in explosively fabricated bulk metal-matrix composites

NASA Technical Reports Server (NTRS)

Murr, L. E.; Niou, C. S.; Pradhan-Advani, M.

1991-01-01

While it is now well established that copper-oxide-based power, or virtually any other ceramic superconductor powder, can be consolidated and encapsulated within a metal matrix by explosive consolidation, the erratic superconductivity following fabrication has posed a major problem for bulk applications. The nature of this behavior was found to arise from microstructural damage created in the shock wave front, and the residual degradation in superconductivity was demonstrated to be directly related to the peak shock pressure. The explosively fabricated or shock loaded YBa2Cu3Ox examples exhibit drastically altered rho (or R) - T curves. The deterioration in superconductivity is even more noticeable in the measurement of ac magnetic susceptibility and flux exclusion or shielding fraction which is also reduced in proportion to increasing peak shock pressure. The high frequency surface resistance (in the GHz range) is also correspondingly compromised in explosively fabricated, bulk metal-matrix composites based on YBa2Cu3O7. Transmission electron microscopy (including lattice imaging techniques) is being applied in an effort to elucidate the fundamental (microstructural) nature of the shock-induced degradation of superconductivity and normal state conductivity. One focus of TEM observations has assumed that oxygen displaced from b-chains rather than oxygen-vacancy disorder in the basal plane of oxygen deficient YBa2Cu3Ox may be a prime mechanism. Shock-wave displaced oxygen may also be locked into new positions or interstitial clusters or chemically bound to displaced metal (possibly copper) atoms to form precipitates, or such displacements may cause the equivalent of local lattice cell changes as a result of stoichiometric changes. While the shock-induced suppression of T(sub c) is not desirable in the explosive fabrication of bulk metal-matrix superconductors, it may be turned into an advantage if the atomic-scale distortion can be understood and controlled as local

Effect of shock pressure on the structure and superconducting properties of Y-Ba-Cu-O in explosively fabricated bulk metal-matrix composites

NASA Technical Reports Server (NTRS)

Murr, L. E.; Niou, C. S.; Pradhan, M.; Schoenlein, L. H.

1990-01-01

While it is now well established that copper-oxide-based powder, or virtually any other ceramic superconductor powder, can be consolidated and encapsulated within a metal matrix by explosive consolidation, the erratic superconductivity following fabrication has posed a major problem for bulk applications. The nature of this behavior was found to arise from microstructural damage created in the shock wave front, and the residual degradation in superconductivity was demonstrated to be directly related to the peak shock pressure. The explosively fabricated or shock loaded YBa2Cu3Ox examples exhibit drastically altered rho (or R) - T curves. The deterioration in superconductivity is even more noticeable in the measurement of ac magnetic susceptibility and flux exclusion or shielding fraction which is also reduced in proportion to increasing peak shock pressure. The high-frequency surface resistance (in the GHz range) is also correspondingly compromised in explosively fabricated, bulk metal-matrix composites based on YBa2Cu3O7. Transmission electron microscopy (including lattice imaging techniques) is being applied in an effort to elucidate the fundamental (microstructural) nature of the shock-induced degradation of superconductivity and normal state conductivity. One focus of TEM observations has assumed that oxygen displaced from b-chains rather than oxygen-vacancy disorder in the basal plane of oxygen deficient YBa2Cu3Ox may be a prime mechanism. Shock-wave displaced oxygen may also be locked into new positions or interstitial clusters or chemically bound to displaced metal (possibly copper) atoms to form precipitates, or such displacements may cause the equivalent of local lattice cell changes as a result of stoichiometric changes. While the shock-induced suppression of T(sub c) is not desirable in the explosive fabrication of bulk metal-matrix superconductors, it may be turned into an advantage if the atomic-scale distortion can be understood and controlled as

PRODUCTION OF METALS

DOEpatents

Spedding, F.H.; Wilhelm, H.A.; Keller, W.H.

1961-09-19

A process is described producing metallic thorium, titanium, zirconium, or hafnium from the fluoride. In the process, the fluoride is reduced with alkali or alkaline earth metal and a booster compound (e.g. iodine or a decomposable oxysalt) in a sealed bomb at superatmospheric pressure and a temperature above the melting point of the metal to be produced.

Cavity resonator for dielectric measurements of high-ɛ, low loss materials, demonstrated with barium strontium zirconium titanate ceramics

NASA Astrophysics Data System (ADS)

Marksteiner, Quinn R.; Treiman, Michael B.; Chen, Ching-Fong; Haynes, William B.; Reiten, M. T.; Dalmas, Dale; Pulliam, Elias

2017-06-01

A resonant cavity method is presented which can measure loss tangents and dielectric constants for materials with dielectric constant from 150 to 10 000 and above. This practical and accurate technique is demonstrated by measuring barium strontium zirconium titanate bulk ferroelectric ceramic blocks. Above the Curie temperature, in the paraelectric state, barium strontium zirconium titanate has a sufficiently low loss that a series of resonant modes are supported in the cavity. At each mode frequency, the dielectric constant and loss tangent are obtained. The results are consistent with low frequency measurements and computer simulations. A quick method of analyzing the raw data using the 2D static electromagnetic modeling code SuperFish and an estimate of uncertainties are presented.

Impedance spectroscopy of water soluble resin modified by zirconium sulphate

NASA Astrophysics Data System (ADS)

Joseph, Anandraj; Joshi, Girish M.

2018-04-01

We successfully modified water soluble resin polyvinyl alcohol (PVA) by loading zirconium sulphate (ZrSO4). We demonstrated the measurement of electrical properties by using impedance analyser across frequency range (10 Hz-1 MHz) and the temperature range of (30°C to 150°C). The impedance spectroscopy demonstrates decrease in bulk resistance as a function of temperature loading of zirconia 2.5 wt. %. Increase in AC (10-5 S/cm and DC conductivity (10- 2 S/m) observed due to ionic contribution of zirconia. However, the electrical properties of PVA/ZrSO4 composite useful to develop battery electrolyte applications.

Copper-acrylic enamel serves as lubricant for cold drawing of refractory metals

NASA Technical Reports Server (NTRS)

Beane, C.; Karasek, F.

1966-01-01

Acrylic enamel spray containing metallic copper pigment lubricates refractory metal tubing during cold drawing operations so that the tubing surface remains free from scratches and nicks and does not seize in the die. Zirconium alloys, zirconium, tantalum alloys, niobium alloys, vanandium alloys and titanium alloys have been drawn using this lubricant.

Three-dimensional ordered titanium dioxide-zirconium dioxide film-based microfluidic device for efficient on-chip phosphopeptide enrichment.

PubMed

Zhao, De; He, Zhongyuan; Wang, Gang; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang

2016-09-15

Microfluidic technology plays a significant role in separating biomolecules, because of its miniaturization, integration, and automation. Introducing micro/nanostructured functional materials can improve the properties of microfluidic devices, and extend their application. Inverse opal has a three-dimensional ordered net-like structure. It possesses a large surface area and exhibits good mass transport, making it a good candidate for bio-separation. This study exploits inverse opal titanium dioxide-zirconium dioxide films for on-chip phosphopeptide enrichment. Titanium dioxide-zirconium dioxide inverse opal film-based microfluidic devices were constructed from templates of 270-, 340-, and 370-nm-diameter poly(methylmethacrylate) spheres. The phosphopeptide enrichments of these devices were determined by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. The device constructed from the 270-nm-diameter sphere template exhibited good comprehensive phosphopeptide enrichment, and was the best among these three devices. Because the size of opal template used in construction was the smallest, the inverse opal film therefore had the smallest pore sizes and the largest surface area. Enrichment by this device was also better than those of similar devices based on nanoparticle films and single component films. The titanium dioxide-zirconium dioxide inverse opal film-based device provides a promising approach for the efficient separation of various biomolecules. Copyright © 2016 Elsevier Inc. All rights reserved.

Biocompatible Ni-free Zr-based bulk metallic glasses with high-Zr-content: compositional optimization for potential biomedical applications.

PubMed

Hua, Nengbin; Huang, Lu; Chen, Wenzhe; He, Wei; Zhang, Tao

2014-11-01

The present study designs and prepares Ni-free Zr60+xTi2.5Al10Fe12.5-xCu10Ag5 (at.%, x=0, 2.5, 5) bulk metallic glasses (BMGs) by copper mold casting for potential biomedical application. The effects of Zr content on the in vitro biocompatibility of the Zr-based BMGs are evaluated by investigating mechanical properties, bio-corrosion behavior, and cellular responses. It is found that increasing the content of Zr is favorable for the mechanical compatibility with a combination of low Young's modulus, large plasticity, and high notch toughness. Electrochemical measurements demonstrate that the Zr-based BMGs are corrosion resistant in a phosphate buffered saline solution. The bio-corrosion resistance of BMGs is improved with the increase in Zr content, which is attributed to the enrichment in Zr and decrease in Al concentration in the surface passive film of alloys. Regular cell responses of mouse MC3T3-E1 cells, including cell adhesion and proliferation, are observed on the Zr-Ti-Al-Fe-Cu-Ag BMGs, which reveals their general biosafety. The high-Zr-based BMGs exhibit a higher cell proliferation activity in comparison with that of pure Zr and Ti-6Al-4V alloy. The effects of Zr content on the in vitro biocompatibility can be used to guide the future design of biocompatible Zr-based BMGs. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of High Strength Ni-Cu-Zr-Ti-Si-Sn In-Situ Bulk Metallic Glass Composites Reinforced by Hard B2 Phase

NASA Astrophysics Data System (ADS)

Park, Hyo Jin; Hong, Sung Hwan; Park, Hae Jin; Kim, Young Seok; Kim, Jeong Tae; Na, Young Sang; Lim, Ka Ram; Wang, Wei-Min; Kim, Ki Buem

2018-03-01

In the present study, the influence of atomic ratio of Zr to Ti on the microstructure and mechanical properties of Ni-Cu-Zr-Ti-Si-Sn alloys is investigated. The alloys were designed by fine replacement of Ti for Zr from Ni39Cu20Zr36-xTixSi2Sn3. The increase of Ti content enhances glass forming ability of the alloy by suppression of formation of (Ni, Cu)10(Zr, Ti)7 phase during solidification. With further increasing Ti content up to 24 at.%, the B2 phase is introduced in the amorphous matrix with a small amount of B19' phase from alloy melt. The bulk metallic glass composite containing B2 phase with a volume fraction of 10 vol% exhibits higher fracture strength ( 2.5 GPa) than that of monolithic bulk metallic glass ( 2.3 GPa). This improvement is associated to the individual mechanical characteristics of the B2 phase and amorphous matrix. The B2 phase exhibits higher hardness and modulus than those of amorphous matrix as well as effective stress accommodation up to the higher stress level than the yield strength of amorphous matrix. The large stress accommodation capacity of the hard B2 phase plays an important factor to improve the mechanical properties of in situ Ni-based bulk metallic glass composites.

Capture of Tritium Released from Cladding in the Zirconium Recycle Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, Barry B.; Walker, T. B.; Bruffey, S. H.

2016-08-31

Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-based cladding and could be released from the cladding when themore » solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using nonradioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.« less

Efficiency and Accuracy in Thermal Simulation of Powder Bed Fusion of Bulk Metallic Glass

NASA Astrophysics Data System (ADS)

Lindwall, J.; Malmelöv, A.; Lundbäck, A.; Lindgren, L.-E.

2018-05-01

Additive manufacturing by powder bed fusion processes can be utilized to create bulk metallic glass as the process yields considerably high cooling rates. However, there is a risk that reheated material set in layers may become devitrified, i.e., crystallize. Therefore, it is advantageous to simulate the process to fully comprehend it and design it to avoid the aforementioned risk. However, a detailed simulation is computationally demanding. It is necessary to increase the computational speed while maintaining accuracy of the computed temperature field in critical regions. The current study evaluates a few approaches based on temporal reduction to achieve this. It is found that the evaluated approaches save a lot of time and accurately predict the temperature history.

SEPARATION OF HAFNIUM FROM ZIRCONIUM

DOEpatents

Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

1960-05-31

The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

Zirconium

USGS Publications Warehouse

Bedinger, G.M.

2013-01-01

Zirconium is the 20th most abundant element in the Earth’s crust. It occurs in a variety of rock types and geologic environments but most often in igneous rocks in the form of zircon (ZrSiO4). Zircon is recovered as a coproduct of the mining and processing of heavy mineral sands for the titanium minerals ilmenite and rutile. The sands are formed by the weathering and erosion of rock containing zircon and titanium heavy minerals and their subsequent concentration in sedimentary systems, particularly in coastal environments. A small quantity of zirconium, less than 10 kt/a (11,000 stpy), compared with total world production of 1.4 Mt (1.5 million st) in 2012, was derived from the mineral baddeleyite (ZrO2), produced from a single source in Kovdor, Russia.

Mechanical, electronic, and thermodynamic properties of zirconium carbide from first-principles calculations

NASA Astrophysics Data System (ADS)

Yang, Xiao-Yong; Lu, Yong; Zheng, Fa-Wei; Zhang, Ping

2015-11-01

Mechanical, electronic, and thermodynamic properties of zirconium carbide have been systematically studied using the ab initio calculations. The calculated equilibrium lattice parameter, bulk modulus, and elastic constants are all well consistent with the experimental data. The electronic band structure indicates that the mixture of C 2p and Zr 4d and 4p orbitals around the Fermi level makes a large covalent contribution to the chemical bonds between the C and Zr atoms. The Bader charge analysis suggests that there are about 1.71 electrons transferred from each Zr atom to its nearest C atom. Therefore, the Zr-C bond displays a mixed ionic/covalent character. The calculated phonon dispersions of ZrC are stable, coinciding with the experimental measurement. A drastic expansion in the volume of ZrC is seen with increasing temperature, while the bulk modulus decreases linearly. Based on the calculated phonon dispersion curves and within the quasi-harmonic approximation, the temperature dependence of the heat capacities is obtained, which gives a good description compared with the available experimental data. Project supported by the National Natural Science Foundation of China (Grant No. 51071032).

The electrochemical Evaluation of a Zr-Based Bulk Metallic Glass in a Phosphate-Buffered Saline Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrison, M. L.; Buchanan, R. A.; Leon, R. V.

2005-01-01

Bulk metallic glasses (BMGs) represent an emerging class of materials with an amorphous structure and a unique combination of properties. The objectives of this investigation were to define the electrochemical behavior of a specific Zr-based BMG alloy in a physiologically relevant environment and to compare these properties to standard, crystalline biomaterials as well as other Zr-based BMG compositions. Cyclic-anodic-polarization studies were conducted with a Zr{sub 52.5}Cu{sub 17.9}Ni{sub 14.6}Al{sub 10.0}Ti{sub 5.0} (at %) BMG in a phosphate-buffered saline electrolyte with a physiologically relevant oxygen content at 37 C. The results were compared to three common, crystalline biomaterials: CoCrMo, 316L stainless steel,more » and Ti-6Al-4V. The BMG alloy was found to have a lower corrosion penetration rate (CPR), as compared to the 316L stainless steel, and an equivalent CPR, as compared to the CoCrMo and Ti-6Al-4V alloys. Furthermore, the BMG alloy demonstrated better localized corrosion resistance than the 316L stainless steel. However, the localized corrosion resistance of the BMG alloy was not as high as those of the CoCrMo and Ti-6Al-4V alloys in the tested environment. The excellent electrochemical properties demonstrated by the BMG alloy are combined with a low modulus and unparalleled strength. This unique combination of properties dramatically demonstrates the potential for amorphous alloys as a new generation of biomaterials.« less

Fluorometric determination of zirconium in minerals

USGS Publications Warehouse

Alford, W.C.; Shapiro, L.; White, C.E.

1951-01-01

The increasing use of zirconium in alloys and in the ceramics industry has created renewed interest in methods for its determination. It is a common constituent of many minerals, but is usually present in very small amounts. Published methods tend to be tedious, time-consuming, and uncertain as to accuracy. A new fluorometric procedure, which overcomes these objections to a large extent, is based on the blue fluorescence given by zirconium and flavonol in sulfuric acid solution. Hafnium is the only element that interferes. The sample is fused with borax glass and sodium carbonate and extracted with water. The residue is dissolved in sulfuric acid, made alkaline with sodium hydroxide to separate aluminum, and filtered. The precipitate is dissolved in sulfuric acid and electrolysed in a Melaven cell to remove iron. Flavonol is then added and the fluorescence intensity is measured with a photo-fluorometer. Analysis of seven standard mineral samples shows excellent results. The method is especially useful for minerals containing less than 0.25% zirconium oxide.

Polyamorphism in Yb-based metallic glass induced by pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Liangliang; Luo, Qiang; Li, Renfeng

2017-04-25

The Yb 62.5Zn 15Mg 17.5Cu 5 metallic glass is investigated using synchrotron x-ray total scattering method up to 38.4 GPa. The polyamorphic transformation from low density to high density with a transition region between 14.1 and 25.2 GPa is observed, accompanying with a volume collapse reflected by a discontinuousness of isothermal bulk modulus. This collapse is caused by that distortional icosahedron short range order precedes to perfect icosahedron, which might link to Yb 4f electron delocalization upon compression, and match the result of in situ electrical resistance measurement under high pressure conditions. Furthermore, this discovery in Yb-based metallic glass, combinedmore » with the previous reports on other metallic glass systems, demonstrates that pressure induced polyamorphism is the general behavior for typical lanthanide based metallic glasses.« less

Detoxification of Chemical Warfare Agents Using a Zr6 -Based Metal-Organic Framework/Polymer Mixture.

PubMed

Moon, Su-Young; Proussaloglou, Emmanuel; Peterson, Gregory W; DeCoste, Jared B; Hall, Morgan G; Howarth, Ashlee J; Hupp, Joseph T; Farha, Omar K

2016-10-10

Owing to their high surface area, periodic distribution of metal sites, and water stability, zirconium-based metal-organic frameworks (Zr 6 -MOFs) have shown promising activity for the hydrolysis of nerve agents GD and VX, as well as the simulant, dimethyl 4-nitrophenylphosphate (DMNP), in buffered solutions. A hurdle to using MOFs for this application is the current need for a buffer solution. Here the destruction of the simulant DMNP, as well as the chemical warfare agents (GD and VX) through hydrolysis using a MOF catalyst mixed with a non-volatile, water-insoluble, heterogeneous buffer is reported. The hydrolysis of the simulant and nerve agents in the presence of the heterogeneous buffer was fast and effective. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of Structural Relaxation Behavior in As-Cast and Pre-Annealed Zr-Based Bulk Metallic Glasses Just below Glass Transition

DOE PAGES

Haruyama, Osami; Yoshikawa, Kazuyoshi; Yamazaki, Yoshikatsu; ...

2015-04-25

In this paper, the α-relaxation of pre-annealed Zr 55Cu 30Ni 5Al 10 bulk metallic glasses (BMGs) was compared with that of as-cast Zr-based BMGs including Zr 55Cu 30Ni 5Al 10. The α-relaxation was investigated by volume relaxation. The relaxation behavior was well described by a stretched exponential relaxation function, Φ (t) ≈ exp [ - (t/τ α ) β α ], with the isothermal relaxation time, τ α, and the Kohlrausch exponent, β α. The β α exhibited the strong temperature dependence for the pre-annealed BMG, while the weak temperature dependence was visualized for the as-cast BMG similar to themore » dynamic relaxation. The τ α’s were modified by Moynihan and Narayanaswamy-Tool-Moynihan methods that reduce the difference in the thermal history of sample. Finally, as a result, the relaxation kinetics in the glass resembled that of a liquid deduced from the behavior of viscosity in the supercooled liquid.« less

The Study of Titanium and Zirconium Ions in Water by MPT-LTQ Mass Spectrometry in Negative Mode

PubMed Central

Yang, Junqing; Zheng, Mei; Liu, Qiuju; Zhu, Meiling; Yang, Chushan; Zhang, Yan; Zhu, Zhiqiang

2017-01-01

Microwave plasma torches (MPTs) can be used as simple and low power-consumption ambient ion sources. When MPT-mass spectrometry (MPT-MS) is applied in the detection of some metal elements, the metallic ions exhibit some novel features which are significantly different with those obtained by the traditional inductively coupled plasma (ICP)-mass spectrometry (ICP-MS) and may be helpful for metal element analysis. As the representative elements of group IVA, titanium and zirconium are both of importance and value in modern industry, and they have impacts on human health. Here, we first provide a study on the complex anions of titanium and zirconium in water by using the MPT as ion source and a linear ion trap mass spectrometer (LTQ-MS). These complex anions were produced in the plasma flame by an aqueous solution flowing through the central tube of the MPT, and were introduced into the inlet of the mass spectrometry working in negative ion mode to get the feature mass spectrometric signals. Moreover, the feature fragment patterns of these ions in multi-step collision- induced dissociation processes have been explained. Under the optimized conditions, the limit of detection (LOD) using the MS2 (the second tandem mass spectrometry) procedure was estimated to be at the level of 10 μg/L for titanium and 20 μg/L for zirconium with linear dynamics ranges that cover at least two orders of magnitude, i.e., between 0–500 μg/L and 20–200 μg/L, respectively. These experimental data demonstrated that the MPT-MS is a promising and useful tool in field analysis of titanium and zirconium ions in water, and can be applied in many fields, such as environmental control, hydrogeology, and water quality inspection. In addition, MPT-MS could also be used as a supplement of ICP-MS for the rapid and on-site analysis of metal ions. PMID:28954404

The Study of Titanium and Zirconium Ions in Water by MPT-LTQ Mass Spectrometry in Negative Mode.

