Half-Heusler (TiZrHf)NiSn Unileg Module with High Powder Density.

PubMed

Populoh, Sascha; Brunko, Oliver C; Gałązka, Krzysztof; Xie, Wenjie; Weidenkaff, Anke

2013-03-27

(TiZrHf)NiSn half-Heusler compounds were prepared by arc melting and their thermoelectric properties characterized in the temperature range between 325 K and 857 K, resulting in a Figure of Merit ZT ≈ 0.45. Furthermore, the prepared samples were used to construct a unileg module. This module was characterized in a homemade thermoelectric module measurement stand and yielded 275 mW/cm² and a maximum volumetric power density of 700 mW/cm³. This was reached using normal silver paint as a contacting material; from an improved contacting, much higher power yields are to be expected.

Half-Heusler (TiZrHf)NiSn Unileg Module with High Powder Density

PubMed Central

Populoh, Sascha; Brunko, Oliver C.; Gałązka, Krzysztof; Xie, Wenjie; Weidenkaff, Anke

2013-01-01

(TiZrHf)NiSn half-Heusler compounds were prepared by arc melting and their thermoelectric properties characterized in the temperature range between 325 K and 857 K, resulting in a Figure of Merit ZT ≈ 0.45. Furthermore, the prepared samples were used to construct a unileg module. This module was characterized in a homemade thermoelectric module measurement stand and yielded 275 mW/cm2 and a maximum volumetric power density of 700 mW/cm3. This was reached using normal silver paint as a contacting material; from an improved contacting, much higher power yields are to be expected. PMID:28809212

Zr and Hf diffusion in rutile

NASA Astrophysics Data System (ADS)

Cherniak, D. J.; Manchester, J.; Watson, E. B.

2007-09-01

Chemical diffusion of Zr and Hf under anhydrous conditions has been measured in synthetic and natural rutile. The sources of diffusant used were hafnon or zircon powders or a hafnon-rutile mixture. Experiments were run in crimped Pt capsules in air, or in sealed silica glass capsules with solid buffers (to buffer at NNO or QFM). Rutherford Backscattering Spectrometry (RBS) was used to measure Zr and Hf diffusion profiles. From these measurements, the following Arrhenius relations were obtained: For Zr diffusion parallel to c, over the temperature range 750-1100 °C DZr¦c = 9.8 × 10 - 15 exp(- 170 ± 30 kJ mol - 1 /RT) m 2 s - 1 For Hf diffusion parallel to c, over the temperature range 800-1000 °C DHf¦c = 9.1 × 10 - 15 exp(- 169 ± 36 kJ mol - 1 /RT) m 2 s - 1 For Hf diffusion normal to c, over the temperature range 750-1050 °C DHf⊥c = 2.5 × 10 - 12 exp(- 227 ± 62 kJ mol - 1 /RT) m 2 s - 1 . Diffusivities for experiments buffered at QFM and NNO are similar to those run in air. Diffusivities in synthetic and natural rutile are likewise similar, indicating that these findings can be applied directly in determining Zr diffusivities in rutile in natural systems. These data indicate that rutile should be moderately retentive of Zr chemical signatures, with Zr diffusivities within an order of magnitude of those for Pb in rutile over most geologic conditions. When applied in evaluation of the relative robustness of the recently developed Zr-in-rutile geothermometer [T. Zack, R. Moraes, A. Kronz, Temperature dependence of Zr in rutile: empirical calibration of a rutile thermometer, Contributions to Mineralogy and Petrology 148 (2004) 471-488., E.B. Watson, D.A. Wark, J.B. Thomas, Crystallization thermometers for zircon and rutile, Contributions to Mineralogy and Petrology 151 (2006) 413-433.], these findings suggest that Zr concentrations in rutile will be somewhat more likely to be affected by later thermal disturbance than the geothermometer based on Zr

Electron-stimulated desorption from polished and vacuum fired 316LN stainless steel coated with Ti-Zr-Hf-V

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

Malyshev, Oleg B., E-mail: oleg.malyshev@stfc.ac.uk; Valizadeh, Reza; Hogan, Benjamin T.