PubMed

Yang, Junqing; Zheng, Mei; Liu, Qiuju; Yang, Meiling Zhu Chushan; Zhang, Yan; Zhu, Zhiqiang

2017-09-26

Microwave plasma torches (MPTs) can be used as simple and low power-consumption ambient ion sources. When MPT-mass spectrometry (MPT-MS) is applied in the detection of some metal elements, the metallic ions exhibit some novel features which are significantly different with those obtained by the traditional inductively coupled plasma (ICP)-mass spectrometry (ICP-MS) and may be helpful for metal element analysis. As the representative elements of group IVA, titanium and zirconium are both of importance and value in modern industry, and they have impacts on human health. Here, we first provide a study on the complex anions of titanium and zirconium in water by using the MPT as ion source and a linear ion trap mass spectrometer (LTQ-MS). These complex anions were produced in the plasma flame by an aqueous solution flowing through the central tube of the MPT, and were introduced into the inlet of the mass spectrometry working in negative ion mode to get the feature mass spectrometric signals. Moreover, the feature fragment patterns of these ions in multi-step collision- induced dissociation processes have been explained. Under the optimized conditions, the limit of detection (LOD) using the MS² (the second tandem mass spectrometry) procedure was estimated to be at the level of 10μg/L for titanium and 20 μg/L for zirconium with linear dynamics ranges that cover at least two orders of magnitude, i.e., between 0-500 μg/L and 20-200 μg/L, respectively. These experimental data demonstrated that the MPT-MS is a promising and useful tool in field analysis of titanium and zirconium ions in water, and can be applied in many fields, such as environmental control, hydrogeology, and water quality inspection. In addition, MPT-MS could also be used as a supplement of ICP-MS for the rapid and on-site analysis of metal ions.

40 CFR 721.9973 - Zirconium dichlorides (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Zirconium dichlorides (generic). 721... Substances § 721.9973 Zirconium dichlorides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as zirconium dichlorides (PMNs P...

Amperometric Biosensor Based on Zirconium Oxide/Polyethylene Glycol/Tyrosinase Composite Film for the Detection of Phenolic Compounds

PubMed Central

Ahmad, Nor Monica; Abdullah, Jaafar; Yusof, Nor Azah; Ab Rashid, Ahmad Hazri; Abd Rahman, Samsulida; Hasan, Md. Rakibul

2016-01-01

A phenolic biosensor based on a zirconium oxide/polyethylene glycol/tyrosinase composite film for the detection of phenolic compounds has been explored. The formation of the composite film was expected via electrostatic interaction between hexacetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and zirconium oxide nanoparticles casted on screen printed carbon electrode (SPCE). Herein, the electrode was treated by casting hexacetyltrimethylammonium bromide on SPCE to promote a positively charged surface. Later, zirconium oxide was mixed with polyethylene glycol and the mixture was dropped cast onto the positively charged SPCE/CTAB. Tyrosinase was further immobilized onto the modified SPCE. Characterization of the prepared nanocomposite film and the modified SPCE surface was investigated by scanning electron microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), and Cyclic voltamogram (CV). The developed biosensor exhibits rapid response for less than 10 s. Two linear calibration curves towards phenol in the concentrations ranges of 0.075–10 µM and 10–55 µM with the detection limit of 0.034 µM were obtained. The biosensor shows high sensitivity and good storage stability for at least 30 days. PMID:27367738

Amperometric Biosensor Based on Zirconium Oxide/Polyethylene Glycol/Tyrosinase Composite Film for the Detection of Phenolic Compounds.

PubMed

Ahmad, Nor Monica; Abdullah, Jaafar; Yusof, Nor Azah; Ab Rashid, Ahmad Hazri; Abd Rahman, Samsulida; Hasan, Md Rakibul

2016-06-29

A phenolic biosensor based on a zirconium oxide/polyethylene glycol/tyrosinase composite film for the detection of phenolic compounds has been explored. The formation of the composite film was expected via electrostatic interaction between hexacetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and zirconium oxide nanoparticles casted on screen printed carbon electrode (SPCE). Herein, the electrode was treated by casting hexacetyltrimethylammonium bromide on SPCE to promote a positively charged surface. Later, zirconium oxide was mixed with polyethylene glycol and the mixture was dropped cast onto the positively charged SPCE/CTAB. Tyrosinase was further immobilized onto the modified SPCE. Characterization of the prepared nanocomposite film and the modified SPCE surface was investigated by scanning electron microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), and Cyclic voltamogram (CV). The developed biosensor exhibits rapid response for less than 10 s. Two linear calibration curves towards phenol in the concentrations ranges of 0.075-10 µM and 10-55 µM with the detection limit of 0.034 µM were obtained. The biosensor shows high sensitivity and good storage stability for at least 30 days.

Atomic-scale bonding of bulk metallic glass to crystalline aluminum

NASA Astrophysics Data System (ADS)

Liu, K. X.; Liu, W. D.; Wang, J. T.; Yan, H. H.; Li, X. J.; Huang, Y. J.; Wei, X. S.; Shen, J.

2008-08-01

A Ti40Zr25Cu12Ni3Be20 bulk metallic glass (BMG) was welded to a crystalline aluminum by the parallel plate explosive welding method. Experimental evidence and numerical simulation show that atomic-scale bonding between the BMG and the crystalline aluminum can be achieved, and the weldment on the BMG side can retain its amorphous state without any indication of crystallization in the welding process. Nanoindentation tests reveal that the interface of the explosive joints exhibits a significant increase in hardness compared to the matrix on its two sides. The joining of BMG and crystalline materials opens a window to the applications of BMGs in engineering.

Phonon dispersion relation of Mg-Cu-Gd bulk metallic glasses

NASA Astrophysics Data System (ADS)

Suthar, P. H.

2016-05-01

Collective dynamics and elastic constants of bulk metallic glasses Mg65Cu25Gd10 and Mg60Cu25Gd15 are computed using the Hubbard -Beeby approach and our well recognized model potential. The important ingredients in the present study are the pair potential and local field correction functions (LFCF). The local field correction functions due to Hartree (H), Farid et al (F) and Sarkar Sen et al (S) are employed to investigation the influence of the screening effects on the longitudinal and traversed of phonon modes of glassy system. The results for the elastic constants are found to be in good agreement with experimental data.

Local melting to design strong and plastically deformable bulk metallic glass composites

PubMed Central

Qin, Yue-Sheng; Han, Xiao-Liang; Song, Kai-Kai; Tian, Yu-Hao; Peng, Chuan-Xiao; Wang, Li; Sun, Bao-An; Wang, Gang; Kaban, Ivan; Eckert, Jürgen

2017-01-01

Recently, CuZr-based bulk metallic glass (BMG) composites reinforced by the TRIP (transformation-induced plasticity) effect have been explored in attempt to accomplish an optimal of trade-off between strength and ductility. However, the design of such BMG composites with advanced mechanical properties still remains a big challenge for materials engineering. In this work, we proposed a technique of instantaneously and locally arc-melting BMG plate to artificially induce the precipitation of B2 crystals in the glassy matrix and then to tune mechanical properties. Through adjusting local melting process parameters (i.e. input powers, local melting positions, and distances between the electrode and amorphous plate), the size, volume fraction, and distribution of B2 crystals were well tailored and the corresponding formation mechanism was clearly clarified. The resultant BMG composites exhibit large compressive plasticity and high strength together with obvious work-hardening ability. This compelling approach could be of great significance for the steady development of metastable CuZr-based alloys with excellent mechanical properties. PMID:28211890

Dynamic mechanical properties of a Ti-based metallic glass matrix composite

NASA Astrophysics Data System (ADS)

Li, Jinshan; Cui, Jing; Qiao, Jichao; Bai, Jie; Kou, Hongchao; Wang, Jun

2015-04-01

Dynamic mechanical behavior of a Ti50Zr20Nb12Cu5Be13 bulk metallic glass composite was investigated using mechanical spectroscopy in both temperature and frequency domains. Storage modulus G' and loss modulus G″ are determined by temperature, and three distinct regions corresponding to different states in the bulk metallic glass composite are characterized. Physical parameters, such as atomic mobility and correlation factor χ, are introduced to analyze dynamic mechanical behavior of the bulk metallic glass composite in the framework of quasi-point defects (QPD) model. The experimental results are in good agreement with the prediction of QPD model.

Numerical comparison of hydrogen desorption behaviors of metal hydride beds based on uranium and on zirconium-cobalt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyoung, S.; Yoo, H.; Ju, H.

2015-03-15

In this paper, the hydrogen delivery capabilities of uranium (U) and zirconium-cobalt (ZrCo) are compared quantitatively in order to find the optimum getter materials for tritium storage. A three-dimensional hydrogen desorption model is applied to two identically designed cylindrical beds with the different materials, and hydrogen desorption simulations are then conducted. The simulation results show superior hydrogen delivery performance and easier thermal management capability for the U bed. This detailed analysis of the hydrogen desorption behaviors of beds with U and ZrCo will help to identify the optimal bed material, bed design, and operating conditions for the storage and deliverymore » system in ITER. (authors)« less

Graphene-based topological insulator with an intrinsic bulk band gap above room temperature.

PubMed

Kou, Liangzhi; Yan, Binghai; Hu, Feiming; Wu, Shu-Chun; Wehling, Tim O; Felser, Claudia; Chen, Changfeng; Frauenheim, Thomas

2013-01-01

Topological insulators (TIs) represent a new quantum state of matter characterized by robust gapless states inside the insulating bulk gap. The metallic edge states of a two-dimensional (2D) TI, known as the quantum spin Hall (QSH) effect, are immune to backscattering and carry fully spin-polarized dissipationless currents. However, existing 2D TIs realized in HgTe and InAs/GaSb suffer from small bulk gaps (<10 meV) well below room temperature, thus limiting their application in electronic and spintronic devices. Here, we report a new 2D TI comprising a graphene layer sandwiched between two Bi2Se3 slabs that exhibits a large intrinsic bulk band gap of 30-50 meV, making it viable for room-temperature applications. Distinct from previous strategies for enhancing the intrinsic spin-orbit coupling effect of the graphene lattice, the present graphene-based TI operates on a new mechanism of strong inversion between graphene Dirac bands and Bi2Se3 conduction bands. Strain engineering leads to effective control and substantial enhancement of the bulk gap. Recently reported synthesis of smooth graphene/Bi2Se3 interfaces demonstrates the feasibility of experimental realization of this new 2D TI structure, which holds great promise for nanoscale device applications.

RECYCLING A NONIONIC AQUEOUS-BASED METAL-CLEANING SOLUTION WITH A CERAMIC MEMBRANE: PILOT SCALE EVALUATION

EPA Science Inventory

The effectiveness of a zirconium dioxide (ZrO2) membrane filter was evaluated for recycling a nonionic aqueous metal cleaning bath under real-world conditions. The pilot-scale study consisted of four 7- to 16-day filtration runs, each processed a portion of the cleaning bath duri...

Determination of bulk and interface density of states in metal oxide semiconductor thin-film transistors by using capacitance-voltage characteristics

NASA Astrophysics Data System (ADS)

Wei, Xixiong; Deng, Wanling; Fang, Jielin; Ma, Xiaoyu; Huang, Junkai

2017-10-01

A physical-based straightforward extraction technique for interface and bulk density of states in metal oxide semiconductor thin film transistors (TFTs) is proposed by using the capacitance-voltage (C-V) characteristics. The interface trap density distribution with energy has been extracted from the analysis of capacitance-voltage characteristics. Using the obtained interface state distribution, the bulk trap density has been determined. With this method, for the interface trap density, it is found that deep state density nearing the mid-gap is approximately constant and tail states density increases exponentially with energy; for the bulk trap density, it is a superposition of exponential deep states and exponential tail states. The validity of the extraction is verified by comparisons with the measured current-voltage (I-V) characteristics and the simulation results by the technology computer-aided design (TCAD) model. This extraction method uses non-numerical iteration which is simple, fast and accurate. Therefore, it is very useful for TFT device characterization.

Investigation of fatigue strength of tool steels in sheet-bulk metal forming

NASA Astrophysics Data System (ADS)

Pilz, F.; Gröbel, D.; Merklein, M.

2018-05-01

To encounter trends regarding an efficient production of complex functional components in forming technology, the process class of sheet-bulk metal forming (SBMF) can be applied. SBMF is characterized by the application of bulk forming operations on sheet metal, often in combination with sheet forming operations [1]. The combination of these conventional process classes leads to locally varying load conditions. The resulting load conditions cause high tool loads, which lead to a reduced tool life, and an uncontrolled material flow. Several studies have shown that locally modified tool surfaces, so-called tailored surfaces, have the potential to control the material flow and thus to increase the die filling of functional elements [2]. A combination of these modified tool surfaces and high tool loads in SBMF is furthermore critical for the tool life and leads to fatigue. Tool fatigue is hardly predictable and due to a lack of data [3], a challenge in tool design. Thus, it is necessary to provide such data for tool steels used in SBMF. The aim of this study is the investigation of the influence of tailored surfaces on the fatigue strength of the powder metallurgical tool steel ASP2023 (1.3344, AISI M3:2), which is typically used in cold forging applications, with a hardness 60 HRC ± 1 HRC. To conduct this investigation, the rotating bending test is chosen. As tailored surfaces, a DLC-coating and a surface manufactured by a high-feed-milling process are chosen. As reference a polished surface which is typical for cold forging tools is used. Before the rotating bending test, the surface integrity is characterized by measuring topography and residual stresses. After testing, the determined values of the surface integrity are correlated with the reached fracture load cycle to derive functional relations. Based on the gained results the investigated tailored surfaces are evaluated regarding their feasibility to modify tool surfaces within SBMF.

Digital data acquisition for a CAD/CAM-fabricated titanium framework and zirconium oxide restorations for an implant-supported fixed complete dental prosthesis.

PubMed

Lin, Wei-Shao; Metz, Michael J; Pollini, Adrien; Ntounis, Athanasios; Morton, Dean

2014-12-01

This dental technique report describes a digital workflow with digital data acquisition at the implant level, computer-aided design and computer-aided manufacturing fabricated, tissue-colored, anodized titanium framework, individually luted zirconium oxide restorations, and autopolymerizing injection-molded acrylic resin to fabricate an implant-supported, metal-ceramic-resin fixed complete dental prosthesis in an edentulous mandible. The 1-step computer-aided design and computer-aided manufacturing fabrication of titanium framework and zirconium oxide restorations can provide a cost-effective alternative to the conventional metal-resin fixed complete dental prosthesis. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Method of making metal matrix composites reinforced with ceramic particulates

DOEpatents

Cornie, James A.; Kattamis, Theodoulos; Chambers, Brent V.; Bond, Bruce E.; Varela, Raul H.

1989-01-01

Composite materials and methods for making such materials are disclosed in which dispersed ceramic particles are at chemical equilibrium with a base metal matrix, thereby permitting such materials to be remelted and subsequently cast or otherwise processed to form net weight parts and other finished (or semi-finished) articles while maintaining the microstructure and mechanical properties (e.g. wear resistance or hardness) of the original composite. The composite materials of the present invention are composed of ceramic particles in a base metal matrix. The ceramics are preferably carbides of titanium, zirconium, tungsten, molybdenum or other refractory metals. The base metal can be iron, nickel, cobalt, chromium or other high temperature metal and alloys thereof. For ferrous matrices, alloys suitable for use as the base metal include cast iron, carbon steels, stainless steels and iron-based superalloys.

Method of making metal matrix composites reinforced with ceramic particulates

DOEpatents

Cornie, J.A.; Kattamis, T.; Chambers, B.V.; Bond, B.E.; Varela, R.H.

1989-08-01

Composite materials and methods for making such materials are disclosed in which dispersed ceramic particles are at chemical equilibrium with a base metal matrix, thereby permitting such materials to be remelted and subsequently cast or otherwise processed to form net weight parts and other finished (or semi-finished) articles while maintaining the microstructure and mechanical properties (e.g. wear resistance or hardness) of the original composite. The composite materials of the present invention are composed of ceramic particles in a base metal matrix. The ceramics are preferably carbides of titanium, zirconium, tungsten, molybdenum or other refractory metals. The base metal can be iron, nickel, cobalt, chromium or other high temperature metal and alloys thereof. For ferrous matrices, alloys suitable for use as the base metal include cast iron, carbon steels, stainless steels and iron-based superalloys. 2 figs.

Layer Protecting the Surface of Zirconium Used in Nuclear Reactors.

PubMed

Ashcheulov, Petr; Skoda, Radek; Skarohlíd, Jan; Taylor, Andrew; Fendrych, Frantisek; Kratochvílová, Irena

2016-01-01

significantly prolong lifetime of Zirconium alloy in nuclear reactors even above Zirconium phase transition temperatures. Even after ion beam irradiation (10 dpa, 3 MeV Fe(2+)) the diamond film still shows satisfactory structural integrity with both sp(3) and sp(2) carbon phases. Zircaloy2 under the carbon-based protective layer after hot steam oxidation test differed from the original Zircaloy2 material composition only very slightly, proving that the diamond coating increases the material resistance to high temperature oxidation. Zirconium alloys nuclear fuel pins' surfaces were covered by compact and homogeneous polycrystalline diamond layers consisting of sp(3) and sp(2) carbon phases with a high crystalline diamond content and low roughness. Diamond withstands very high temperatures, has excellent thermal conductivity and low chemical reactivity, it does not degrade over time and (important for the nuclear fuel cladding) being pure carbon, it has perfect neutron cross-section properties. Moreover, polycrystalline diamond layers consisting of crystalline (sp(3)) and amorphous (sp(2)) carbon phases could have suitable thermal expansion. Zirconium alloys coated with polycrystalline diamond film are protected against undesirable changes and processes. Further, the polycrystalline diamond layer prevents the reaction between the alloy surface and water vapor. During such reaction, water molecules dissociate and initiate formation of zirconium dioxide and hydrogen, accompanied by the release of large amount of heat. Thus the protective layer prevents the formation of hydrogen and the release of reaction heat. Few relevant patents to the topic have been reviewed and cited.

Dynamic mechanical properties of a Ti-based metallic glass matrix composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jinshan, E-mail: ljsh@nwpu.edu.cn; Cui, Jing; Bai, Jie

2015-04-21

Dynamic mechanical behavior of a Ti{sub 50}Zr{sub 20}Nb{sub 12}Cu{sub 5}Be{sub 13} bulk metallic glass composite was investigated using mechanical spectroscopy in both temperature and frequency domains. Storage modulus G′ and loss modulus G″ are determined by temperature, and three distinct regions corresponding to different states in the bulk metallic glass composite are characterized. Physical parameters, such as atomic mobility and correlation factor χ, are introduced to analyze dynamic mechanical behavior of the bulk metallic glass composite in the framework of quasi-point defects (QPD) model. The experimental results are in good agreement with the prediction of QPD model.

Zn(2+)-Triggered Drug Release from Biocompatible Zirconium MOFs Equipped with Supramolecular Gates.

PubMed

Tan, Li-Li; Li, Haiwei; Zhou, Yue; Zhang, Yuanyuan; Feng, Xiao; Wang, Bo; Yang, Ying-Wei

2015-08-01

A new theranostic nanoplatform, comprising of monodisperse zirconium metal-organic frameworks (MOFs) as drug carriers and carboxylatopillar[5]arene-based supramolecular switches as gating entities, is constructed, and controlled drug release triggered by bio-friendly Zn(2+) ions (abundant in synaptic vesicles) and auxiliary thermal stimulus is realized. This on-command drug delivery system exhibits large pore sizes for drug encapsulation, excellent biodegradability and biocompatibility, extremely low cytotoxicity and premature drug release, and superior dual-stimuli responsiveness, opening a new avenue in targeted drug delivery and controlled release of therapeutic agents, especially in the treatment of central nervous system diseases. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intercalation chemistry of zirconium 4-sulfophenylphosphonate

NASA Astrophysics Data System (ADS)

Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

2013-12-01

Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4‧-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules.

Modeling deformation behavior of Cu-Zr-Al bulk metallic glass matrix composites

NASA Astrophysics Data System (ADS)

Pauly, S.; Liu, G.; Wang, G.; Das, J.; Kim, K. B.; Kühn, U.; Kim, D. H.; Eckert, J.

2009-09-01

In the present work we prepared an in situ Cu47.5Zr47.5Al5 bulk metallic glass matrix composite derived from the shape memory alloy CuZr. We use a strength model, which considers percolation and a three-microstructural-element body approach, to understand the effect of the crystalline phase on the yield stress and the fracture strain under compressive loading, respectively. The intrinsic work-hardenability due to the martensitic transformation of the crystalline phase causes significant work hardening also of the composite material.

Lattice dynamics and thermomechanical properties of zirconium(IV) chloride: Evidence for low-temperature negative thermal expansion

NASA Astrophysics Data System (ADS)

Kim, Eunja; Weck, Philippe F.; Borjas, Rosendo; Poineau, Frederic

2018-01-01

The crystal structure, lattice dynamics and themomechanical properties of bulk monoclinic zirconium tetrachloride (ZrCl4) have been investigated using zero-damping dispersion-corrected density functional theory [DFT-D3(zero)]. Phonon analysis reveals that ZrCl4 (cr) undergoes negative thermal expansion (NTE) near T ≈ 10 K, with a coefficient of thermal expansion of α = - 1.2 ppm K-1 and a Grüneisen parameter of γ = - 1.1 . The bulk modulus is predicted to vary from K0 = 8.7 to 7.0 GPa in the temperature range 0-550 K. The isobaric molar heat capacity derived from phonon calculations within the quasi-harmonic approximation is in fair agreement with existing calorimetric data.

The effect of Nb addition on mechanical properties, corrosion behavior, and metal-ion release of ZrAlCuNi bulk metallic glasses in artificial body fluid.

PubMed

Qiu, C L; Liu, L; Sun, M; Zhang, S M

2005-12-15

Bulk metallic glasses (BMGs) of Zr(65 - x)Nb(x)- Cu(17.5)Ni(10)Al(7.5) with Nb = 0, 2, and 5 at % were prepared by copper mold casting. Compression tests reveal that the two BMGs containing Nb exhibited superior strength and plasticity to the base alloy. The corrosion behavior of the alloys obtained was investigated in artificial body fluid by electrochemical measurements. It was found that the addition of Nb significantly enhanced the corrosion resistance of the Zr-based BMG, as indicated by a remarkable increase in corrosion potential and pitting potential. XPS analysis revealed that the passive film formed after anodic polarization was enriched in aluminum oxide and depleted in phosphate ions for the BMGs containing Nb, which accounts for the improvement of corrosion resistance. On the other hand, metal-ion release of different BMGs were determined in PPb (ng/mL) level with inductively coupled plasma mass spectrometry (ICP-MS) after being immersed in artificial body fluid at 37 degrees C for 20 days. It was found that the addition of Nb considerably reduced the ion release of all kinds of metals of the base system. This is probably attributed to the promoting effect of Nb on a rapid formation of highly protective film.

Localized atomic segregation in the spalled area of a Zr50Cu40Al10 bulk metallic glasses induced by laser-shock experiment

NASA Astrophysics Data System (ADS)

Jodar, B.; Loison, D.; Yokoyama, Y.; Lescoute, E.; Nivard, M.; Berthe, L.; Sangleboeuf, J.-C.

2018-02-01

Laser-shock experiments were performed on a ternary {Zr50{Cu}40{Al}10} bulk metallic glass. A spalling process was studied through post-mortem analyses conducted on a recovered sample and spall. Scanning electron microscopy magnification of fracture surfaces revealed the presence of a peculiar feature known as cup-cone. Cups are found on sample fracture surface while cones are observed on spall. Two distinct regions can be observed on cups and cones: a smooth viscous-like region in the center and a flat one with large vein-pattern in the periphery. Energy dispersive spectroscopy measurements conducted on these features emphasized atomic distribution discrepancies both on the sample and spall. We propose a mechanism for the initiation and the growth of these features but also a process for atomic segregation during spallation. Cup and cones would originate from cracks arising from shear bands formation (softened paths). These shear bands result from a quadrupolar-shaped atomic disorder engendered around an initiation site by shock wave propagation. This disorder turns into a shear band when tensile front reaches spallation plane. During the separation process, temperature gain induced by shock waves and shear bands generation decreases material viscosity leading to higher atomic mobility. Once in a liquid-like form, atomic clusters migrate and segregate due to inertial effects originating from particle velocity variation (interaction of release waves). As a result, a high rate of copper is found in sample cups and high zirconium concentration is found on spall cones.

High thermal stability and sluggish crystallization kinetics of high-entropy bulk metallic glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, M.; Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon; Liu, X. J.

2016-06-28

Metallic glasses are metastable and their thermal stability is critical for practical applications, particularly at elevated temperatures. The conventional bulk metallic glasses (BMGs), though exhibiting high glass-forming ability (GFA), crystallize quickly when being heated to a temperature higher than their glass transition temperature. This problem may potentially be alleviated due to the recent developments of high-entropy (or multi-principle-element) bulk metallic glasses (HE-BMGs). In this work, we demonstrate that typical HE-BMGs, i.e., ZrTiHfCuNiBe and ZrTiCuNiBe, have higher kinetic stability, as compared with the benchmark glass Vitreoy1 (Zr{sub 41.2}Ti{sub 13.8}Cu{sub 12.5}Ni{sub 10}Be{sub 22.5}) with a similar chemical composition. The measured activation energymore » for glass transition and crystallization of the HE-BMGs is nearly twice that of Vitreloy 1. Moreover, the sluggish crystallization region ΔT{sub pl-pf}, defined as the temperature span between the last exothermic crystallization peak temperature T{sub pl} and the first crystallization exothermic peak temperature T{sub pf}, of all the HE-BMGs is much wider than that of Vitreloy 1. In addition, high-resolution transmission electron microscopy characterization of the crystallized products at different temperatures and the continuous heating transformation diagram which is proposed to estimate the lifetime at any temperature below the melting point further confirm high thermal stability of the HE-BMGs. Surprisingly, all the HE-BMGs show a small fragility value, which contradicts with their low GFA, suggesting that the underlying diffusion mechanism in the liquid and the solid of HE-BMGs is different.« less

SEPARATING HAFNIUM FROM ZIRCONIUM

DOEpatents

Lister, B.A.J.; Duncan, J.F.

1956-08-21

A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

Acquisition of a Modified Suction Casting Instrument for the Fabrication of Radiation Tolerant Bulk nNanostructured Metallic Materials

DTIC Science & Technology

2015-01-13

Cu/ Nb films”, Philos. Mag., 84, 1021-1028, (2004). [23] D. H. Ryan, J. M. D. Coey, “Magnetic properties of iron-rich Fe- Zr glasses”, Phys. Rev. B...2226, (1982). [26] K. Fukamichi, R. J. Gambino, T. R. McGuire, “ Electrical resistivity and Hall effect in FeZr amorphous sputtered films”, J. Appl...fabricate several bulk nanostructured metallic materials. In particular we fabricated bulk nanostructured Fe- Zr alloys via suction casting technique. The as

Chemoelectronic circuits based on metal nanoparticles

NASA Astrophysics Data System (ADS)

Yan, Yong; Warren, Scott C.; Fuller, Patrick; Grzybowski, Bartosz A.

2016-07-01

To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the ‘jammed’ nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems ‘chemoelectronic’. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also ‘green’, in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

Chemoelectronic circuits based on metal nanoparticles.

PubMed

Yan, Yong; Warren, Scott C; Fuller, Patrick; Grzybowski, Bartosz A

2016-07-01

To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the 'jammed' nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems 'chemoelectronic'. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also 'green', in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

Sub-second thermoplastic forming of bulk metallic glasses by ultrasonic beating

PubMed Central

Ma, Jiang; Liang, Xiong; Wu, Xiaoyu; Liu, Zhiyuan; Gong, Feng

2015-01-01

The work proposed a novel thermoplastic forming approach–the ultrasonic beating forming (UBF) method for bulk metallic glasses (BMGs) in present work. The rapid forming approach can finish the thermoplastic forming of BMGs in less than one second, avoiding the time-dependent crystallization and oxidation to the most extent. Besides, the UBF is also proved to be competent in the fabrication of structures with the length scale ranging from macro scale to nano scale. Our results propose a novel route for the thermoplastic forming of BMGs and have promising applications in the rapid fabrication of macro to nano scale products and devices. PMID:26644149

Evaluation of artifacts generated by zirconium implants in cone-beam computed tomography images.

PubMed

Vasconcelos, Taruska Ventorini; Bechara, Boulos B; McMahan, Clyde Alex; Freitas, Deborah Queiroz; Noujeim, Marcel

2017-02-01

To evaluate zirconium implant artifact production in cone beam computed tomography images obtained with different protocols. One zirconium implant was inserted in an edentulous mandible. Twenty scans were acquired with a ProMax 3D unit (Planmeca Oy, Helsinki, Finland), with acquisition settings ranging from 70 to 90 peak kilovoltage (kVp) and voxel sizes of 0.32 and 0.16 mm. A metal artifact reduction (MAR) tool was activated in half of the scans. An axial slice through the middle region of the implant was selected for each dataset. Gray values (mean ± standard deviation) were measured in two regions of interest, one close to and the other distant from the implant (control area). The contrast-to-noise ratio was also calculated. Standard deviation decreased with greater kVp and when the MAR tool was used. The contrast-to-noise ratio was significantly higher when the MAR tool was turned off, except for low resolution with kVp values above 80. Selection of the MAR tool and greater kVp resulted in an overall reduction of artifacts in images acquired with low resolution. Although zirconium implants do produce image artifacts in cone-bean computed tomography scans, the setting that best controlled artifact generation by zirconium implants was 90 kVp at low resolution and with the MAR tool turned on. Copyright © 2016 Elsevier Inc. All rights reserved.

An In Vivo Evaluation of the Fit of Zirconium-Oxide Based, Ceramic Single Crowns with Vertical and Horizontal Finish Line Preparations.

PubMed

Vigolo, Paolo; Mutinelli, Sabrina; Biscaro, Leonello; Stellini, Edoardo

2015-12-01

Different types of tooth preparations influence the marginal precision of zirconium-oxide based ceramic single crowns. In this in vivo study, the marginal fits of zirconium-oxide based ceramic single crowns with vertical and horizontal finish lines were compared. Forty-six teeth were chosen in eight patients indicated for extraction for implant placement. CAD/CAM technology was used for the production of 46 zirconium-oxide-based ceramic single crowns: 23 teeth were prepared with vertical finishing lines, 23 with horizontal finishing lines. One operator accomplished all clinical procedures. The zirconia crowns were cemented with glass ionomer cement. The teeth were extracted 1 month later. Marginal gaps along vertical planes were measured for each crown, using a total of four landmarks for each tooth by means of a microscope at 50× magnification. On conclusion of microscopic assessment, ESEM evaluation was completed on all specimens. The comparison of the gap between the two types of preparation was performed with a nonparametric test (two-sample Wilcoxon rank-sum test) with a level of significance fixed at p < 0.05. All data were analyzed with STATA12. In the group with horizontal finish line preparations, the median value of the gap was 35.45 μm (Iqr, 0.33); for the vertical finish line group, the median value of the gap was 35.44 μm (Iqr, 0.40). The difference between the two groups was not statistically significant (two-sample Wilcoxon rank-sum test, p = 0.0872). Within the limitations of this study, the gaps of the zirconium-oxide-based ceramic CAD/CAM crowns with vertical and horizontal finish line preparations were not different. © 2015 by the American College of Prosthodontists.

Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra [On the Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra

DOE PAGES

Gilroy, Kyle D.; Elnabawy, Ahmed O.; Yang, Tung -Han; ...

2017-04-27

Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wavemore » density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200–400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. As a result, the mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.« less

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

Lattice dynamics and thermomechanical properties of zirconium(IV) chloride: Evidence for low-temperature negative thermal expansion

DOE PAGES

Kim, Eunja; Weck, Philippe F.; Borjas, Rosendo; ...

2017-11-01

For this research, the crystal structure, lattice dynamics and themomechanical properties of bulk monoclinic zirconium tetrachloride (ZrCl 4) have been investigated using zero-damping dispersion-corrected density functional theory [DFT-D3(zero)]. Phonon analysis reveals that ZrCl 4(cr) undergoes negative thermal expansion (NTE) near T≈10 K, with a coefficient of thermal expansion of α=-1.2 ppm K -1 and a Grüneisen parameter of γ=-1.1. The bulk modulus is predicted to vary from K 0=8.7 to 7.0 GPa in the temperature range 0–550 K. Lastly, the isobaric molar heat capacity derived from phonon calculations within the quasi-harmonic approximation is in fair agreement with existing calorimetric data.

Lattice dynamics and thermomechanical properties of zirconium(IV) chloride: Evidence for low-temperature negative thermal expansion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Eunja; Weck, Philippe F.; Borjas, Rosendo

For this research, the crystal structure, lattice dynamics and themomechanical properties of bulk monoclinic zirconium tetrachloride (ZrCl 4) have been investigated using zero-damping dispersion-corrected density functional theory [DFT-D3(zero)]. Phonon analysis reveals that ZrCl 4(cr) undergoes negative thermal expansion (NTE) near T≈10 K, with a coefficient of thermal expansion of α=-1.2 ppm K -1 and a Grüneisen parameter of γ=-1.1. The bulk modulus is predicted to vary from K 0=8.7 to 7.0 GPa in the temperature range 0–550 K. Lastly, the isobaric molar heat capacity derived from phonon calculations within the quasi-harmonic approximation is in fair agreement with existing calorimetric data.

IMPROVEMENT OF THE EXTRACTION SEPARATION OF URANIUM AND ZIRCONIUM USING ZIRCONIUM-MASKING REAGENTS (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyrs, M.; Caletka, R.; Selucky, P.

1963-12-01

The masking capacities of a series of reagents were studied in the zirconium extraction with tributyl phosphate solution in the presence of nitric acid. It was established that with many reagents an improvement of the separation of uranium from zirconium could be obtained. The efficiency of the reagents increases in the series tannin, oxalic acid, tiron, pyrogallol, and Arsenazo I. (tr-auth)

Bayesian model selection validates a biokinetic model for zirconium processing in humans

PubMed Central

2012-01-01

Background In radiation protection, biokinetic models for zirconium processing are of crucial importance in dose estimation and further risk analysis for humans exposed to this radioactive substance. They provide limiting values of detrimental effects and build the basis for applications in internal dosimetry, the prediction for radioactive zirconium retention in various organs as well as retrospective dosimetry. Multi-compartmental models are the tool of choice for simulating the processing of zirconium. Although easily interpretable, determining the exact compartment structure and interaction mechanisms is generally daunting. In the context of observing the dynamics of multiple compartments, Bayesian methods provide efficient tools for model inference and selection. Results We are the first to apply a Markov chain Monte Carlo approach to compute Bayes factors for the evaluation of two competing models for zirconium processing in the human body after ingestion. Based on in vivo measurements of human plasma and urine levels we were able to show that a recently published model is superior to the standard model of the International Commission on Radiological Protection. The Bayes factors were estimated by means of the numerically stable thermodynamic integration in combination with a recently developed copula-based Metropolis-Hastings sampler. Conclusions In contrast to the standard model the novel model predicts lower accretion of zirconium in bones. This results in lower levels of noxious doses for exposed individuals. Moreover, the Bayesian approach allows for retrospective dose assessment, including credible intervals for the initially ingested zirconium, in a significantly more reliable fashion than previously possible. All methods presented here are readily applicable to many modeling tasks in systems biology. PMID:22863152

Titanium-Zirconium-Nickel Alloy Inside Marshall's Electrostatic Levitator (ESL)

NASA Technical Reports Server (NTRS)

2003-01-01

This Photo, which appeared on the July cover of `Physics Today', is of the Electrostatic Levitator (ESL) at NASA's Marshall Space Flight Center (MSFC). The ESL uses static electricity to suspend an object (about 3-4 mm in diameter) inside a vacuum chamber allowing scientists to record a wide range of physical properties without the sample contracting the container or any instruments, conditions that would alter the readings. Once inside the chamber, a laser heats the sample until it melts. The laser is then turned off and the sample cools, changing from a liquid drop to a solid sphere. In this particular shot, the ESL contains a solid metal sample of titanium-zirconium-nickel alloy. Since 1977, the ESL has been used at MSFC to study the characteristics of new metals, ceramics, and glass compounds. Materials created as a result of these tests include new optical materials, special metallic glasses, and spacecraft components.

Macroscopic tensile plasticity by scalarizating stress distribution in bulk metallic glass

PubMed Central

Gao, Meng; Dong, Jie; Huan, Yong; Wang, Yong Tian; Wang, Wei-Hua

2016-01-01

The macroscopic tensile plasticity of bulk metallic glasses (BMGs) is highly desirable for various engineering applications. However, upon yielding, plastic deformation of BMGs is highly localized into narrow shear bands and then leads to the “work softening” behaviors and subsequently catastrophic fracture, which is the major obstacle for their structural applications. Here we report that macroscopic tensile plasticity in BMG can be obtained by designing surface pore distribution using laser surface texturing. The surface pore array by design creates a complex stress field compared to the uniaxial tensile stress field of conventional glassy specimens, and the stress field scalarization induces the unusual tensile plasticity. By systematically analyzing fracture behaviors and finite element simulation, we show that the stress field scalarization can resist the main shear band propagation and promote the formation of larger plastic zones near the pores, which undertake the homogeneous tensile plasticity. These results might give enlightenment for understanding the deformation mechanism and for further improvement of the mechanical performance of metallic glasses. PMID:26902264

Strong, ductile, and thermally stable Cu-based metal-intermetallic nanostructured composites.

PubMed

Dusoe, Keith J; Vijayan, Sriram; Bissell, Thomas R; Chen, Jie; Morley, Jack E; Valencia, Leopolodo; Dongare, Avinash M; Aindow, Mark; Lee, Seok-Woo

2017-01-09

Bulk metallic glasses (BMGs) and nanocrystalline metals (NMs) have been extensively investigated due to their superior strengths and elastic limits. Despite these excellent mechanical properties, low ductility at room temperature and poor microstructural stability at elevated temperatures often limit their practical applications. Thus, there is a need for a metallic material system that can overcome these performance limits of BMGs and NMs. Here, we present novel Cu-based metal-intermetallic nanostructured composites (MINCs), which exhibit high ultimate compressive strengths (over 2 GPa), high compressive failure strain (over 20%), and superior microstructural stability even at temperatures above the glass transition temperature of Cu-based BMGs. Rapid solidification produces a unique ultra-fine microstructure that contains a large volume fraction of Cu 5 Zr superlattice intermetallic compound; this contributes to the high strength and superior thermal stability. Mechanical and microstructural characterizations reveal that substantial accumulation of phase boundary sliding at metal/intermetallic interfaces accounts for the extensive ductility observed.

Study of phonon modes and elastic properties of Sc36Al24Co20Y20 and Gd36Al24Co20Y20 rare-earth bulk metallic glasses

NASA Astrophysics Data System (ADS)

Suthar, P. H.; Gajjar, P. N.; Thakore, B. Y.; Jani, A. R.

2013-04-01

A phonon modes and elastic properties of two different rare-earth based bulk metallic glasses Sc36Al24Co20Y20 and Gd36Al24Co20Y20 are computed using Hubbard-Beeby approach and our well established model potential. The local field correlation functions due to Hartree (H), Taylor (T), Ichimaru and Utsumi (IU), Farid et al (F) and Sarkar Sen et al (S) are employed to investigate the influence of the screening effects on the vibrational dynamics of Sc36Al24Co20Y20 and Gd36Al24Co20Y20 bulk metallic glasses. The results for bulk modulus BT, modulus of rigidity G, Poisson's ratio ξ, Young's modulus Y, Debye temperature ΘD, propagation velocity of elastic waves and dispersion curves are reported. The computed elastic properties are found to be in good agreement with experimental and other available data.

No difference in in vivo polyethylene wear particles between oxidized zirconium and cobalt-chromium femoral component in total knee arthroplasty.