2014-11-01

In this study, two identical 316LN stainless steel tubular samples, which had previously been polished and vacuum-fired and then used for the electron-stimulated desorption (ESD) experiments, were coated with Ti-Zr-Hf-V with different morphologies: columnar and dense. ESD measurement results after nonevaporable getter (NEG) activation to 150, 180, 250, and 350 °C indicated that the values for the ESD yields are significantly (2–20 times) lower than the data from our previous study with similar coatings on nonvacuum-fired samples. Based on these results, the lowest pressure and best long-term performance in particle accelerators will be achieved with a vacuum-fired vacuum chamber coated withmore » dense Ti-Zr-Hf-V coating activated at 180 °C. This is likely due to the following facts: after NEG activation, the hydrogen concentration inside the NEG was lower than in the bulk stainless steel substrate; the NEG coating created a barrier for gas diffusion from the sample bulk to vacuum; the dense NEG coating performed better as a barrier than the columnar NEG coating.« less

Electronic structure and energetics of the tetragonal distortion for TiH2, ZrH2 and HfH2: a first principles study

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

Quijano, Ramiro; DeCoss, Romeo; Singh, David J

2009-01-01

The electronic structure and energetics of the tetragonal distortion for the fluorite-type dihydrides TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} are studied by means of highly accurate first-principles total-energy calculations. For HfH{sub 2}, in addition to the calculations using the scalar relativistic (SR) approximation, calculations including the spin-orbit coupling have also been performed. The results show that TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} in the cubic phase are unstable against tetragonal strain. For the three systems, the total energy shows two minima as a function of the c/a ratio with the lowest-energy minimum at c/a < 1 in agreementmore » with the experimental observations. The band structure of TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} (SR) around the Fermi level shows two common features along the two major symmetry directions of the Brillouin zone, {Lambda}?L and {Lambda}?K, a nearly flat doubly degenerate band, and a van Hove singularity, respectively. In cubic HfH{sub 2} the spin-orbit coupling lifts the degeneracy of the partially filled bands in the {Lambda}?L path, while the van Hove singularity in the {Lambda}?K path remains unchanged. The density of states of the three systems in the cubic phase shows a sharp peak at the Fermi level. We found that the tetragonal distortion produces a strong reduction in the density of states at the Fermi level resulting mainly from the splitting of the doubly-degenerate bands in the {Lambda}?L direction and the shift of the van Hove singularity to above the Fermi level. The validity of the Jahn-Teller model in explaining the tetragonal distortion in this group of dihydrides is discussed.« less

Aqueous Isolation of 17-Nuclear Zr-/Hf- Oxide Clusters during the Hydrothermal Synthesis of ZrO2/HfO2.

PubMed

Sung, Qing; Liu, Caiyun; Zhang, Guanyun; Zhang, Jian; Tung, Chen-Ho; Wang, Yifeng

2018-06-21

Novel 17-nuclear Zr-/Hf- oxide clusters ({Zr17} and {Hf17}) are isolated from aqueous systems. In the clusters, Zr/Hf ions are connected via μ3-O, μ3-OH and μ2-OH linkages into a pinwheel core which is wrapped with SO42-, HCOO- and aqua ligands. Octahedral hexanuclear Zr-/Hf- oxide clusters ({Zr6}oct and {Hf6}oct) are also isolated from the same hydrothermal system by decreasing the synthesis temperature. Structural analysis, synthetic conditions, vibrational spectra and ionic conductivity of the clusters are studied. Structural studies and synthesis inspection suggest that formation of {Zr6}oct and {Zr17} involves assembly of the same transferable building blocks, but the condensation degree and thermodynamic stability of the products increase with hydrothermal temperature. The role of {Zr6}oct and {Zr17} in the formation of ZrO2 nanocrystals are then discussed in the scenario of nonclassical nucleation theory. Besides, the Zr-oxide clusters exhibit ionic conductivity due to the mobility of protons. This study not only adds new members to the Zr-/Hf- oxide cluster family, but also establishes a connection from Zr4+ ions to ZrO2 in the hydrothermal preparation of zirconium oxide nanomaterials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Site preference of ternary alloying additions to NiTi: Fe, Pt, Pd, Au, Al, Cu, Zr and Hf

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Noebe, Ronald D.; Mosca, Hugo O.