PubMed

Minoda, Yukihide; Hata, Kanako; Iwaki, Hiroyoshi; Ikebuchi, Mitsuhiko; Hashimoto, Yusuke; Inori, Fumiaki; Nakamura, Hiroaki

2014-03-01

Polyethylene wear particle generation is one of the most important factors affecting mid- to long-term results of total knee arthroplasties. Oxidized zirconium was introduced as a material for femoral components to reduce polyethylene wear generation. However, an in vivo advantage of oxidized zirconium on polyethylene wear particle generation is still controversial. The purpose of this study was to compare in vivo polyethylene wear particles between oxidized zirconium total knee prosthesis and conventional cobalt-chromium (Co-Cr) total knee prosthesis. Synovial fluid was obtained from the knees of 6 patients with oxidized zirconium total knee prosthesis and from 6 patients with conventional cobalt-chromium (Co-Cr) total knee prosthesis 12 months after the operation. Polyethylene particles were isolated and examined using a scanning electron microscope and image analyser. Total number of particles in each knee was 3.3 ± 1.3 × 10(7) in the case of oxidized zirconium (mean ± SD) and 3.4 ± 1.2 × 10(7) in that of Co-Cr (n.s.). The particle size (equivalent circle diameter) was 0.8 ± 0.3 μm in the case of oxidized zirconium and 0.6 ± 0.1 μm in that of Co-Cr (n.s.). The particle shape (aspect ratio) was 1.4 ± 0.0 in the case of oxidized zirconium and 1.4 ± 0.0 in that of metal Co-Cr (n.s). Although newly introduced oxidized zirconium femoral component did not reduce the in vivo polyethylene wear particles in early clinical stage, there was no adverse effect of newly introduced material. At this moment, there is no need to abandon oxidized zirconium femoral component. However, further follow-up of polyethylene wear particle generation should be performed to confirm the advantage of the oxidized zirconium femoral component. Therapeutic study, Level III.

Synthesis, characterization and analytical application of hybrid; acrylamide zirconium (IV) arsenate a cation exchanger, effect of dielectric constant on distribution coefficient of metal ions.

PubMed

Nabi, Syed A; Shalla, Aabid H

2009-04-30

A new hybrid inorganic-organic cation exchanger acrylamide zirconium (IV) arsenate has been synthesized, characterized and its analytical application explored. The effect of experimental parameters such as mixing ratio of reagents, temperature, and pH on the properties of material has been studied. FTIR, TGA, X-ray, UV-vis spectrophotometry, SEM and elemental analysis were used to determine the physiochemical properties of this hybrid ion exchanger. The material behaves as a monofunctional acid with ion-exchange capacity of 1.65 meq/g for Na(+) ions. The chemical stability data reveals that the exchanger is quite stable in mineral acids, bases and fairly stable in organic solvents, while as thermal analysis shows that the material retain 84% of its ion-exchange capacity up to 600 degrees C. Adsorption behavior of metal ions in solvents with increasing dielectric constant has also been explored. The sorption studies reveal that the material is selective for Pb(2+) ions. The analytical utility of the material has been explored by achieving some binary separations of metal ions on its column. Pb(2+) has been selectively removed from synthetic mixtures containing Mg(2+), Ca(2+), Sr(2+), Zn(2+) and Cu(2+), Al(3+), Ni(2+), Fe(3+). In order to demonstrate practical utility of the material quantitative separation of the Cu(2+) and Zn(2+) in brass sample has been achieved on its columns.

Atmospherically deposited trace metals from bulk mineral concentrate port operations.

PubMed

Taylor, Mark Patrick

2015-05-15

Although metal exposures in the environment have declined over the last two decades, certain activities and locations still present a risk of harm to human health. This study examines environmental dust metal and metalloid hazards (arsenic, cadmium, lead and nickel) associated with bulk mineral transport, loading and unloading port operations in public locations and children's playgrounds in the inner city of Townsville, northern Queensland. The mean increase in lead on post-play hand wipes (965 μg/m(2)/day) across all sites was more than 10-times the mean pre-play loadings (95 μg/m(2)/day). Maximum loading values after a 10-minute play period were 3012 μg/m(2), more than seven times the goal of 400 μg/m(2) used by the Government of Western Australia (2011). Maximum daily nickel post-play hand loadings (404 μg/m(2)) were more than 26 times above the German Federal Immission Control Act 2002 annual benchmark of 15 μg/m(2)/day. Repeat sampling over the 5-day study period showed that hands and surfaces were re-contaminated daily from the deposition of metal-rich atmospheric dusts. Lead isotopic composition analysis of dust wipes ((208)Pb/(207)Pb and (206)Pb/(207)Pb) showed that surface dust lead was similar to Mount Isa type ores, which are exported through the Port of Townsville. While dust metal contaminant loadings are lower than other mining and smelting towns in Australia, they exceeded national and international benchmarks for environmental quality. The lessons from this study are clear - even where operations are considered acceptable by managing authorities, targeted assessment and monitoring can be used to evaluate whether current management practices are truly best practice. Reassessment can identify opportunities for improvement and maximum environmental and human health protection. Copyright © 2015 Elsevier B.V. All rights reserved.

Metal concentrations in aggregate interiors, exteriors, whole aggregates, and bulk of Costa Rican soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilcke, W.; Kretzschmar, S.; Bundt, M.

1999-10-01

In many temperate soils the preferential weathering and leaching of aggregate surfaces and the nonaggregated material between aggregates depletes geogenic metals. It also shifts metals from strongly to more weakly bound metal forms. Deposited metals are sorbed preferentially on aggregate surfaces and between aggregates. The authors examined whether preferential desilication under tropical climate causes an enrichment in the aggregate exteriors in oxidic forms of metals. They also studied where deposited metals are bound in these soils. Aggregates (2--20 mm) were selected manually from the A horizons of eight Oxisols, six Andisols, two Mollisols, and two Inceptisols in Costa Rica. Allmore » samples were fractionated into interior and exterior portions and treated with a seven-step sequence to extract Al, Cd, Cu, Fe, Mn, Pb, and Zn. Total concentrations of all metals except Zn were higher in the aggregate exteriors than in the interiors. The average Cd and Pb concentrations in easily extractable fractions were significantly higher in the aggregate exteriors. There were no significant differences in metal partitioning between interiors and exteriors except for Pb, which had higher proportions in extractable forms with NH{sub 2}OH {center{underscore}dot} HCl {gt} NH{sub 4} - acetate, pH 6.0 {gt} EDTA in the exteriors. There were few significant differences in metal concentrations and partitioning between bulk soil and whole aggregates. The results may be explained by (i) preferential desilication of the aggregate exteriors and (ii) preferential sorption of deposited heavy metals mainly in easily extractable forms.« less

On Temperature Rise Within the Shear Bands in Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Bazlov, A. I.; Churyumov, A. Yu.; Buchet, M.; Louzguine-Luzgin, D. V.

2018-05-01

Room temperature deformation process in a bulk metallic glassy sample was studied by using a hydraulic thermomechanical simulator. The temperature rise during each separate shear band propagation event was measured with a high data acquisition frequency by a thermocouple welded to the sample. Calculation showed that when propagation of the well developed shear bands takes place along the entire sample the temperature inside the shear band should be close to the glass-transition temperature. It was also possible to resolve the temporal stress distribution and a double-stage character of stress drops was also observed. The obtained results are compared with the literature data obtained by infrared camera measurements and the results of finite elements modeling.

On Temperature Rise Within the Shear Bands in Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Bazlov, A. I.; Churyumov, A. Yu.; Buchet, M.; Louzguine-Luzgin, D. V.

2018-03-01

Room temperature deformation process in a bulk metallic glassy sample was studied by using a hydraulic thermomechanical simulator. The temperature rise during each separate shear band propagation event was measured with a high data acquisition frequency by a thermocouple welded to the sample. Calculation showed that when propagation of the well developed shear bands takes place along the entire sample the temperature inside the shear band should be close to the glass-transition temperature. It was also possible to resolve the temporal stress distribution and a double-stage character of stress drops was also observed. The obtained results are compared with the literature data obtained by infrared camera measurements and the results of finite elements modeling.

Effects of geometric factors and shear band patterns on notch sensitivity in bulk metallic glasses

DOE PAGES

Li, Weidong; Bei, Hongbin; Gao, Yanfei

2016-09-21

Our recent experiments in notched bulk metallic glasses have found reduced, or insensitive, or improved strengths, while in many of these cases the ductile strain prior to final failure is enhanced. First, although the inverse notch effect is explained by a shift from shear localization to cavitation failure, it is suggested in this work that the synergistic effect between cohesive fracture at the notched area and shear bands emanating from the notch roots may extend the parametric space for the notch insensitive behavior. Second, the dependence of shear band patterns on notch geometric factors is determined by the Rudnicki-Rice theorymore » and the free-volume-based finite element simulations. Our results suggest conditions for shear band multiplication to take place and for the shear-localization-induced failure to be delayed.« less

Effects of geometric factors and shear band patterns on notch sensitivity in bulk metallic glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Weidong; Bei, Hongbin; Gao, Yanfei

Our recent experiments in notched bulk metallic glasses have found reduced, or insensitive, or improved strengths, while in many of these cases the ductile strain prior to final failure is enhanced. First, although the inverse notch effect is explained by a shift from shear localization to cavitation failure, it is suggested in this work that the synergistic effect between cohesive fracture at the notched area and shear bands emanating from the notch roots may extend the parametric space for the notch insensitive behavior. Second, the dependence of shear band patterns on notch geometric factors is determined by the Rudnicki-Rice theorymore » and the free-volume-based finite element simulations. Our results suggest conditions for shear band multiplication to take place and for the shear-localization-induced failure to be delayed.« less

Molecular Dynamics Simulations of Grain Boundary and Bulk Diffusion in Metals.

NASA Astrophysics Data System (ADS)

Plimpton, Steven James

Diffusion is a microscopic mass transport mechanism that underlies many important macroscopic phenomena affecting the structural, electrical, and mechanical properties of metals. This thesis presents results from atomistic simulation studies of diffusion both in bulk and in the fast diffusion paths known as grain boundaries. Using the principles of molecular dynamics single boundaries are studied and their structure and dynamic properties characterized. In particular, tilt boundary bicrystal and bulk models of fcc Al and bcc alpha-Fe are simulated. Diffusion coefficients and activation energies for atomic motion are calculated for both models and compared to experimental data. The influence of the interatomic pair potential on the diffusion is studied in detail. A universal relation between the melting temperature that a pair potential induces in a simulated bulk model and the potential energy barrier height for atomic hopping is derived and used to correlate results for a wide variety of pair potentials. Using these techniques grain boundary and bulk diffusion coefficients for any fcc material can be estimated from simple static calculations without the need to perform more time-consuming dynamic simulations. The influences of two other factors on grain boundary diffusion are also studied because of the interest of the microelectronics industry in the diffusion related reliability problem known as electromigration. The first factor, known to affect the self diffusion rate of Al, is the presence of Cu impurity atoms in Al tilt boundaries. The bicrystal model for Al is seeded randomly with Cu atoms and a simple hybrid Morse potential used to model the Al-Cu interaction. While some effect due to the Cu is noted, it is concluded that pair potentials are likely an inadequate approximation for the alloy system. The second factor studied is the effect of the boundary orientation angle on the diffusion rate. Symmetric bcc Fe boundaries are relaxed to find optimal

Raman spectroscopy analysis of air grown oxide scale developed on pure zirconium substrate

NASA Astrophysics Data System (ADS)

Kurpaska, L.; Favergeon, J.; Lahoche, L.; El-Marssi, M.; Grosseau Poussard, J.-L.; Moulin, G.; Roelandt, J.-M.

2015-11-01

Using Raman spectroscopy technique, external and internal parts of zirconia oxide films developed at 500 °C and 600 °C on pure zirconium substrate under air at normal atmospheric pressure have been examined. Comparison of Raman peak positions of tetragonal and monoclinic zirconia phases, recorded during the oxide growth at elevated temperature, and after cooling at room temperature have been presented. Subsequently, Raman peak positions (or shifts) were interpreted in relation with the stress evolution in the growing zirconia scale, especially closed to the metal/oxide interface, where the influence of compressive stress in the oxide is the biggest. Reported results, for the first time show the presence of a continuous layer of tetragonal zirconia phase developed in the proximity of pure zirconium substrate. Based on the Raman peak positions we prove that this tetragonal layer is stabilized by the high compressive stress and sub-stoichiometry level. Presence of the tetragonal phase located in the outer part of the scale have been confirmed, yet its Raman characteristics suggest a stress-free tetragonal phase, therefore different type of stabilization mechanism. Presented study suggest that its stabilization could be related to the lattice defects introduced by highstoichiometry of zirconia or presence of heterovalent cations.

Wear Analysis in THA Utilizing Oxidized Zirconium and Crosslinked Polyethylene

PubMed Central

Garvin, Kevin L.; Mangla, Jimmi; Murdoch, Nathan; Martell, John M.

2008-01-01

Oxidized zirconium, a material with a ceramic surface on a metal substrate, and highly cross-linked polyethylene are two materials developed to reduce wear. We measured in vivo femoral head penetration in patients with these advanced bearings. We hypothesized the linear wear rates would be lower than those published for cobalt-chrome and standard polyethylene. We retrospectively reviewed a select series of 56 THAs in a relatively young, active patient population utilizing oxidized zirconium femoral heads and highly cross-linked polyethylene acetabular liners. Femoral head penetration was determined using the Martell computerized edge-detection method. All patients were available for 2-year clinical and radiographic followup. True linear wear was 4 μm/year (95% confidence intervals, ± 59 μm/year). The early wear rates in this cohort of relatively young, active patients were low and we believe justify the continued study of these alternative bearing surfaces. Level of Evidence: Level IV, therapeutic study. See the Guidelines for Authors for a complete description of levels of evidence. PMID:18946711

Structure and Thermodynamical Properties of Zirconium Hydrides from First-Principle

NASA Astrophysics Data System (ADS)

Blomqvist, Jakob; Olofsson, Johan; Alvarez, Anna-Maria; Bjerkén, Christina

Zirconium alloys are used as nuclear fuel cladding material due to their mechanical and corrosion resistant properties together with their favorable cross-section for neutron scattering. At running conditions, however, there will be an increase of hydrogen in the vicinity of the cladding surface at the water side of the fuel. The hydrogen will diffuse into the cladding material and at certain conditions, such as lower temperatures and external load, hydrides will precipitate out in the material and cause well known embrittlement, blistering and other unwanted effects. Using phase-field methods it is now possible to model precipitation buildup in metals, for example as a function of hydrogen concentration, temperature and external load, but the technique relies on input of parameters, such as the formation energy of the hydrides and matrix. To that end, we have computed, using the density functional theory (DFT) code GPAW, the latent heat of fusion as well as solved the crystal structure for three zirconium hydride polymorphs: δ-ZrH1.6, γ-ZrH, and Є-ZrH2.

Quercetin as colorimetric reagent for determination of zirconium

USGS Publications Warehouse

Grimaldi, F.S.; White, C.E.

1953-01-01

Methods described in the literature for the determination of zirconium are generally designed for relatively large amounts of this element. A good procedure using colorimetric reagent for the determination of trace amounts is desirable. Quercetin has been found to yield a sensitive color reaction with zirconium suitable for the determination of from 0.1 to 50?? of zirconium dioxide. The procedure developed involves the separation of zirconium from interfering elements by precipitation with p-dimethylaminoazophenylarsonic acid prior to its estimation with quercetin. The quercetin reaction is carried out in 0.5N hydrochloric acid solution. Under the operating conditions it is indicated that quercetin forms a 2 to 1 complex with zirconium; however, a 2 to 1 and a 1 to 1 complex can coexist under special conditions. Approximate values for the equilibrium constants of the complexes are K1 = 0.33 ?? 10-5 and K2 = 1.3 ?? 10-9. Seven Bureau of Standards samples of glass sands and refractories were analyzed with excellent results. The method described should find considerable application in the analysis of minerals and other materials for macro as well as micro amounts of zirconium.

CHARACTERISTICS OF ANODIC AND CORROSION FILMS ON ZIRCONIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Misch, R.D.

1960-05-01

Zirconium anodizes similarly to tungsten in respect to the change of interference colors with applied voltage. However, the oxide layer on tungsten cannot reach as great a thickness. Hafnium does not anodize in the same way as zirconium but is similar to tantalum. By measuring the interference color and capacitative thicknesses on zirconium (Grades I and III) and a 2.5 wt.% tin ailoy, the film was found to grow less rapidly in terms of capacitance than in terms of iaterference colors. This was interpreted to mean that cracks develop in the oxide as it thickens. The effect was most pronouncedmore » on Grade III zirconium and least pronounced on the tin alloy. The reduction in capacitative thickness was especially noticeable when white oxide appeared. Comparative measurements on Grade I zirconium and 2.5 wt.% tin alloy indicated that the thickness of the oxide film on the tin alloy (after 16 hours in water) increased more rapidly with temperature than the film on zirconium. Tin is believed to act in ways to counteract the tendency of the oxide to form cracks, and to produce vacancies which promote ionic diffusion. (auth)« less

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

PubMed

Li, H F; Zhou, F Y; Li, L; Zheng, Y F

2016-04-19

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

PubMed Central

Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

2016-01-01

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

Influence of the Ag concentration on the medium-range order in a CuZrAlAg bulk metallic glass

DOE PAGES

Gammer, C.; Escher, B.; Ebner, C.; ...

2017-03-21

Fluctuation electron microscopy of bulk metallic glasses of CuZrAl(Ag) demonstrates that medium-range order is sensitive to minor compositional changes. Furthermore, by analyzing nanodiffraction patterns medium-range order is detected with crystal-like motifs based on the B2 CuZr structure and its distorted structures resembling the martensitic ones. This result thus demonstrates some structural homology between the metallic glass and its high temperature crystalline phase. The amount of medium-range order seems slightly affected with increasing Ag concentration (0, 2, 5 at.%) but the structural motifs of the medium-range ordered clusters become more diverse at the highest Ag concentration. The decrease of dominant clustersmore » is consistent with the destabilization of the B2 structure measured by calorimetry and accounts for the increased glass-forming ability.« less

Influence of the Ag concentration on the medium-range order in a CuZrAlAg bulk metallic glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gammer, C.; Escher, B.; Ebner, C.

Fluctuation electron microscopy of bulk metallic glasses of CuZrAl(Ag) demonstrates that medium-range order is sensitive to minor compositional changes. Furthermore, by analyzing nanodiffraction patterns medium-range order is detected with crystal-like motifs based on the B2 CuZr structure and its distorted structures resembling the martensitic ones. This result thus demonstrates some structural homology between the metallic glass and its high temperature crystalline phase. The amount of medium-range order seems slightly affected with increasing Ag concentration (0, 2, 5 at.%) but the structural motifs of the medium-range ordered clusters become more diverse at the highest Ag concentration. The decrease of dominant clustersmore » is consistent with the destabilization of the B2 structure measured by calorimetry and accounts for the increased glass-forming ability.« less

Reduced-Gravity Measurements of the Effect of Oxygen on Properties of Zirconium

NASA Technical Reports Server (NTRS)

Zhao, J.; Lee, J.; Wunderlich, R.; Fecht, H.-J.; Schneider, S.; SanSoucie, M.; Rogers, J.; Hyers, R.

2016-01-01

The influence of oxygen on the thermophysical properties of zirconium is being investigated using MSL-EML (Material Science Laboratory - Electromagnetic Levitator) on ISS (International Space Station) in collaboration with NASA, ESA (European Space Agency), and DLR (German Aerospace Center). Zirconium samples with different oxygen concentrations will be put into multiple melt cycles, during which the density, viscosity, surface tension, heat capacity, and electric conductivity will be measured at various undercooled temperatures. The facility check-up of MSL-EML and the first set of melting experiments have been successfully performed in 2015. The first zirconium sample will be tested near the end of 2015. As part of ground support activities, the thermophysical properties of zirconium and ZrO were measured using a ground-based electrostatic levitator located at the NASA Marshall Space Flight Center. The influence of oxygen on the measured surface tension was evaluated. The results of this research will serve as reference data for those measured in ISS.

Monitoring bisphosphonate surface functionalization and acid stability of hierarchically porous titanium zirconium oxides.

PubMed

Ide, Andreas; Drisko, Glenna L; Scales, Nicholas; Luca, Vittorio; Schiesser, Carl H; Caruso, Rachel A

2011-11-01

To take advantage of the full potential of functionalized transition metal oxides, a well-understood nonsilane based grafting technique is required. The functionalization of mixed titanium zirconium oxides was studied in detail using a bisphosphonic acid, featuring two phosphonic acid groups with high surface affinity. The bisphosphonic acid employed was coupled to a UV active benzamide moiety in order to track the progress of the surface functionalization in situ. Using different material compositions, altering the pH environment, and looking at various annealing conditions, key features of the functionalization process were identified that consequently will allow for intelligent material design. Loading with bisphosphonic acid was highest on supports calcined at 650 °C compared to lower calcination temperatures: A maximum capacity of 0.13 mmol g(-1) was obtained and the adsorption process could be modeled with a pseudo-second-order rate relationship. Heating at 650 °C resulted in a phase transition of the mixed binary oxide to a ternary oxide, titanium zirconium oxide in the srilankite phase. This phase transition was crucial in order to achieve high loading of the bisphosphonic acid and enhanced chemical stability in highly acidic solutions. Due to the inert nature of phosphorus-oxygen-metal bonds, materials functionalized by bisphosphonic acids showed increased chemical stability compared to their nonfunctionalized counterparts in harshly acidic solutions. Leaching studies showed that the acid stability of the functionalized material was improved with a partially crystalline srilankite phase. The materials were characterized using nitrogen sorption, X-ray powder diffraction, and UV-vis spectroscopy; X-ray photoelectron spectroscopy was used to study surface coverage with the bisphosphonic acid molecules.

Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

NASA Astrophysics Data System (ADS)

Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

2016-07-01

A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

Metal alkoxides and methods of making same

DOEpatents

Hentges, Patrick J.; Greene, Laura H.; Pafford, Margaret Mary; Westwood, Glenn; Klemperer, Walter G.

2005-01-04

A method of making a superconducting structure includes depositing a metal alkoxide on a surface of a metal and hydrolyzing the metal alkoxide on the surface to form a pinhole-free film. The metal is a superconductor. The metal alkoxide may be a compound of formula (I): where M is zirconium or hafnium, and the purity of the compound is at least 97% as measured by NMR spectroscopy.

Bulk and edge spin transport in topological magnon insulators

NASA Astrophysics Data System (ADS)

Rückriegel, Andreas; Brataas, Arne; Duine, Rembert A.

2018-02-01

We investigate the spin transport properties of a topological magnon insulator, a magnetic insulator characterized by topologically nontrivial bulk magnon bands and protected magnon edge modes located in the bulk band gaps. Employing the Landau-Lifshitz-Gilbert phenomenology, we calculate the spin current driven through a normal metal |topological magnon insulator |normal metal heterostructure by a spin accumulation imbalance between the metals, with and without random lattice defects. We show that bulk and edge transport are characterized by different length scales. This results in a characteristic system size where the magnon transport crosses over from being bulk dominated for small systems to edge dominated for larger systems. These findings are generic and relevant for topological transport in systems of nonconserved bosons.

Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larsen, Randy W., E-mail: rwlarsen@usf.edu; Wojtas, Lukasz

2017-03-15

The ability to encapsulate photo-active guest molecules within the pores of metal organic frameworks (MOFs) affords the opportunity to develop robust photocatalysts as well as solar energy conversion systems. An important criteria for such systems is stability of the new materials towards moisture, high temperatures, etc which preclude the use of many MOF frameworks. Here, the ability to encapsulate [Ru(II)(2,2′-bipyridine){sub 3}]{sup 2+}([Ru(bpy){sub 3}]{sup 2+}) into the cavities of the zirconium based MOF Uio-66 as well as the photophysical properties of the complex are reported. The X-ray powder diffraction data of the orange Uio-66 powder are consistent with the formation ofmore » Uio-66 in the presence of [Ru(bpy){sub 3}]{sup 2+}. The steady state emission exhibits a significant bathochromic shift from 603 nm in ethanol to 610 nm in Uio-66. The corresponding emission decay of the encapsulated [Ru(bpy){sub 3}]{sup 2+} complex is biexponential with a fast component of 128 ns and a slower component of 1176 ns (20 deg C). The slow component is consistent with encapsulation of [Ru(bpy){sub 3}]{sup 2+} into cavities with restricted volume that prevents the population of a triplet ligand field transition that is anti-bonding with respect to the Ru-N bonds. The origin of the fast component is unclear but may involve interactions of the [Ru(bpy){sub 3}]{sup 2+} encapsulated within large cavities formed through missing ligand defect sites within the Uio-66 materials. Co-encapsulated quenchers contained within these larger cavities gives rise to the reduced lifetimes of the [Ru(bpy){sub 3}]{sup 2+} complexes. - Graphical abstract: One-pot synthesis of Ru(II)tris(2,2-bipyridine)@Uio-66 (left) and the effects of encapsulation on the excited state energy levels and decay pathways of the Ru(II)tris(2,2-bipyridine) complex (right).« less

Developing and Characterizing Bulk Metallic Glasses for Extreme Applications

NASA Astrophysics Data System (ADS)

Roberts, Scott Nolan

Metallic glasses have typically been treated as a "one size fits all" type of material. Every alloy is considered to have high strength, high hardness, large elastic limits, corrosion resistance, etc. However, similar to traditional crystalline materials, properties are strongly dependent upon the constituent elements, how it was processed, and the conditions under which it will be used. An important distinction which can be made is between metallic glasses and their composites. Charpy impact toughness measurements are performed to determine the effect processing and microstructure have on bulk metallic glass matrix composites (BMGMCs). Samples are suction cast, machined from commercial plates, and semi-solidly forged (SSF). The SSF specimens have been found to have the highest impact toughness due to the coarsening of the dendrites, which occurs during the semi-solid processing stages. Ductile to brittle transition (DTBT) temperatures are measured for a BMGMC. While at room temperature the BMGMC is highly toughened compared to a fully glassy alloy, it undergoes a DTBT by 250 K. At this point, its impact toughness mirrors that of the constituent glassy matrix. In the following chapter, BMGMCs are shown to have the capability of being capacitively welded to form single, monolithic structures. Shear measurements are performed across welded samples, and, at sufficient weld energies, are found to retain the strength of the parent alloy. Cross-sections are inspected via SEM and no visible crystallization of the matrix occurs. Next, metallic glasses and BMGMCs are formed into sheets and eggbox structures are tested in hypervelocity impacts. Metallic glasses are ideal candidates for protection against micrometeorite orbital debris due to their high hardness and relatively low density. A flat single layer, flat BMG is compared to a BMGMC eggbox and the latter creates a more diffuse projectile cloud after penetration. A three tiered eggbox structure is also tested by firing

DISSOLUTION OF ZIRCONIUM-CONTAINING FUEL ELEMENTS

DOEpatents

Horn, F.L.

1961-12-12

Uranium is recovered from spent uranium fuel elements containing or clad with zirconium. These fuel elements are placed in an anhydrous solution of hydrogen fluoride and nitrogen dioxide. Within this system uranium forms a soluble complex and zirconium forms an insoluble complex. The uranium can then be separated, treated, and removed from solution as uranium hexafluoride. (AEC)

Titanium-Zirconium-Nickel Alloy Inside Marshall's Electrostatic Levitator (ESL)

NASA Technical Reports Server (NTRS)

2003-01-01

This is a close-up of a sample of titanium-zirconium-nickel alloy inside the Electrostatic Levitator (ESL) vacuum chamber at NASA's Marshall Space Flight Center (MSFC). The ESL uses static electricity to suspend an object (about 3-4 mm in diameter) inside a vacuum chamber allowing scientists to record a wide range of physical properties without the sample contracting the container or any instruments, conditions that would alter the readings. Once inside the chamber, a laser heats the sample until it melts. The laser is then turned off and the sample cools, changing from a liquid drop to a solid sphere. Since 1977, the ESL has been used at MSFC to study the characteristics of new metals, ceramics, and glass compounds. Materials created as a result of these tests include new optical materials, special metallic glasses, and spacecraft components.

Human biokinetic data and a new compartmental model of zirconium--a tracer study with enriched stable isotopes.

PubMed

Greiter, Matthias B; Giussani, Augusto; Höllriegl, Vera; Li, Wei Bo; Oeh, Uwe

2011-09-01

Biokinetic models describing the uptake, distribution and excretion of trace elements are an essential tool in nutrition, toxicology, or internal dosimetry of radionuclides. Zirconium, especially its radioisotope (95)Zr, is relevant to radiation protection due to its production in uranium fission and neutron activation of nuclear fuel cladding material. We present a comprehensive set of human data from a tracer study with stable isotopes of zirconium. The data are used to refine a biokinetic model of zirconium. Six female and seven male healthy adult volunteers participated in the study. It includes 16 complete double tracer investigations with oral ingestion and intravenous injection, and seven supplemental investigations. Tracer concentrations were measured in blood plasma and urine collected up to 100 d after tracer administration. The four data sets (two chemical tracer forms in plasma and urine) each encompass 105-240 measured concentration values above detection limits. Total fractional absorption of ingested zirconium was found to be 0.001 for zirconium in citrate-buffered drinking solution and 0.007 for zirconium oxalate solution. Biokinetic models were developed based on the linear first-order kinetic compartmental model approach used by the International Commission on Radiological Protection (ICRP). The main differences of the optimized systemic model of zirconium to the current ICRP model are (1) recycling into the transfer compartment made necessary by the observed tracer clearance from plasma, (2) different parameters related to fractional absorption for each form of the ingested tracer, and (3) a physiologically based excretion pathway to urine. The study considerably expands the knowledge on the biokinetics of zirconium, which was until now dominated by data from animal studies. The proposed systemic model improves the existing ICRP model, yet is based on the same principles and fits well into the ICRP radiation protection approach. Copyright © 2011

Processing fissile material mixtures containing zirconium and/or carbon

DOEpatents

Johnson, Michael Ernest; Maloney, Martin David

2013-07-02

A method of processing spent TRIZO-coated nuclear fuel may include adding fluoride to complex zirconium present in a dissolved TRIZO-coated fuel. Complexing the zirconium with fluoride may reduce or eliminate the potential for zirconium to interfere with the extraction of uranium and/or transuranics from fission materials in the spent nuclear fuel.

Conducting metal oxide and metal nitride nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

DiSalvo, Jr., Francis J.; Subban, Chinmayee V.

Conducting metal oxide and nitride nanoparticles that can be used in fuel cell applications. The metal oxide nanoparticles are comprised of for example, titanium, niobium, tantalum, tungsten and combinations thereof. The metal nitride nanoparticles are comprised of, for example, titanium, niobium, tantalum, tungsten, zirconium, and combinations thereof. The nanoparticles can be sintered to provide conducting porous agglomerates of the nanoparticles which can be used as a catalyst support in fuel cell applications. Further, platinum nanoparticles, for example, can be deposited on the agglomerates to provide a material that can be used as both an anode and a cathode catalyst supportmore » in a fuel cell.« less

A General Bioinspired, Metals-Based Synergic Cross-Linking Strategy toward Mechanically Enhanced Materials.

PubMed

Chen, Ke; Ding, Jin; Zhang, Shuhao; Tang, Xuke; Yue, Yonghai; Guo, Lin

2017-03-28

Creating lightweight engineering materials combining high strength and great toughness remains a significant challenge. Despite possessing-enhanced strength and stiffness, bioinspired/polymeric materials usually suffer from clearly reduced extensibility and toughness when compared to corresponding bulk polymer materials. Herein, inspired by tiny amounts of various inorganic impurities for mechanical improvement in natural materials, we present a versatile and effective metal ion (M n+ )-based synergic cross-linking (MSC) strategy incorporating eight types of metal ions into material bulks that can drastically enhance the tensile strength (∼24.1-70.8%), toughness (∼18.6-110.1%), modulus (∼21.6-66.7%), and hardness (∼6.4-176.5%) of multiple types of pristine materials (from hydrophilic to hydrophobic and from unary to binary). More importantly, we also explore the primarily elastic-plastic deformation mechanism and brittle fracture behavior (indentation strain of >5%) of the synergic cross-linked graphene oxide (Syn-GO) paper by means of in situ nanoindentation SEM. The MSC strategy for mechanically enhanced integration can be readily attributed to the formation of the complicated metals-based cross-linking/complex networks in the interfaces and intermolecules between functional groups of materials and various metal ions that give rise to efficient energy dissipation. This work suggests a promising MSC strategy for designing advanced materials with outstanding mechanical properties by adding low amounts (<1.0 wt %) of synergic metal ions serving as synergic ion-bonding cross-linkers.

FORMING PROTECTIVE FILMS ON METAL

DOEpatents

Gurinsky, D.H.; Kammerer, O.F.; Sadofsky, J.; Weeks, J.R.

1958-12-16

Methods are described of inhibiting the corrosion of ferrous metal by contact with heavy liquid metals such as bismuth and gallium at temperatures above 500 icient laborato C generally by bringing nltrogen and either the metal zirconium, hafnium, or titanium into reactlve contact with the ferrous metal to form a thin adherent layer of the nitride of the metal and thereafter maintaining a fractional percentage of the metal absorbed in the heavy liquid metal in contact with the ferrous metal container. The general purpose for uslng such high boiling liquid metals in ferrous contalners would be as heat transfer agents in liquid-metal-fueled nuclear reactors.

Physical characterization of a new composition of oxidized zirconium-2.5 wt% niobium produced using a two step process for biomedical applications

NASA Astrophysics Data System (ADS)

Pawar, V.; Weaver, C.; Jani, S.

2011-05-01

Zirconium and particularly Zr-2.5 wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step process that forms a thicker DHZ and thus increased depth of hardening than that can be obtained using a one step oxidation process. The first step is thermal oxidation in air and the second step is a heat treatment in vacuum. The second step drives oxygen from the oxide formed in the first step deeper into the substrate to form a thicker DHZ. During the process only a portion of the oxide is dissolved. This new composition (DHOxZr) has approximately 4-6 μm oxide similar to that of OxZr. The nano-hardness of the oxide is similar but the DHZ is approximately 10 times thicker. The stoichiometry of the oxide is similar and a secondary phase rich in oxygen is present through the entire thickness. Due to the increased depth of hardening, the critical load required for the onset of oxide cracking is approximately 1.6 times more than that of the oxide of OxZr. This new composition has a potential to be used as a bearing surface in applications where greater depth of hardening is required.

Microstructure Effects on Spall Strength of Titanium-based Bulk Metallic Glass Composites

NASA Astrophysics Data System (ADS)

Diaz, Rene; Hofmann, Douglas; Thadhani, Naresh; Georgia Tech Team; GT-JPL Collaboration

2017-06-01

The spall strength of Ti-based metallic glass composites is investigated as a function of varying volume fractions (0-80%) of in-situ formed crystalline dendrites. With increasing dendrite content, the topology changes such that neither the harder glass nor the softer dendrites dominate the microstructure. Plate-impact experiments were performed using the 80-mm single-stage gas gun over impact stresses up to 18 GPa. VISAR interferometry was used to obtain rear free-surface velocity profiles revealing the velocity pullback spall failure signals. The spall strengths were higher than for Ti-6Al-4V alloy, and remained high up to impact stress. The influence of microstructure on the spall strength is indicated by the constants of the power law fit with the decompression strain rate. Differences in fracture behavior reveal void nucleation as a dominant mechanism affecting the spall strength. The microstructure with neither 100% glass nor with very high crystalline content, provides the most tortuous path for fracture and therefore highest spall strength. The results allow projection of spall strength predictions for design of in-situ formed metallic glass composites. ARO Grant # W911NF-09 ``1-0403 NASA JPL Contract # 1492033 ``Prime # NNN12AA01C; NSF GRFP Grant #DGE-1148903; and NDSE & G.

AC Calorimetry and Thermophysical Properties of Bulk Glass-Forming Metallic Liquids

NASA Technical Reports Server (NTRS)

Johnson, William L.

2000-01-01

Thermo-physical properties of two bulk metallic glass forming alloys, Ti34Zr11Cu47Ni8 (VIT 101) and Zr57Nb5Ni12.6Al10CU15.4 (VIT 106), were investigated in the stable and undercooled melt. Our investigation focused on measurements of the specific heat in the stable and undercooled liquid using the method of AC modulation calorimetry. The VIT 106 exhibited a maximum undercooling of 140 K in free radiative cooling. Specific heat measurements could be performed in stable melt down to an undercooling of 80 K. Analysis of the specific heat data indicate an anomaly near the equilibrium liquidus temperature. This anomaly is also observed in y the temperature dependencies of the external relaxation time, the specific volume, and the surface tension; it is tentatively attributed to a phase separation in the liquid state. The VIT 101 specimen exhibited a small undercooling of about 50 K. Specific heat measurements were performed in the stable and undercooled melt. These various results will be combined with ground based work such as the measurement of T-T-T curves in the electrostatic levitator and low temperature viscosity and specific heat measurements for modeling the nucleation kinetics of these alloys.

Friction and surface chemistry of some ferrous-base metallic glasses

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

The friction properties of some ferrous-base metallic glasses were measured both in argon and in vacuum to a temperature of 350 C. The alloy surfaces were also analyzed with X-ray photoelectron spectroscopy to identify the compounds and elements present on the surface. The results of the investigation indicate that even when the surfaces of the amorphous alloys, or metallic glasses, are atomically clean, bulk contaminants such as boric oxide and silicon dioxide diffuse to the surfaces. Friction measurements in both argon and vacuum indicate that the alloys exhibit higher coefficients of friction in the crystalline state than they do in the amorphous state.

Zirconium tetrachloride revisited

DOE PAGES

Borjas Nevarez, Rosendo; Balasekaran, Samundeeswari Mariappan; Kim, Eunja; ...

2018-02-19

We present that zirconium tetrachloride, ZrCl 4, is a strategic material with wide-ranging applications. Until now, only one crystallographic study on ZrCl 4has been reported [Krebs (1970).Z. Anorg. Allg. Chem.378, 263–272] and that was more than 40 years ago. The compound used for the previous determination was prepared from ZrO 2 and Cl 2–CCl 4, and single-crystal X-ray diffraction (SCXRD) studies on ZrCl 4 obtained from Zr metal have not yet been reported. In this context, we prepared ZrCl 4 from the reaction of Zr metal and Cl 2 gas in a sealed tube and investigated its structure at 100,more » 150, 200, 250, and 300 K. At 300 K, the SCXRD analysis indicates that ZrCl 4 crystallizes in the orthorhombic space group Pca2 1 [a= 6.262 (9),b= 7.402 (11),c= 12.039 (17) Å, andV= 558.0 (14) Å 3] and consists of infinite zigzag chains of edge-sharing ZrCl 6 octahedra. This chain motif is similar to that observed previously in ZrCl 4, but the structural parameters and space group differ. Finally, in the temperature range 100–300 K, no phase transformation was identified, while elongation of intra-chain Zr...Zr [3.950 (1) Å at 100 K and 3.968 (5) Å at 300 K] and inter-chain Cl...Cl [3.630 (3) Å at 100 K and 3.687 (9) Å at 300 K] distances occurred.« less

40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under this...

40 CFR 721.10089 - Modified salicylic acid, zirconium complex (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified salicylic acid, zirconium... Specific Chemical Substances § 721.10089 Modified salicylic acid, zirconium complex (generic). (a) Chemical... as modified salicylic acid, zirconium complex (PMN P-00-552) is subject to reporting under this...

Buoyancy and Pressure Effects on Bulk Metal-Oxygen Reactions

NASA Technical Reports Server (NTRS)

Abbud-Madrid, A.; McKnight, C.; Branch, M. C.; Daily, J. W.; Friedman, R. (Technical Monitor)

1998-01-01

The combustion behavior of metal-oxygen reactions if a weakly buoyant environment is studied to understand the rate-controlling mechanisms in the homogeneous and heterogeneous combustion of bulk metals. Cylindrical titanium and magnesium specimens are ignited in pure-oxygen at pressures ranging from 0.1 to 4.0 atm. Reduced gravity is obtained from an aircraft flying parabolic trajectories. A weakly buoyant environment is generated at low pressures under normal gravity and also at 1 atm under reduced gravity (0.01g). The similarity between these two experimental conditions comes from the p(exp 2)g buoyancy scale extracted from the Grashof number. Lower propagation rates of the molten interface on titanium samples are found at progressively lower pressures at 1 g. These rates are compared to theoretical results from heat conduction analyses with a diffusion/convection controlled reaction. The close agreement found between experimental and theoretical values indicate the importance values indicate the importance of natural convection enhanced oxygen transport on combustion rates. For magnesium, progressively longer burning times are experienced at lower pressures and 1 g. Under reduced gravity conditions at 1 atm, a burning time twice as long as in 1 g is exhibited. However, in this case, the validity of the p(exp 2)g buoyancy scale remains untested due to the inability to obtain steady gas-phase burning of the magnesium sample at 0.1 atm. Nevertheless, longer burning times and larger flame standoff distance at low pressures and at low gravity points to a diffusion/convection controlled reaction.