2004-01-01

Atomistic modeling of the site substitution behavior of Pd in NiTi (J. Alloys and Comp. (2004), in press) has been extended to examine the behavior of several other alloying additions, namely, Fe, Pt, Au, Al, Cu, Zr and Hf in this important shape memory alloy. It was found that all elements, to a varying degree, displayed absolute preference for available sites in the deficient sublattice. How- ever, the energetics of the different substitutional schemes, coupled with large scale simulations indicate that the general trend in all cases is for the ternary addition to want to form stronger ordered structures with Ti.

THERMODYNAMIC PROPERTIES OF Zr AND Hf HALIDES (in Rumanian)

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

Lungu, S.N.

1962-01-01

The following standard heats of formation were found: ZrCl/sub 3/, 178.6 plus or minus 3.2; ZrCl/sub 2/, 124.3 plus or minus 3; ZrBr/sub 3/, 151 plus or minus 7; Zr Br/sbu 2/, 100 plus or minus 6; ZrI/sub 3/, 103 plus or minus 6; ZrI/sub 2/, 68 plus or minus 4; and HfCl/sub 4/, 239.4 plus or minus 5.5; HfCl/sub 3/, 186.6; HfCl/sub 2/, 130; HfBr/sub 4/, 200; HfBr/sub 3/, 157; HfBr / sub 2/, 108; HfI/sub 4/, 140; HfI/sub 3/, 113; and HfI/sub 2/, 72 kcal/mole. (R.V.J.)

Adsorption and diffusion of Au atoms on the (001) surface of Ti, Zr, Hf, V, Nb, Ta, and Mo carbides.

PubMed

Florez, Elizabeth; Viñes, Francesc; Rodriguez, Jose A; Illas, Francesc

2009-06-28

The adsorption of atomic Au on the (001) surface of TiC, ZrC, HfC, VC, NbC, TaC, and delta-MoC and the mechanism of diffusion of this adatom through the surface have been studied in terms of a periodic density functional theory based approach. In all the cases, the Au adsorption energies are in the range of 1.90-2.35 eV. The moderately large adsorption energies allow the Au diffusion before desorption could take place. For TiC(001), ZrC(001), and HfC(001), atomic Au is adsorbed directly on top of C atoms and diffusion takes place along the diagonal of the squares formed by M-C-M-C atoms with the transition state located above the hollow sites. For the rest of transition metal carbides the situation is less simple with the appearance of more than one stable adsorption site, as for NbC and TaC, of a small energy barrier for diffusion around the most stable adsorption site and of a more complex diffusion pathway. The small energy barrier for diffusion around the most stable site will result in a highly mobile Au species which could be observed in scanning tunnel microscope experiments. After depositing Au on metal-carbide surfaces, there is a noticeable charge transfer from the substrate to the adsorbed Au atom. The electronic perturbations on Au increase when going from TiC to ZrC or TaC. Our results indicate that metal carbides should be better supports for the chemical activation of Au than metal oxides.

Effect of Thermal Treatments on Ni-Mn-Ga and Ni-Rich Ni-Ti-Hf/Zr High-Temperature Shape Memory Alloys

NASA Astrophysics Data System (ADS)

Santamarta, Ruben; Evirgen, Alper; Perez-Sierra, Aquilina M.; Pons, Jaume; Cesari, Eduard; Karaman, Ibrahim; Noebe, Ron D.