RECOVERY OF URANIUM FROM ZIRCONIUM-URANIUM NUCLEAR FUELS

DOEpatents

Gens, T.A.

1962-07-10

An improvement was made in a process of recovering uranium from a uranium-zirconium composition which was hydrochlorinated with gsseous hydrogen chloride at a temperature of from 350 to 800 deg C resulting in volatilization of the zirconium, as zirconium tetrachloride, and the formation of a uranium containing nitric acid insoluble residue. The improvement consists of reacting the nitric acid insoluble hydrochlorination residue with gaseous carbon tetrachloride at a temperature in the range 550 to 600 deg C, and thereafter recovering the resulting uranium chloride vapors. (AEC)

Structural and mechanical modifications induced on Zr-based bulk metallic glass by laser shock peening

NASA Astrophysics Data System (ADS)

Zhu, Yunhu; Fu, Jie; Zheng, Chao; Ji, Zhong

2016-12-01

In this study, surface modification of a Zr41.2Ti13.8Cu12.5Ni10Be22.5 (vit1) bulk metallic glass (BMG) has been studied in an effort to improve the mechanical properties by laser shock peening (LSP) treatment. The phase structure, mechanical properties, and microstructural evolution of the as-cast and LSP treated specimens were systematically investigated. It was found that the vit1 BMG still consisted of fully amorphous structure after LSP treatment. Measurements of the heat relaxation indicate that a large amount of free volume is introduced into vit1 BMG during LSP process. LSP treatment causes a decrease of hardness attributable to generation of free volume. The plastic deformation ability of vit1 BMG was investigated under three-point bending conditions. The results demonstrate that the plastic strain of LSP treated specimen is 1.83 times as large as that of the as-cast specimen. The effect of LSP technology on the hardness and plastic deformation ability of vit1 BMG is discussed on the basis of free volume theory. The high dense shear bands on the side surface, the increase of striations and critical shear displacement on the tensile fracture region, and more uniform dimples structure on the compressive fracture region also demonstrate that the plasticity of vit1 BMG can be enhanced by LSP.

A study into the impact of interface roughness development on mechanical degradation of oxides formed on zirconium alloys

NASA Astrophysics Data System (ADS)

Platt, P.; Wedge, S.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

2015-04-01

As a cladding material used to encapsulate nuclear fuel pellets, zirconium alloys are the primary barrier separating the fuel and a pressurised steam or lithiated water environment. Degradation mechanisms such as oxidation can be the limiting factor in the life-time of the fuel assembly. Key to controlling oxidation, and therefore allowing increased burn-up of fuel, is the development of a mechanistic understanding of the corrosion process. In an autoclave, the oxidation kinetics for zirconium alloys are typically cyclical, with periods of accelerated kinetics being observed in steps of ∼2 μm oxide growth. These periods of accelerated oxidation are immediately preceded by the development of a layer of lateral cracks near the metal-oxide interface, which may be associated with the development of interface roughness. The present work uses scanning electron microscopy to carry out a statistical analysis of changes in the metal-oxide interface roughness between three different alloys at different stages of autoclave oxidation. The first two alloys are Zircaloy-4 and ZIRLO™ for which analysis is carried out at stages before, during and after first transition. The third alloy is an experimental low tin alloy, which under the same oxidation conditions and during the same time period does not appear to go through transition. Assessment of the metal-oxide interface roughness is primarily carried out based on the root mean square of the interface slope known as the Rdq parameter. Results show clear trends with relation to transition points in the corrosion kinetics. Discussion is given to how this relates to the existing mechanistic understanding of the corrosion process, and the components required for possible future modelling approaches.

PROCESS OF DISSOLVING ZIRCONIUM ALLOYS

DOEpatents

Shor, R.S.; Vogler, S.

1958-01-21

A process is described for dissolving binary zirconium-uranium alloys where the uranium content is about 2%. In prior dissolution procedures for these alloys, an oxidizing agent was added to prevent the precipitation of uranium tetrafluoride. In the present method complete dissolution is accomplished without the use of the oxidizing agent by using only the stoichiometric amount or slight excess of HF required by the zirconium. The concentration of the acid may range from 2M to 10M and the dissolution is advatageously carried out at a temperature of 80 deg C.

A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors

PubMed Central

Chen, Weifeng; Wu, Weijing; Zhou, Lei; Xu, Miao; Wang, Lei; Peng, Junbiao

2018-01-01

A semi-analytical extraction method of interface and bulk density of states (DOS) is proposed by using the low-frequency capacitance–voltage characteristics and current–voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs). In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson’s equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco). As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS) simultaneously. PMID:29534492

Pseudopotential theoretical study of the alkali metals under arbitrary pressure: Density, bulk modulus, and shear moduli

NASA Astrophysics Data System (ADS)

Rasky, Daniel J.; Milstein, Frederick

1986-02-01

Milstein and Hill previously derived formulas for computing the bulk and shear moduli, κ, μ, and μ', at arbitrary pressures, for cubic crystals in which interatomic interaction energies are modeled by pairwise functions, and they carried out the moduli computations using the complete family of Morse functions. The present study extends their work to a pseudopotential description of atomic binding. Specifically: (1) General formulas are derived for determining these moduli under hydrostatic loading within the framework of a pseudopotential model. (2) A two-parameter pseudopotential model is used to describe atomic binding of the alkali metals, and the two parameters are determined from experimental data (the model employs the Heine-Abarenkov potential with the Taylor dielectric function). (3) For each alkali metal (Li, Na, K, Rb, and Cs), the model is used to compute the pressure-versus-volume behavior and, at zero pressure, the binding energy, the density, and the elastic moduli and their pressure derivatives; the theoretical behavior is found to be in excellent agreement with experiment. (4) Calculations are made of κ, μ, and μ' of the bcc alkali metals over wide ranges of hydrostatic compression and expansion. (5) The pseudopotential results are compared with those of arbitrary-central-force models (wherein κ-(2/3)μ=μ'+2P) and with the specific Morse-function results. The pressures, bulk moduli, and zero-pressure shear moduli (as determined for the Morse and pseudopotential models) are in excellent agreement, but important differences appear in the shear moduli under high compressions. The computations in the present paper are for the bcc metals; a subsequent paper will extend this work to include both the bcc and fcc structures, at compressions and expansions where elastic stability or lattice cohesion is, in practice, lost.

Process for production of a metal hydride

DOEpatents

Allen, Nathan Tait; Butterick, III, Robert; Chin, Arthur Achhing; Millar, Dean Michael; Molzahn, David Craig

2014-08-12

A process for production of a metal hydride compound MH.sub.x, wherein x is one or two and M is an alkali metal, Be or Mg. The process comprises combining a compound of formula (R.sup.1O).sub.xM with aluminum, hydrogen and at least one metal selected from among titanium, zirconium, hafnium, niobium, vanadium, tantalum and iron to produce a compound of formula MH.sub.x. R.sup.1 is phenyl or phenyl substituted by at least one alkyl or alkoxy group. A mole ratio of aluminum to (R.sup.1O).sub.xM is from 0.1:1 to 1:1. The catalyst is present at a level of at least 200 ppm based on weight of aluminum.

Surface functionalization of mesoporous silica SBA-15 by liquid-phase grafting of zirconium phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Sheng; Hagaman, Edward; Ma, Zhen

2010-01-01

The introduction of mesoporous silicas in the 1990s has offered new opportunities for the engineering of ordered catalytic nanoreactors, but the acid properties of mesoporous silicas are rather poor. Herein, mesoporous silica (SBA-15) surfaces were functionalized by zirconium phosphate via two methods recently developed in our group. Zr(OPr){sub 4} and POCl{sub 3} were used as appropriate precursors in both methods. The main difference between these methods lies in whether Zr(OPr){sub 4} is grafted onto SBA-15 first and POCl{sub 3} second (method 1) or the grafting process takes place in one pot, with SBA-15, Zr(OPr){sub 4}, and POCl{sub 3} altogether (methodmore » 2). More zirconium phosphate could be grafted by repeating the above procedures. The materials were characterized by ICP-OES, XRD, N{sub 2} adsorption-desorption, TEM, {sup 31}P and {sup 29}Si MAS NMR, and NH{sub 3}-TPD, and their applications in catalytic isopropanol dehydration, cumene cracking, and metal-ion adsorption were demonstrated. Aluminum phosphate-modified SBA-15 samples could be obtained via these two methods as well. This work enriches the family of metal phosphate-functionalized mesoporous silicas as new solid acid catalysts.« less

Electronic structure of metals and semiconductors: bulk, surface, and interface properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Louie, S.G.S.

1976-09-01

A theoretical study of the electronic structure of various metals and semiconductors is presented with the emphasis on understanding the properties of these materials when they are subjected to extreme conditions and in various different configurations. Among the bulk systems studied, the properties of cesium under high pressure are discussed in terms of the electronic structure calculated at various cell volumes using the pseudopotential method. Local fields or umklapp processes in semiconductors are studied within the random phase approximation (RPA). Specifically the dielectric response matrix epsilon/sub GG'/ (q = 0,omega) is evaluated numerically to determine the effects of local-field correctionsmore » in the optical spectrum of Si. Also, some comments on the excitonic mechanism of superconductivity are presented and the role of local fields is discussed. The pseudo-potential method is next extended to calculate the electronic structure of a transition metal Nb. The calculation is performed self-consistently with the use of a non-local ionic potential determined from atomic spectra. Finally the theory of the superconducting transition temperature T/sub c/ is discussed in the strong-coupling formulation of the BCS theory. The Eliashberg equations in the Matsubara representation are solved analytically and a general T/sub c/ equation is obtained. A new method is developed using pseudopotentials in a self-consistent manner to describe non-periodic systems. The method is applicable to localized configurations such as molecules, surfaces, impurities, vacancies, finite chains of atoms, adsorbates, and solid interfaces. Specific applications to surfaces, metal-semiconductor interfaces and vacancies are presented.« less

Ubiquitous formation of bulk Dirac cones and topological surface states from a single orbital manifold in transition-metal dichalcogenides

NASA Astrophysics Data System (ADS)

Bahramy, M. S.; Clark, O. J.; Yang, B.-J.; Feng, J.; Bawden, L.; Riley, J. M.; Marković, I.; Mazzola, F.; Sunko, V.; Biswas, D.; Cooil, S. P.; Jorge, M.; Wells, J. W.; Leandersson, M.; Balasubramanian, T.; Fujii, J.; Vobornik, I.; Rault, J. E.; Kim, T. K.; Hoesch, M.; Okawa, K.; Asakawa, M.; Sasagawa, T.; Eknapakul, T.; Meevasana, W.; King, P. D. C.

2018-01-01

Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied bulk properties, while their single-layer variants have become one of the most prominent examples of two-dimensional materials beyond graphene. Their disparate ground states largely depend on transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date. Here, we focus on the chalcogen-derived states. From density-functional theory calculations together with spin- and angle-resolved photoemission, we find that these generically host a co-existence of type-I and type-II three-dimensional bulk Dirac fermions as well as ladders of topological surface states and surface resonances. We demonstrate how these naturally arise within a single p-orbital manifold as a general consequence of a trigonal crystal field, and as such can be expected across a large number of compounds. Already, we demonstrate their existence in six separate TMDs, opening routes to tune, and ultimately exploit, their topological physics.

Atomically dispersed metal sites in MOF-based materials for electrocatalytic and photocatalytic energy conversion.

PubMed

Liang, Zibin; Qu, Chong; Xia, Dingguo; Zou, Ruqiang; Xu, Qiang

2018-02-19

Metal sites play an essential role for both electrocatalytic and photocatalytic energy conversion applications. The highly ordered arrangements of the organic linkers and metal nodes and the well-defined pore structures of metal-organic frameworks (MOFs) make them ideal substrates to support atomically dispersed metal sites (ADMSs) located in their metal nodes, linkers, and pores. Besides, porous carbon materials doped with ADMSs can be derived from these ADMS-incorporated MOF precursors through controlled treatments. These ADMSs incorporated in pristine MOFs and MOF-derived carbon materials possess unique merits over the molecular or the bulk metal-based catalysts, bridging the gap between homogeneous and heterogeneous catalysts for energy conversion applications. In this review, recent progress and perspective of design and incorporation of ADMSs in pristine MOFs and MOF-derived materials for energy conversion applications are highlighted, which will hopefully promote further developments of advanced MOF-based catalysts in foreseeable future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calculation of density of states of transition metals: From bulk sample to nanocluster

NASA Astrophysics Data System (ADS)

Krasavin, Andrey V.; Borisyuk, Petr V.; Vasiliev, Oleg S.; Zhumagulov, Yaroslav V.; Kashurnikov, Vladimir A.; Kurelchuk, Uliana N.; Lebedinskii, Yuriy Yu.

2018-03-01

A technique is presented of restoring the electronic density of states of the valence band from data of X-ray photoelectron spectroscopy (XPS). The originality of the technique consists in using a stochastic procedure to solve an integral equation relating the density of states and the experimental X-ray photoelectron spectra via the broadening function. To obtain the broadening function, only the XPS spectra of the core levels are needed. The results are presented for bulk sample of gold and tungsten and nanoclusters of tantalum; the possibility of using the results to determine the density of states of low-dimensional structures, including ensembles of metal nanoclusters, is demonstrated.

In vitro assessment of artifacts induced by titanium, titanium-zirconium and zirconium dioxide implants in cone-beam computed tomography.

PubMed

Sancho-Puchades, Manuel; Hämmerle, Christoph H F; Benic, Goran I

2015-10-01

The aim of this study was to test whether or not the intensity of artifacts around implants in cone-beam computed tomography (CBCT) differs between titanium, titanium-zirconium and zirconium dioxide implants. Twenty models of a human mandible, each containing one implant in the single-tooth gap position 45, were cast in dental stone. Five test models were produced for each of the following implant types: titanium 4.1 mm diameter (Ti4.1 ), titanium 3.3 mm diameter (Ti3.3 ), titanium-zirconium 3.3 mm diameter (TiZr3.3 ) and zirconium dioxide 3.5-4.5 mm diameter (ZrO3.5-4.5 ) implants. For control purposes, three models without implants were produced. Each model was scanned using a CBCT device. Gray values (GV) were recorded at eight circumferential positions around the implants at 0.5 mm, 1 mm and 2 mm from the implant surface (GVT est ). GV were assessed in the corresponding volumes of interest (VOI) in the control models without implants (GVC ontrol ). Differences of gray values (ΔGV) between GVT est and GVC ontrol were calculated as percentages. One-way ANOVA and post hoc tests were applied to detect differences between implant types. Mean ΔGV for ZrO3.5-4.5 presented the highest absolute values, generally followed by TiZr3.3 , Ti4.1 and Ti3.3 implants. The differences of ΔGV between ZrO3.5-4.5 and the remaining groups were statistically significant in the majority of the VOI (P ≤ 0.0167). ΔGV for TiZr3.3 , Ti4.1 and Ti3.3 implants did not differ significantly in the most VOI. For all implant types, ΔGV showed positive values buccally, mesio-buccally, lingually and disto-lingually, whereas negative values were detected mesially and distally. Zirconium dioxide implants generate significantly more artifacts as compared to titanium and titanium-zirconium implants. The intensity of artifacts around zirconium dioxide implants exhibited in average the threefold in comparison with titanium implants. © 2014 John Wiley & Sons A/S. Published by John Wiley

Fracture Mechanisms of Zirconium Diboride Ultra-High Temperature Ceramics under Pulse Loading

NASA Astrophysics Data System (ADS)

Skripnyak, Vladimir V.; Bragov, Anatolii M.; Skripnyak, Vladimir A.; Lomunov, Andrei K.; Skripnyak, Evgeniya G.; Vaganova, Irina K.

2015-06-01

Mechanisms of failure in ultra-high temperature ceramics (UHTC) based on zirconium diboride under pulse loading were studied experimentally by the method of SHPB and theoretically using the multiscale simulation method. The obtained experimental and numerical data are evidence of the quasi-brittle fracture character of nanostructured zirconium diboride ceramics under compression and tension at high strain rates and the room temperatures. Damage of nanostructured porous zirconium diboride -based UHTC can be formed under stress pulse amplitude below the Hugoniot elastic limit. Fracture of nanostructured ultra-high temperature ceramics under pulse and shock-wave loadings is provided by fast processes of intercrystalline brittle fracture and relatively slow processes of quasi-brittle failure via growth and coalescence of microcracks. A decrease of the shear strength can be caused by nano-voids clusters in vicinity of triple junctions between ceramic matrix grains and ultrafine-grained ceramics. This research was supported by grants from ``The Tomsk State University Academic D.I. Mendeleev Fund Program'' and also N. I. Lobachevski State University of Nizhny Novgorod (Grant of post graduate mobility).

Higher Order Multipole Potentials and Electrostatic Screening Effects on Cohesive Energy and Bulk Modulus of Metallic Nanoparticles

NASA Astrophysics Data System (ADS)

Barakat, T.

2011-12-01

Higher order multipole potentials and electrostatic screening effects are introduced to incorporate the dangling bonds on the surface of a metallic nanopaticle and to modify the coulomb like potential energy terms, respectively. The total interaction energy function for any metallic nanoparticle is represented in terms of two- and three-body potentials. The two-body part is described by dipole-dipole interaction potential, and in the three-body part, triple-dipole (DDD) and dipole-dipole-quadrupole (DDQ) terms are included. The size-dependent cohesive energy and bulk modulus are observed to decrease with decreasing sizes, a result which is in good agreement with the experimental values of Mo and W nanoparticles.

Revisiting Zirconium: New Abundance Determinations with Improved Oscillator Strengths

NASA Astrophysics Data System (ADS)

Burris, Debra L.; Jones, M.; Nichols, R.

2006-12-01

The element Zirconium is produced via neutron capture (n-capture). It resides in the mass range where there is uncertainty about the production mechanism at early time. The rapid n-capture process (r-process) was believed to be responsible for the production, but no study (Burris et al 2000, Gilroy et al 1988 and others) has been able to successfully use the r-process to reproduce the abundance signature for elements in this mass range for metal-poor halo stars. It has been suggested (Sneden and Cowan 2003) that there may be an undiscovered component to the r-process. New transition probabilities for Zr II have been reported by Malcheva et al (2006). We utilize these values to make new abundance determinations for Zr in the Sun and the metal-poor halo star BD +17 3248. This work is supported in part by the AAS Small Grant Program, the Arkansas Space Grant Consortium and the UCA Undergraduate Research Council.

Understanding the Irradiation Behavior of Zirconium Carbide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Motta, Arthur; Sridharan, Kumar; Morgan, Dane

2013-10-11

Zirconium carbide (ZrC) is being considered for utilization in high-temperature gas-cooled reactor fuels in deep-burn TRISO fuel. Zirconium carbide possesses a cubic B1-type crystal structure with a high melting point, exceptional hardness, and good thermal and electrical conductivities. The use of ZrC as part of the TRISO fuel requires a thorough understanding of its irradiation response. However, the radiation effects on ZrC are still poorly understood. The majority of the existing research is focused on the radiation damage phenomena at higher temperatures (>450{degree}C) where many fundamental aspects of defect production and kinetics cannot be easily distinguished. Little is known aboutmore » basic defect formation, clustering, and evolution of ZrC under irradiation, although some atomistic simulation and phenomenological studies have been performed. Such detailed information is needed to construct a model describing the microstructural evolution in fast-neutron irradiated materials that will be of great technological importance for the development of ZrC-based fuel. The goal of the proposed project is to gain fundamental understanding of the radiation-induced defect formation in zirconium carbide and irradiation response by using a combination of state-of-the-art experimental methods and atomistic modeling. This project will combine (1) in situ ion irradiation at a specialized facility at a national laboratory, (2) controlled temperature proton irradiation on bulk samples, and (3) atomistic modeling to gain a fundamental understanding of defect formation in ZrC. The proposed project will cover the irradiation temperatures from cryogenic temperature to as high as 800{degree}C, and dose ranges from 0.1 to 100 dpa. The examination of this wide range of temperatures and doses allows us to obtain an experimental data set that can be effectively used to exercise and benchmark the computer calculations of defect properties. Combining the examination of radiation

Computational studies of the glass-forming ability of model bulk metallic glasses

NASA Astrophysics Data System (ADS)

Zhang, Kai; Wang, Minglei; Papanikolaou, Stefanos; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O'Hern, Corey S.