2015-11-01

Among all the promising high-temperature shape memory alloys (HTSMAs), the Ni-Mn-Ga and the Ni-Ti-Hf/Zr systems exhibit interesting shape memory and superelastic properties that may place them in a good position for potential applications. The present work shows that thermal treatments play a crucial role in controlling the martensitic phase transformation characteristics of both systems, but in different ways. On one hand, the equilibrium phase diagram of the Ni-Mn-Ga family allows selecting compositions with high transformation temperatures and outstanding thermal stability at relatively high temperatures in air, showing no significant changes in the transformation behavior for continuous aging up to ˜5 years at 500 °C. Moreover, the excellent thermal stability correlates with a good thermal cyclic stability and an exceptional oxidation resistance of the parent phase. On the other hand, precipitation processes controlled by thermal treatments are needed to manipulate the transformation temperatures, mechanical properties, and thermal stability of Ni-rich Ni-Ti-Hf/Zr alloys to become HTSMAs. These changes in the functional properties are a consequence of the competition between the mechanical and compositional effects of the precipitates on the martensitic transformation.

Corrosion Protection of Copper Using Al2O3, TiO2, ZnO, HfO2, and ZrO2 Atomic Layer Deposition.

PubMed

Daubert, James S; Hill, Grant T; Gotsch, Hannah N; Gremaud, Antoine P; Ovental, Jennifer S; Williams, Philip S; Oldham, Christopher J; Parsons, Gregory N

2017-02-01

Atomic layer deposition (ALD) is a viable means to add corrosion protection to copper metal. Ultrathin films of Al 2 O 3 , TiO 2 , ZnO, HfO 2 , and ZrO 2 were deposited on copper metal using ALD, and their corrosion protection properties were measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Analysis of ∼50 nm thick films of each metal oxide demonstrated low electrochemical porosity and provided enhanced corrosion protection from aqueous NaCl solution. The surface pretreatment and roughness was found to affect the extent of the corrosion protection. Films of Al 2 O 3 or HfO 2 provided the highest level of initial corrosion protection, but films of HfO 2 exhibited the best coating quality after extended exposure. This is the first reported instance of using ultrathin films of HfO 2 or ZrO 2 produced with ALD for corrosion protection, and both are promising materials for corrosion protection.

Tunneling STM/STS and break-junction spectroscopy of the layered nitro-chloride superconductors MNCl (M = Ti, Hf, Zr)

NASA Astrophysics Data System (ADS)

Ekino, Toshikazu; Sugimoto, Akira; Gabovich, Alexander M.; Zheng, Zhanfeng; Zhang, Shuai; Yamanaka, Shoji

2014-05-01

The layered superconductors β-MNCl with the critical temperatures Tc = 14 K (M = Zr) - 25 K (M = Hf) were investigated by means of scanning-tunneling microscopy/spectroscopy and break-junction tunneling spectroscopy. The STM/STS was used to investigate the surface electronic structures in nanometer length scale, while the BJTS was employed to precisely determine the gap characteristics. Both techniques consistently clarified the unusually large size of the superconducting gap. Wide gap distributions with large-scale maximum gap values were also revealed in α-KyTiNCl with a different crystal structure.

Enhancement of thermoelectric figure-of-merit at low temperatures by titanium substitution for hafnium in n-type half-Heuslers Hf0.75-xTixZr0.25NiSn0.99Sb0.01

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

Joshi, Giri; Dahal, Tulashi; Chen, Shuo

The effect of titanium (Ti) substitution for hafnium (Hf) on thermoelectric properties of (Hf, Zr)-based n-type half-Heuslers: Hf 0.75-xTi xZr 0.25NiSn 0.99Sb 0.01, has been studied. The samples are made by arc melting followed by ball milling and hot pressing via the nanostructuring approach. A peak thermoelectric figure-of-merit (ZT) of ~1.0 is achieved at 500 °C in samples with a composition of Hf 0.5Zr 0.25Ti 0.25NiSn 0.99Sb 0.01 due to a slight increase in carrier concentration and also a lower thermal conductivity caused by Ti. TheZT values below 500 °C of hot pressed Hf 0.5Zr 0.25Ti 0.25NiSn 0.99Sb 0.01 samplesmore » are significantly higher than those of the same way prepared Hf 0.75Zr 0.25NiSn 0.99Sb 0.01samples at each temperature, which are very much desired for mid-range temperature applications such as waste heat recovery in automobiles.« less

Impact of mechanical stress on ferroelectricity in (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films

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

Shiraishi, Takahisa; Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577; Katayama, Kiliha