2013-09-01

Bulk metallic glasses (BMGs) are produced by rapidly thermally quenching supercooled liquid metal alloys below the glass transition temperature at rates much faster than the critical cooling rate Rc below which crystallization occurs. The glass-forming ability of BMGs increases with decreasing Rc, and thus good glass-formers possess small values of Rc. We perform molecular dynamics simulations of binary Lennard-Jones (LJ) mixtures to quantify how key parameters, such as the stoichiometry, particle size difference, attraction strength, and heat of mixing, influence the glass-formability of model BMGs. For binary LJ mixtures, we find that the best glass-forming mixtures possess atomic size ratios (small to large) less than 0.92 and stoichiometries near 50:50 by number. In addition, weaker attractive interactions between the smaller atoms facilitate glass formation, whereas negative heats of mixing (in the experimentally relevant regime) do not change Rc significantly. These results are tempered by the fact that the slowest cooling rates achieved in our simulations correspond to ˜1011 K/s, which is several orders of magnitude higher than Rc for typical BMGs. Despite this, our studies represent a first step in the development of computational methods for quantitatively predicting glass-formability.

Thermomechanical properties of zirconium tungstate/hydrogenated nitrile butadiene rubber (HNBR) composites for low-temperature applications

NASA Astrophysics Data System (ADS)

Akulichev, Anton G.; Alcock, Ben; Tiwari, Avinash; Echtermeyer, Andreas T.

2016-12-01

Rubber compounds for pressure sealing application typically have inferior dimensional stability with temperature fluctuations compared with their steel counterparts. This effect may result in seal leakage failures when subjected to decreases in temperature. Composites of hydrogenated nitrile butadiene rubber (HNBR) and zirconium tungstate as a negative thermal expansion filler were prepared in order to control the thermal expansivity of the material. The amount of zirconium tungstate (ZrW2O8) was varied in the range of 0 to about 40 vol%. The coefficient of thermal expansion (CTE), bulk modulus, uniaxial extension and compression set properties were measured. The CTE of the ZrW2O8-filled HNBR decreases with the filler content and it is reduced by a factor of 2 at the highest filler concentration used. The filler effect on CTE is found to be stronger when HNBR is below the glass transition temperature. The experimental thermal expansion data of the composites are compared with the theoretical estimates and predictions given by FEA. The effect of ZrW2O8 on the mechanical characteristics and compression set of these materials is also discussed.

Producing Magnesium Metallic Glass By Disintegrated Melt Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shanthi, M.; Dept. of Mechanical Engineering, National University of Singapore, Singapore 117576; Gupta, M.

Bulk metallic glasses are new class of engineering materials that exhibit high resistance to crystallization in the under cooled liquid state. The development of bulk metallic glasses of thickness 1cm or less has opened new doors for fundamental studies of both liquid state and glass transition previously not feasible in metallic materials. Moreover, bulk metallic glasses exhibit superior hardness, strength, specific strength, and elastic strain limit, along with good corrosion and wear resistance. Thus they are potential candidates in various sports, structural, engineering and medical applications. Among several BMGs investigated, magnesium-based BMGs have attracted considerable attention because of their lowmore » density and superior mechanical properties. The major drawback of this magnesium based BMGs is poor ductility. This can be overcome by the addition of ductile particles/reinforcement to the matrix. In this study, a new technique named disintegrated melt deposition technique was used to synthesize magnesium based BMGs. Rods of different sizes are cast using the current method. Mechanical characterization studies revealed that the amorphous rods produced by the current technique showed superior mechanical properties.« less

Producing Magnesium Metallic Glass By Disintegrated Melt Deposition

NASA Astrophysics Data System (ADS)

Shanthi, M.; Gupta, M.; Jarfors, A. E. W.; Tan, M. J.

2011-01-01

Bulk metallic glasses are new class of engineering materials that exhibit high resistance to crystallization in the under cooled liquid state. The development of bulk metallic glasses of thickness 1cm or less has opened new doors for fundamental studies of both liquid state and glass transition previously not feasible in metallic materials. Moreover, bulk metallic glasses exhibit superior hardness, strength, specific strength, and elastic strain limit, along with good corrosion and wear resistance. Thus they are potential candidates in various sports, structural, engineering and medical applications. Among several BMGs investigated, magnesium-based BMGs have attracted considerable attention because of their low density and superior mechanical properties. The major drawback of this magnesium based BMGs is poor ductility. This can be overcome by the addition of ductile particles/reinforcement to the matrix. In this study, a new technique named disintegrated melt deposition technique was used to synthesize magnesium based BMGs. Rods of different sizes are cast using the current method. Mechanical characterization studies revealed that the amorphous rods produced by the current technique showed superior mechanical properties.

METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

DOEpatents

Vetrano, J.B.

1962-01-23

A method is given for preparing large, sound bodies of delta zirconium hydride. The method includes the steps of heating a zirconium body to a temperature of not less than l000 deg C, providing a hydrogen atmosphere for the zirconium body at a pressure not greater than one atmosphere, reducing the temperature slowly to 800 deg C at such a rate that cracks do not form while maintaining the hydrogen pressure substantially constant, and cooling in an atmosphere of hydrogen. (AEC)

Zirconium fluoride glass - Surface crystals formed by reaction with water

NASA Technical Reports Server (NTRS)

Doremus, R. H.; Bansal, N. P.; Bradner, T.; Murphy, D.

1984-01-01

The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.

Minimalistic Liquid-Assisted Route to Highly Crystalline α-Zirconium Phosphate.

PubMed

Cheng, Yu; Wang, Xiaodong Tony; Jaenicke, Stephan; Chuah, Gaik-Khuan

2017-08-24

Zirconium phosphates have potential applications in areas of ion exchange, catalysis, photochemistry, and biotechnology. However, synthesis methodologies to form crystalline α-zirconium phosphate (Zr(HPO 4 ) 2 ⋅H 2 O) typically involve the use of excess phosphoric acid, addition of HF or oxalic acid and long reflux times or hydrothermal conditions. A minimalistic sustainable route to its synthesis has been developed by using only zirconium oxychloride and concentrated phosphoric acid to form highly crystalline α-zirconium phosphate within hours. The morphology can be changed from platelets to rod-shaped particles by fluoride addition. By varying the temperature and time, α-zirconium phosphate with particle sizes from nanometers to microns can be obtained. Key features of this minimal solvent synthesis are the excellent yields obtained with high atom economy under mild conditions and ease of scalability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic analysis of the non-isothermal crystallization process, magnetic and mechanical properties of FeCoBSiNb and FeCoBSiNbCu bulk metallic glasses

NASA Astrophysics Data System (ADS)

Ramasamy, Parthiban; Stoica, Mihai; Taghvaei, A. H.; Prashanth, K. G.; Ravi Kumar, Eckert, Jürgen

2016-02-01

The crystallization kinetics of [(Fe0.5Co0.5)0.75B0.2Si0.05]96Nb4 and {[(Fe0.5Co0.5)0.75B0.2Si0.05]0.96Nb0.04}99.5Cu0.5 bulk metallic glasses were evaluated using differential scanning calorimetry under non-isothermal condition. The fully glassy rods with diameters up to 2 mm were obtained by copper mold injection casting. Both glasses show good thermal stability, but the addition of only 0.5% Cu completely changes the crystallization behavior. The average activation energy required for crystallization decreases from 645 kJ/mol to 425 kJ/mol after Cu addition. Upon heating, the Cu-free alloy forms only the metastable Fe23B6 phase. In contrast, two well-separated exothermic events are observed for the Cu-added bulk glassy samples. First, the (Fe,Co) phase nucleates and then (Fe,Co)2B and/or (Fe,Co)3B crystallize from the remaining glassy matrix. The Cu-added alloy exhibits a lower coercivity and a higher magnetic saturation than the base alloy, both in as-cast as well as in annealed condition. Besides, the Cu-added glassy sample with 2 mm diameter exhibits a maximum compressive fracture strength of 3913 MPa together with a plastic strain of 0.6%, which is highest plastic strain ever reported for 2 mm diameter ferromagnetic bulk metallic glass sample. Although Cu addition improves the magnetic and mechanical properties of the glass, it affects the glass-forming ability of the base alloy.

DISSOLUTION OF ZIRCONIUM AND ALLOYS THEREFOR

DOEpatents

Swanson, J.L.

1961-07-11

The dissolution of zirconium cladding in a water solution of ammonium fluoride and ammonium nitrate is described. The method finds particular utility in processing spent fuel elements for nuclear reactors. The zirconium cladding is first dissolved in a water solution of ammonium fluoride and ammonium nitrate; insoluble uranium and plutonium fiuorides formed by attack of the solvent on the fuel materiai of the fuel element are then separated from the solution, and the fuel materiai is dissolved in another solution.

The Crystal Structure of Thorium and Zirconium Dihydrides by X-ray and Neutron Diffraction

DOE R&D Accomplishments Database

Rundle, R.E.; Shull, C.G.; Wollan, E.O.

1951-04-20

Thorium forms a tetragonal lower hydride of composition ThH{sub 2}. The hydrides ThH{sub 2}, ThD{sub 2}, and ZrD{sub 2} have been studied by neutron diffraction in order that hydrogen positions could be determined. The hydrides are isomorphous, and have a deformed fluorite structure. Metal-hydrogen distances in thorium hydride are unusually large, as in UH{sub 3}. Thorium and zirconium scattering amplitudes and a revised scattering amplitude for deuterium are reported.

Self-ion irradiation effects on mechanical properties of nanocrystalline zirconium films

DOE PAGES

Wang, Baoming; Haque, M. A.; Tomar, Vikas; ...

2017-07-13

Zirconium thin films were irradiated at room temperature with an 800 keV Zr + beam using a 6 MV HVE Tandem accelerator to 1.36 displacement per atom damage. Freestanding tensile specimens, 100 nm thick and 10 nm grain size, were tested in-situ inside a transmission electron microscope. Significant grain growth (>300%), texture evolution, and displacement damage defects were observed. Here, stress-strain profiles were mostly linear elastic below 20 nm grain size, but above this limit the samples demonstrated yielding and strain hardening. Experimental results support the hypothesis that grain boundaries in nanocrystalline metals act as very effective defect sinks.

A size-dependent constitutive model of bulk metallic glasses in the supercooled liquid region

PubMed Central

Yao, Di; Deng, Lei; Zhang, Mao; Wang, Xinyun; Tang, Na; Li, Jianjun

2015-01-01

Size effect is of great importance in micro forming processes. In this paper, micro cylinder compression was conducted to investigate the deformation behavior of bulk metallic glasses (BMGs) in supercooled liquid region with different deformation variables including sample size, temperature and strain rate. It was found that the elastic and plastic behaviors of BMGs have a strong dependence on the sample size. The free volume and defect concentration were introduced to explain the size effect. In order to demonstrate the influence of deformation variables on steady stress, elastic modulus and overshoot phenomenon, four size-dependent factors were proposed to construct a size-dependent constitutive model based on the Maxwell-pulse type model previously presented by the authors according to viscosity theory and free volume model. The proposed constitutive model was then adopted in finite element method simulations, and validated by comparing the micro cylinder compression and micro double cup extrusion experimental data with the numerical results. Furthermore, the model provides a new approach to understanding the size-dependent plastic deformation behavior of BMGs. PMID:25626690

Fast and robust standard-deviation-based method for bulk motion compensation in phase-based functional OCT.

PubMed

Wei, Xiang; Camino, Acner; Pi, Shaohua; Cepurna, William; Huang, David; Morrison, John C; Jia, Yali

2018-05-01

Phase-based optical coherence tomography (OCT), such as OCT angiography (OCTA) and Doppler OCT, is sensitive to the confounding phase shift introduced by subject bulk motion. Traditional bulk motion compensation methods are limited by their accuracy and computing cost-effectiveness. In this Letter, to the best of our knowledge, we present a novel bulk motion compensation method for phase-based functional OCT. Bulk motion associated phase shift can be directly derived by solving its equation using a standard deviation of phase-based OCTA and Doppler OCT flow signals. This method was evaluated on rodent retinal images acquired by a prototype visible light OCT and human retinal images acquired by a commercial system. The image quality and computational speed were significantly improved, compared to two conventional phase compensation methods.

Reaction of Titanium and Zirconium Particles in Cylindrical Explosive Charges

NASA Astrophysics Data System (ADS)

Frost, David; Cairns, Malcolm; Goroshin, Samuel; Zhang, Fan

2007-06-01

The critical conditions for the reaction of high melting-point metallic particles (Ti, Zr) dispersed during the detonation of long cylindrical explosive charges have been investigated experimentally. The charges consisted of packed beds of either spherical titanium particles (with diameters of 35, 90, or 215 μm; AP&C, Inc.) or nonspherical zirconium particles (250 -- 500 μm or 500 -- 600 μm, Atlantic Equipment Eng., NJ) saturated with sensitized liquid nitromethane. For the titanium particles, a threshold particle diameter exists, above which self-sustained particle reaction is not observed, although some particle reaction occurs immediately behind the detonation front then rapidly quenches. For the smallest particles, the proportion of the conical particle cloud that reacts increases with charge diameter, suggesting that the reaction initiation is a competition between particle heating and expansion cooling of the products. For zirconium particles, no critical conditions exist; particle ignition was observed for all particle and charge diameters tested. In this case, interaction of the high pressure detonation wave with the particles is sufficient to initiate reaction at the particle surface after a delay time (˜ 10's μs), which is much less than the time required for thermal equilibration of the particles.

In Vivo Evaluation of Bulk Metallic Glasses for Osteosynthesis Devices

PubMed Central

Imai, Kazuhiro; Hiromoto, Sachiko

2016-01-01

Bulk metallic glasses (BMGs) show higher strength and lower Young’s modulus than Ti-6Al-4V alloy and SUS 316L stainless steel. This study aimed to perform in vivo evaluations of Zr65Al7.5Ni10Cu17.5 BMGs for osteosynthesis devices. In the study for intramedullary implants, osteotomies of the femoral bones were performed in male Wistar rats and were stabilized with Zr65Al7.5Ni10Cu17.5 BMGs, Ti-6Al-4V alloy, or 316L stainless steel intramedullary nails for 12 weeks. In the study for bone surface implants, Zr65Al7.5Ni10Cu17.5 BMGs ribbons were implanted on the femur surface for 6 weeks. Local effects on the surrounding soft tissues of the implanted BMGs were assessed by histological observation. Implanted materials’ surfaces were examined using scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM-EDS). In the study for intramedullary implants, bone healing after osteotomy was assessed by peripheral quantitative computed tomography (QCT) and mechanical tests. Histological observation showed no findings of the biological effects. SEM-EDS showed no noticeable change on the surface of BMGs, while Ca and P deposition was seen on the Ti-6Al-4V alloy surface, and irregularities were seen on the 316L stainless steel surface. Mechanical test and peripheral QCT showed that, although there was no significant difference, bone healing of BMGs was more than that of Ti-6Al-4V alloy. The results indicated that Zr-based BMGs can lead to bone healing equal to or greater than Ti-6Al-4V alloy. Zr-based BMGs exhibited the advantage of less bone bonding and easier implant removal compared with Ti-6Al-4V alloy. In conclusion, Zr-based BMGs are promising for osteosynthesis devices that are eventually removed. PMID:28773792

ZrCuAl Bulk Metallic Glass spall induced by laser shock

NASA Astrophysics Data System (ADS)

Jodar, Benjamin; Loison, Didier; Yokoyama, Yoshihiko; Lescoute, Emilien; Berthe, Laurent; Sangleboeuf, Jean-Christophe

2017-06-01

To face High Velocity Impacts, the aerospace industry is always seeking for innovative materials usable as debris shielding components. Bulk Metallic Glasses (BMG) revealed interesting mechanical properties in case of static and quasi-static loading conditions: high elasticity, high tenacity, low density and high fracture threshold... The department of Mechanics and Glass of the Institut of Physics Rennes conducted on the ELFIE facility, laser shock experiments to study the behavior of a ternary ZrCuAl BMG under high strain rate, up-to fragmentation process. On the one hand, in-situ diagnostics were used to measure ejection velocities with PDV and debris morphologies were observed by Shadowgraphy. On the other hand, spalled areas (dimensions and features) were characterized through post-mortem analysis (optical observations, profilometry and SEM). These results are compared to experimental and numerical data on the crystalline forms of the ZrCuAl basic compounds.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties

NASA Astrophysics Data System (ADS)

Marcellini, Moreno; Fernandes, Francisco M.; Dedovets, Dmytro; Deville, Sylvain

2017-04-01

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties.

PubMed

Marcellini, Moreno; Fernandes, Francisco M; Dedovets, Dmytro; Deville, Sylvain

2017-04-14

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Metal matrix composite of an iron aluminide and ceramic particles and method thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneibel, Joachim H.

A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1450.degree. C. for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

Metal matrix composite of an iron aluminide and ceramic particles and method thereof

DOEpatents

Schneibel, J.H.

1997-06-10

A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1,450 C for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

Metal matrix composite of an iron aluminide and ceramic particles and method thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneibel, J.H.

A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1,450 C for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of the...

Direct synthesis of zirconium powder by magnesium reduction

NASA Astrophysics Data System (ADS)

Lee, Dong-Won; Yun, Jung-Yeul; Yoon, Sung-Won; Wang, Jei-Pil

2013-05-01

The direct synthesis of zirconium powder has been conducted through an analysis of the chemical reaction between evaporated ZrCl4 and molten magnesium over a range of reduction temperatures, concentration of hydrochloric acid, and stirring time. The observed results indicated that the purity of zirconium powder increased with increased stirring time, and Mg and MgCl2 were removed by 10 wt% of hydrochloric acid solution. The pure zirconium powder was obtained by stirring again for 5 h using 5 wt% of hydrochloric acid solution. It was noted that the mean particle size increased when the reaction temperature was increased, and the size of the powder at 1,123 K and 1,173 K was found to be 10 μm and 15 μm, respectively. In addition, the purity of the powder was also improved with temperature, and its purity finally reached up to 99.5% at 1,250 K. Overall, pure zirconium powder was obtained after a stirring stage for 5 hours using 5 wt% of hydrochloric acid solution.

Probing elastically or plastically induced structural heterogeneities in bulk metallic glasses by nanoindentation pop-in tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Tingkun; Gao, Yanfei; Bei, Hongbin

Shear banding dynamics in bulk metallic glasses (BMGs) is manifested by the spatiotemporal evolution of strain fields which in turn depend on structural heterogeneities. The spacing of these heterogeneities, as a characteristic length scale, was determined from the analysis of nanoindentation pop-in tests using a stochastic model. Furthermore, the pre-stress by elastic bending and residual stress by plastic bending of BMG plates were found to dramatically decrease such spacings, thus increasing heterogeneity density and mechanically rejuvenating the glass structure.

Probing elastically or plastically induced structural heterogeneities in bulk metallic glasses by nanoindentation pop-in tests

DOE PAGES

Liu, Tingkun; Gao, Yanfei; Bei, Hongbin

2017-07-21

Shear banding dynamics in bulk metallic glasses (BMGs) is manifested by the spatiotemporal evolution of strain fields which in turn depend on structural heterogeneities. The spacing of these heterogeneities, as a characteristic length scale, was determined from the analysis of nanoindentation pop-in tests using a stochastic model. Furthermore, the pre-stress by elastic bending and residual stress by plastic bending of BMG plates were found to dramatically decrease such spacings, thus increasing heterogeneity density and mechanically rejuvenating the glass structure.

Achieving high energy absorption capacity in cellular bulk metallic glasses

PubMed Central

Chen, S. H.; Chan, K. C.; Wu, F. F.; Xia, L.

2015-01-01

Cellular bulk metallic glasses (BMGs) have exhibited excellent energy-absorption performance by inheriting superior strength from the parent BMGs. However, how to achieve high energy absorption capacity in cellular BMGs is vital but mysterious. In this work, using step-by-step observations of the deformation evolution of a series of cellular BMGs, the underlying mechanisms for the remarkable energy absorption capacity have been investigated by studying two influencing key factors: the peak stress and the decay of the peak stress during the plastic-flow plateau stages. An analytical model of the peak stress has been proposed, and the predicted results agree well with the experimental data. The decay of the peak stress has been attributed to the geometry change of the macroscopic cells, the formation of shear bands in the middle of the struts, and the “work-softening” nature of BMGs. The influencing factors such as the effect of the strut thickness and the number of unit cells have also been investigated and discussed. Strategies for achieving higher energy absorption capacity in cellular BMGs have been proposed. PMID:25973781

Nuclear-grade zirconium prepared by combining combustion synthesis with molten-salt electrorefining technique

NASA Astrophysics Data System (ADS)

Li, Hui; Nersisyan, Hayk H.; Park, Kyung-Tae; Park, Sung-Bin; Kim, Jeong-Guk; Lee, Jeong-Min; Lee, Jong-Hyeon

2011-06-01

Zirconium has a low absorption cross-section for neutrons, which makes it an ideal material for use in nuclear reactor applications. However, hafnium typically contained in zirconium causes it to be far less useful for nuclear reactor materials because of its high neutron-absorbing properties. In the present study, a novel effective method has been developed for the production of hafnium-free zirconium. The process includes two main stages: magnesio-thermic reduction of ZrSiO 4 under a combustion mode, to produce zirconium silicide (ZrSi), and recovery of hafnium-free zirconium by molten-salt electrorefining. It was found that, depending on the electrorefining procedure, it is possible to produce zirconium powder with a low hafnium content: 70 ppm, determined by ICP-AES analysis.