2016-06-27

To investigate the impact of mechanical stress on their ferroelectric properties, polycrystalline (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films were deposited on (111)Pt-coated SiO{sub 2}, Si, and CaF{sub 2} substrates with thermal expansion coefficients of 0.47, 4.5, and 22 × 10{sup −6}/ °C, respectively. In-plane X-ray diffraction measurements revealed that the (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films deposited on SiO{sub 2} and Si substrates were under in-plane tensile strain and that their volume fraction of monoclinic phase decreased as this strain increased. In contrast, films deposited on CaF{sub 2} substrates were under in-plane compressive strain, and their volume fraction of monoclinic phasemore » was the largest among the three kinds of substrates. The maximum remanent polarization of 9.3 μC/cm{sup 2} was observed for Pt/(Hf{sub 0.5}Zr{sub 0.5})O{sub 2}/Pt/TiO{sub 2}/SiO{sub 2}, while ferroelectricity was barely observable for Pt/(Hf{sub 0.5}Zr{sub 0.5})O{sub 2}/Pt/TiO{sub 2}/SiO{sub 2}/CaF{sub 2}. This result suggests that the in-plane tensile strain effectively enhanced the ferroelectricity of the (Hf{sub 0.5}Zr{sub 0.5})O{sub 2} thin films.« less

Kinetics of Glass Transition and Crystallization of a Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 Bulk Metallic Glass with High Mixing Entropy

NASA Astrophysics Data System (ADS)

Gong, Pan; Wang, Sibo; Li, Fangwei; Wang, Xinyun

2018-04-01

The kinetics of glass transition and crystallization of a novel Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 bulk metallic glass (BMG) with high mixing entropy have been studied by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The continuous DSC curves show five stages of crystallization at lower heating rates (≤ 20 K/min). The activation energies of glass transition were determined by Moynihan and Kissinger methods, while the activation energies of crystallization were calculated utilizing Kissinger, Ozawa, and Boswell models. The crystalline phases corresponding to each crystallization step have been found out. The kinetic fragility of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG has also been evaluated. Based on the isothermal DSC curves, the Avrami exponent, evaluated from the Johnson-Mehl-Avrami equation, has been analyzed in detail. The current study reveals that the crystallization behavior of Zr40Hf10Ti4Y1Al10Cu25Ni7Co2Fe1 BMG exhibits characteristics of both the high entropy BMGs and traditional BMGs with a single principal element, leading to its high glass-forming ability.

Enhancement of thermoelectric figure-of-merit at low temperatures by titanium substitution for hafnium in n-type half-Heuslers Hf0.75-xTixZr0.25NiSn0.99Sb0.01

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

Joshi, Giri; Dahal, Tulashi; Chen, Shuo

The effect of titanium (Ti) substitution for hafnium (Hf) on thermoelectric properties of (Hf, Zr)-based n-type half-Heuslers: Hf0.75-xTixZr0.25NiSn0.99Sb0.01, has been studied. The samples are made by arc melting followed by ball milling and hot pressing via the nanostructuring approach. A peak thermoelectric figure-of-merit (ZT) of ~1.0 is achieved at 500 °C in samples with a composition of Hf0.5Zr0.25Ti0.25NiSn0.99Sb0.01 due to a slight increase in carrier concentration and also a lower thermal conductivity caused by Ti. The ZT values below 500 °C of hot pressed Hf0.5Zr0.25Ti0.25NiSn0.99Sb0.01 samples are significantly higher than those of the same way prepared Hf0.75Zr0.25NiSn0.99Sb0.01 samples at eachmore » temperature, which are very much desired for mid-range temperature applications such as waste heat recovery in automobiles.« less

Mixing effects in a ternary Hf-Zr-Ni metallic melt

NASA Astrophysics Data System (ADS)

Nowak, B.; Holland-Moritz, D.; Yang, F.; Evenson, Z.; Meyer, A.