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Capture of Tritium Released from Cladding in the Zirconium Recycle Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, Barry B.; Walker, T. B.; Bruffey, Stephanie H.

2016-08-31

This report is issued as the first revision to FCRD-MRWFD-2016-000297. Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-basedmore » cladding and could be released from the cladding when the solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using non-radioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.« less

Impacts of Long-Range Transport of Metals from East Asia in Bulk Aerosols Collected at the Okinawa Archipelago, Japan

NASA Astrophysics Data System (ADS)

A, Sotaro; S, Yuka; I, Moriaki; N, Fumiya; H, Daishi; A, Takemitsu; T, Akira

2010-05-01

Economy of East Asia has been growing rapidly, and atmospheric aerosols discharged from this region have been transported to Japan. Okinawa island is situated approximately 1500 km south of Tokyo, Japan, 2000 km southeast of Beijing, China, and 1000 km of south Korea. Its location in Asian is well suited for studying long-range transport of air pollutants in East Asia because maritime air mass prevails during summer, while continental air mass dominates during fall, winter, and spring. The maritime air mass data can be seen as background and can be compared with continental air mass which has been affected by anthropogenic activities. Therefore, Okinawa region is suitable area for studying impacts of air pollutants from East Asia. We simultaneously collected bulk aerosol samples by using the same type of high volume air samplers at Cape Hedo Atmospheric Aerosol Monitoring Station (CHAAMS, Okinawa island), Kume island (ca. 160 km south-west of CHAAMS), and Minami-Daitou island (ca. 320 km south-east of CHAAMS). We determined the concentrations of acid-digested metals using atomic absorption spectrometer and inductively-coupled plasma mass spectrometry (ICP-MS). We report and discuss spatial and temporal distribution of metals in the bulk atmospheric aerosols collected at CHAAMS, Kume island and Minami-Daitou island during June, 2008 to June 2009. We also determined 'background' concentration of metals in Okinawa archipelago. We then compare each chemical component among CHAAMS, Kume island and Minami-Daitou island to elucidate the influence of the transport processes and distances from Asian continent on metal concentrations.

Effect of high strain rates on peak stress in a Zr-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Sunny, George; Yuan, Fuping; Prakash, Vikas; Lewandowski, John

2008-11-01

The mechanical behavior of Zr41.25Ti13.75Cu12.5Ni10Be22.5 (LM-1) has been extensively characterized under quasistatic loading conditions; however, its mechanical behavior under dynamic loading conditions is currently not well understood. A Split-Hopkinson pressure bar (SHPB) and a single-stage gas gun are employed to characterize the mechanical behavior of LM-1 in the strain-rate regime of 102-105/s. The SHPB experiments are conducted with a tapered insert design to mitigate the effects of stress concentrations and preferential failure at the specimen-insert interface. The higher strain-rate plate-impact compression-and-shear experiments are conducted by impacting a thick tungsten carbide (WC) flyer plate with a sandwich sample comprising a thin bulk metallic glass specimen between two thicker WC target plates. Specimens employed in the SHPB experiments failed in the gage-section at a peak stress of approximately 1.8 GPa. Specimens in the high strain-rate plate-impact experiments exhibited a flow stress in shear of approximately 0.9 GPa, regardless of the shear strain-rate. The flow stress under the plate-impact conditions was converted to an equivalent flow stress under uniaxial compression by assuming a von Mises-like material behavior and accounting for the plane strain conditions. The results of these experiments, when compared to the previous work conducted at quasistatic loading rates, indicate that the peak stress of LM-1 is essentially strain rate independent over the strain-rate range up to 105/s.

The effect of environmental factors on selected mechanical properties of zirconium dioxide

NASA Astrophysics Data System (ADS)

Wirwicki, W.; Andrzejewska, A.; Andryszczyk, M.; Siemianowski, P.

2018-04-01

In many centers around the world, research studies are carried out on the mechanical strength of dental materials and glued joints. A literature review shows the variety of testing techniques related to analyzing the strength and durability of the material itself and the glued joints. In dental ceramics, zirconium dioxide is most often used as a base material, and chemically it consists of 97% ZrO2 and 3% Y2O3. This study was to determine the mechanical properties of zirconium dioxide under different environmental conditions. The material is used for the production of dental crowns and tooth bridges in the CAD/CAM technology. This medium is currently one of the most advanced-generation materials used for prosthetic and implant restorations. They were then subjected to a three-point bending test on the Instron ElektroPlus E3000 durability machine. Storage conditions and time have a positive influence on reducing variation in zirconium resistance for active forces and destructive stresses.

Amorphous metal alloy

DOEpatents

Wang, R.; Merz, M.D.

1980-04-09

Amorphous metal alloys of the iron-chromium and nickel-chromium type have excellent corrosion resistance and high temperature stability and are suitable for use as a protective coating on less corrosion resistant substrates. The alloys are stabilized in the amorphous state by one or more elements of titanium, zirconium, hafnium, niobium, tantalum, molybdenum, and tungsten. The alloy is preferably prepared by sputter deposition.

Regulation of Mesenchymal Stem Cell Differentiation by Nanopatterning of Bulk Metallic Glass.

PubMed

Loye, Ayomiposi M; Kinser, Emily R; Bensouda, Sabrine; Shayan, Mahdis; Davis, Rose; Wang, Rui; Chen, Zheng; Schwarz, Udo D; Schroers, Jan; Kyriakides, Themis R

2018-06-08

Mesenchymal stem cell (MSC) differentiation is regulated by surface modification including texturing, which is applied to materials to enhance tissue integration. Here, we used Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 bulk metallic glass (Pt-BMG) with nanopatterned surfaces achieved by thermoplastic forming to influence differentiation of human MSCs. Pt-BMGs are a unique class of amorphous metals with high strength, elasticity, corrosion resistance, and an unusual plastic-like processability. It was found that flat and nanopattened Pt-BMGs induced osteogenic and adipogenic differentiation, respectively. In addition, osteogenic differentiation on flat BMG exceeded that observed on medical grade titanium and was associated with increased formation of focal adhesions and YAP nuclear localization. In contrast, cells on nanopatterned BMGs exhibited rounded morphology, formed less focal adhesions and had mostly cytoplasmic YAP. These changes were preserved on nanopatterns made of nanorods with increased stiffness due to shorter aspect ratios, suggesting that MSC differentiation was primarily influenced by topography. These observations indicate that both elemental composition and nanotopography can modulate biochemical cues and influence MSCs. Moreover, the processability and highly tunable nature of Pt-BMGs enables the creation of a wide range of surface topographies that can be reproducibly and systematically studied, leading to the development of implants capable of engineering MSC functions.

High performance polymer solar cells with as-prepared zirconium acetylacetonate film as cathode buffer layer

PubMed Central

Tan, Zhan'ao; Li, Shusheng; Wang, Fuzhi; Qian, Deping; Lin, Jun; Hou, Jianhui; Li, Yongfang

2014-01-01

Low-work-function active metals are commonly used as cathode in polymer solar cells (PSCs), but sensitivity of the active metals towards moisture and oxygen results in poor stability of the devices. Therefore, solution-proceessable and stable cathode buffer layer is of great importance for the application of PSCs. Here we demonstrate high performance PSCs by employing as-prepared zirconium acetylacetonate (a-ZrAcac) film spin-cast from its ethanol solution as cathode buffer layer. The PSCs based on a low bandgap polymer PBDTBDD as donor and PC60BM as acceptor with a-ZrAcac/Al cathode demonstrated an average power conversion efficiency (PCE) of 8.75% which is significantly improved than that of the devices with traditional Ca/Al cathode. The improved photovoltaic performance is benefitted from the decreased series resistance and enhanced light harvest of the PSCs with the a-ZrAcac/Al cathode. The results indicate that a-ZrAcac is a promising high performance cathode buffer layer for fabricating large area flexible PSCs. PMID:24732976

40 CFR 721.10598 - Lead strontium titanium zirconium oxide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lead strontium titanium zirconium... Specific Chemical Substances § 721.10598 Lead strontium titanium zirconium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as lead strontium...

40 CFR 721.10598 - Lead strontium titanium zirconium oxide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lead strontium titanium zirconium... Specific Chemical Substances § 721.10598 Lead strontium titanium zirconium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as lead strontium...

Dual self-organised shear banding behaviours and enhanced ductility in phase separating Zr-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Zhang, Z. Q.; Song, K. K.; Sun, B. A.; Wang, L.; Cui, W. C.; Qin, Y. S.; Han, X. L.; Xue, Q. S.; Peng, C. X.; Sarac, B.; Spieckermann, F.; Kaban, I.; Eckert, J.

2018-07-01

The multiplication and interaction of self-organised shear bands often transform to a stick-slip behaviour of a major shear band along the primary shear plane, and ultimately the major shear band becomes runaway and terminates the plasticity of bulk metallic glasses (BMGs). Here, we examined the deformation behaviours of the nanoscale phase-separating Zr65-xCu25Al10Fex (x = 5 and 7.5 at.%) BMGs. The formation of multi-step phase separation, being mainly governed by nucleation and growth, results in the microstructural inhomogeneity on a wide range of length-scales and leads to obviously macroscopic and repeatable ductility. The good deformability can be attributed to two mechanisms for stabilizing shear banding process, i.e. the mutual interaction of multiple shear bands away from the major shear band and the delaying slip-to-failure of dense fine shear bands around the major shear band, both of which show a self-organised criticality yet with different power-law exponents. The two mechanisms could come into effect in the intermediate (stable) and later plastic deformation regime, respectively. Our findings provide a possibility to enhance the shear banding stability over the whole plastic deformation through a proper design of microstructure heterogeneities.

Layer Formation On Metal Surfaces In Lead-Bismuth At High Temperatures In Presence Of Zirconium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loewen, Eric Paul; Yount, Hannah J.; Volk, Kevin

If the operating temperature lead–bismuth cooled fission reactor could be extended to 800 °C, they could produce hydrogen directly from water. A key issue for the deployment of this technology at these temperatures is the corrosion of the fuel cladding and structural materials by the lead–bismuth. Corrosion studies of several metals were performed to correlate the interaction layer formation rate as a function of time, temperature, and alloy compositions. The interaction layer is defined as the narrow band between the alloy substrate and the solidified lead–bismuth eutectic on the surface. Coupons of HT-9, 410, 316L, and F22 were tested atmore » 550 and 650 °C for 1000 h inside a zirconium corrosion cell. The oxygen potential ranged from approximately 10-22 to 10-19 Pa. Analyses were performed on the coupons to determine the depth of the interaction layer and the composition, at each time step (100, 300, and 1000 h). The thickness of the interaction layer on F22 at 550 °C was 25.3 µm, the highest of all the alloys tested, whereas at 650 °C, the layer thickness was only 5.6 µm, the lowest of all the alloys tested. The growth of the interaction layer on F22 at 650 °C was suppressed, owing to the presence of Zr (at 1500 wppm) in the LBE. In the case of 316L, the interaction layers of 4.9 and 10.6 µm were formed at 550 and 650 °C, respectively.« less

Synthesis of UiO-66-OH zirconium metal-organic framework and its application for selective extraction and trace determination of thorium in water samples by spectrophotometry

NASA Astrophysics Data System (ADS)

Moghaddam, Zahra Safaei; Kaykhaii, Massoud; Khajeh, Mostafa; Oveisi, Ali Reza

2018-04-01

In this study, a zirconium-based metal-organic framework (Zr-MOF), named UiO-66-OH, was synthesized by the solvo-thermal method and characterized by Fourier transform-infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). This Zr-MOF was then employed as a sorbent for selective extraction and preconcentration of thorium ions after their complexation with 2-(2,4-dihydroxyphenyl)-3,5,7-trihydroxychromen-4-one (morin) from environmental water samples prior to its spectrophotometrical determination. The experimental parameters affecting extraction, such as pH of sample solution, amount of Zr-MOF, type and volume of eluting solvent, adsorption and desorption time, and concentration of complexing agent were evaluated and optimized. Under the optimized conditions, an enrichment factor of 250 was achieved. The limit of detection was calculated to be 0.35 μg·L- 1 with a linear range between 10 and 2000 μg·L- 1of thorium. The maximum sorption capacity of MOF toward thorium was found to be 47.5 mg·g- 1. The proposed procedure was successfully applied to the analysis of real water samples.

Zirconium oxocluster/polymer hybrid nanoparticles prepared by photoactivated miniemulsion copolymerization

NASA Astrophysics Data System (ADS)

Benedetti, Cesare; Flouda, Paraskevi; Antonello, Alice; Rosenauer, Christine; Pérez-Pla, Francisco F.; Landfester, Katharina; Gross, Silvia; Muñoz-Espí, Rafael

2017-09-01

The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate)12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free radical miniemulsion copolymerization. The kinetics of the polymerization process in the absence and in the presence of the oxocluster is also investigated.

Remanufacture of Zirconium-Based Conversion Coatings on the Surface of Magnesium Alloy

NASA Astrophysics Data System (ADS)

Liu, Zhe; Jin, Guo; Song, Jiahui; Cui, Xiufang; Cai, Zhaobing

2017-04-01

Brush plating provides an effective method for creating a coating on substrates of various shapes. A corroded zirconium-based conversion coating was removed from the surface of a magnesium alloy and then replaced with new coatings prepared via brush plating. The structure and composition of the remanufactured coating were determined via x-ray photoelectron spectroscopy, x-ray diffraction, and Fourier transform infrared spectroscopy. The results revealed that the coatings consist of oxide, fluoride, and tannin-related organics. The composition of the coatings varied with the voltage. Furthermore, as revealed via potentiodynamic polarization spectroscopy, these coatings yielded a significant increase in the corrosion resistance of the magnesium alloy. The friction coefficient remained constant for almost 300s during wear resistance measurements performed under a 1-N load and dry sliding conditions, indicating that the remanufactured coatings provide effective inhibition to corrosion.

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Combined treatment with laser sintering and zirconium: a case report of dentinogenesis imperfecta.

PubMed

Ayyildiz, Simel; Sahin, Cem; Akgün, Ozlem Marti; Basak, Feridun

2013-01-01

Osteogenesis imperfecta (OI) is a heterogeneous disorder of connective tissue that manifests mainly as skeletal deformity and bone fragility. Dentinogenesis imperfecta (DI) is sometimes an accompanying symptom of OI. The treatment protocol of these patients varies according to the clinical appearance. The case report here describes complete mouth rehabilitation of an 18-year-old male patient with OI and DI using direct metal laser sintering (DMLS) technique of metal-ceramic restorations and zirconium all-ceramic crowns. DMLS is an additive metal fabrication technology that is simpler, more precise, and healthier than conventional manufacturing and can be remarkably cost effective. Moreover, the technique affords highly accurate production of fixed partial dentures with ideal marginal fit and excellent mechanical properties. The patient was treated using a multidisciplinary strategy that focused on controlling caries, protecting teeth from further wear, obtaining an appropriate vertical dimension, and providing soft tissue support to return the facial profile to a normal appearance using new technology in the field of prosthetics.

Combined Treatment with Laser Sintering and Zirconium: A Case Report of Dentinogenesis Imperfecta

PubMed Central

Sahin, Cem; Akgün, Özlem Marti; Basak, Feridun

2013-01-01

Osteogenesis imperfecta (OI) is a heterogeneous disorder of connective tissue that manifests mainly as skeletal deformity and bone fragility. Dentinogenesis imperfecta (DI) is sometimes an accompanying symptom of OI. The treatment protocol of these patients varies according to the clinical appearance. The case report here describes complete mouth rehabilitation of an 18-year-old male patient with OI and DI using direct metal laser sintering (DMLS) technique of metal-ceramic restorations and zirconium all-ceramic crowns. DMLS is an additive metal fabrication technology that is simpler, more precise, and healthier than conventional manufacturing and can be remarkably cost effective. Moreover, the technique affords highly accurate production of fixed partial dentures with ideal marginal fit and excellent mechanical properties. The patient was treated using a multidisciplinary strategy that focused on controlling caries, protecting teeth from further wear, obtaining an appropriate vertical dimension, and providing soft tissue support to return the facial profile to a normal appearance using new technology in the field of prosthetics. PMID:23533828

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, A.B. Jr.; Levy, I.S.; Trimble, D.J.; Lanning, D.D.; Gerber, F.S.

1990-04-10

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-based materials is disclosed. Samples of zirconium-based materials having different compositions and/or fabrication methods are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280 to 316 C). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hydriding for the same materials when subject to in-reactor (irradiated) corrosion. 1 figure.

Unified bulk-boundary correspondence for band insulators

NASA Astrophysics Data System (ADS)

Rhim, Jun-Won; Bardarson, Jens H.; Slager, Robert-Jan

2018-03-01

The bulk-boundary correspondence, a topic of intensive research interest over the past decades, is one of the quintessential ideas in the physics of topological quantum matter. Nevertheless, it has not been proven in all generality and has in certain scenarios even been shown to fail, depending on the boundary profiles of the terminated system. Here, we introduce bulk numbers that capture the exact number of in-gap modes, without any such subtleties in one spatial dimension. Similarly, based on these 1D bulk numbers, we define a new 2D winding number, which we call the pole winding number, that specifies the number of robust metallic surface bands in the gap as well as their topological character. The underlying general methodology relies on a simple continuous extrapolation from the bulk to the boundary, while tracking the evolution of Green's function's poles in the vicinity of the bulk band edges. As a main result we find that all the obtained numbers can be applied to the known insulating phases in a unified manner regardless of the specific symmetries. Additionally, from a computational point of view, these numbers can be effectively evaluated without any gauge fixing problems. In particular, we directly apply our bulk-boundary correspondence construction to various systems, including 1D examples without a traditional bulk-boundary correspondence, and predict the existence of boundary modes on various experimentally studied graphene edges, such as open boundaries and grain boundaries. Finally, we sketch the 3D generalization of the pole winding number by in the context of topological insulators.

Metal Organic Framework-Metal Oxide Composites for Toxic Gas Adsorption and Sensing

DTIC Science & Technology

2014-05-01

zeolitic imidazolate framework Zn(NO3)2 zinc nitrate ZrCl4 zirconium chloride 21 SUMMARY Metal organic frameworks (MOFs) and metal oxide-MOF...performed better for the other gases and conditions. Compared to the standard adsorbents BPL carbon and zeolite 13X, the cobalt and magnesium MOF...g)24 and zeolite 5A (1.25 mmol/g),25 compared to 3.5 mmol/g for Ni-MOF-74, 4 mmol/g for Mg-MOF-74, and 6 mmol/g for Co-MOF-74. Mg-MOF-74 shows the

Mechanical resistance of zirconium implant abutments: A review of the literature

PubMed Central

Vaquero-Aguilar, Cristina; Torres-Lagares, Daniel; Jiménez-Melendo, Manuel; Gutiérrez-Pérez, José L.

2012-01-01

The increase of aesthetic demands, together with the successful outcome of current implants, has renewed interest in the search for new materials with enough mechanical properties and better aesthetic qualities than the materials customarily used in implanto-prosthetic rehabilitation. Among these materials, zirconium has been used in different types of implants, including prosthetic abutments. The aim of the present review is to analyse current scientific evidence supporting the use of this material for the above mentioned purposes. We carried out the review of the literature published in the last ten years (2000 through 2010) of in vitro trials of dynamic and static loading of zirconium abutments found in the databases of Medline and Cochrane using the key words zirconium abutment, fracture resistance, fracture strength, cyclic loading. Although we have found a wide variability of values among the different studies, abutments show favourable clinical behaviour for the rehabilitation of single implants in the anterior area. Such variability may be explained by the difficulty to simulate daily mastication under in vitro conditions. The clinical evidence, as found in our study, does not recommend the use of implanto-prosthetic zirconium abutments in the molar area. Key words: Zirconium abutment, zirconium implant abutment, zirconia abutment, fracture resistance, fracture strength, cyclic loading. PMID:22143702

40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges resulting...

Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.