2018-03-01

We study the effect of the substitution of Zr by Hf on the dynamical behavior in the Zr36Ni64 melt. A reduced measured self-diffusion coefficient and a higher measured melt viscosity for an increased amount of Hf were observed. The ternary Hf10Zr25Ni65 melt, which exhibits a pronounced deviation from Arrhenius behavior over a studied temperature range of 550 K, can be accurately described by the scaling law of mode-coupling theory (MCT) with almost equal parameters for the self-diffusion and the viscosity. Although we only substitute alloy components with a nearly equal atomic size and the measured overall packing fraction remains almost unchanged, the dynamics in Hf10Zr25Ni65 are slower compared to Zr36Ni64 . This corresponds also to a higher critical temperature Tc and might be induced by different chemical interactions in the melts. The increased Tc results in a significantly smaller difference between liquidus and critical temperature Δ TLC=TL-Tc for the ternary melt in comparison with Zr36Ni64 , which may favor the glass formation in the Hf10Zr25Ni65 melt.

Energy efficient microwave synthesis of mesoporous Ce 0.5M 0.5O 2 (Ti, Zr, Hf) nanoparticles for low temperature CO oxidation in an ionic liquid – a comparative study

DOE PAGES

Alammar, Tarek; Chow, Ying -Kit; Mudring, Anja -Verena

2014-11-19

Ce 0.5M 0.5O 2 (M = Ti, Zr, Hf) nanoparticles have been successfully synthesized by microwave irradiation in the ionic liquid [C 4mim][Tf 2N] (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide). The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N 2–adsorption measurements. XRD and Raman spectroscopy analyses confirmed the formation of solid solutions with cubic fluorite structure. The catalytic activities of the Ce 0.5M 0.5O 2 (M = Ti, Zr, Hf) nanoparticles were investigated in the low-temperature oxidation of CO. Ce 0.5Zr 0.5O 2 nanospheresmore » exhibit the best performance (100% conversion at 350 °C), followed by Ce 0.5Hf 0.5O 2 (55% conversion at 360 °C) and Ce 0.5Ti 0.5O 2 (11% conversion at 350 °C). Heating the as-prepared Ce 0.5Zr 0.5O 2 to 600 °C for extended time leads to a decrease in surface area and, as expected decreased catalytic activity. Depending on the ionic liquid the obtained Ce 0.5Zr 0.5O 2 exhibits different morphologies, varying from nano-spheres in [C 4mim][Tf 2N] and [P 66614][Tf 2N] (P 66614 = trishexyltetradecylphosphonium) to sheet-like assemblies in [C 3mimOH][Tf 2N] (C 3mimOH = 1-(3-hydroxypropyl)-3-methylimidazolium). As a result, the microwave synthesis superiority to other heating methods like sonochemical synthesis and conventional heating was proven by comparative experiments where the catalytic activity of Ce 0.5Zr 0.5O 2 obtained by alternate methods such as conventional heating was found to be poorer than that of the microwave-synthesised material.« less

Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms.

PubMed

Xu, Bing; Shi, Peipei; Huang, Tengfei; Wang, Xuefeng; Andrews, Lester

2017-05-25

Infrared spectra of matrix isolated dibridged Si(μ-H) 2 MH 2 and tribridged Si(μ-H) 3 MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH 4 during condensation in excess argon and neon, but only the latter species was observed with titanium. Assignments of the major vibrational modes, which included terminal MH, MH 2 and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD 4 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). The Si-H-M hydrogen bridge bond is calculated as weak covalent interaction and compared with the C-H···M agostic interaction in terms of electron localization function (ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH 4 are discussed in detail.

Characteristics of high-k gate dielectric formed by the oxidation of sputtered Hf/Zr/Hf thin films on the Si substrate

NASA Astrophysics Data System (ADS)

Kim, H. D.; Roh, Y.; Lee, J. E.; Kang, H.-B.; Yang, C.-W.; Lee, N.-E.

2004-07-01

We have investigated the effects of high temperature annealing on the physical and electrical properties of multilayered high-k gate oxide [HfSixOy/HfO2/intermixed-layer(IL)/ZrO2/intermixed-layer(IL)/HfO2] in metal-oxide-semiconductor device. The multilayered high-k films were formed after oxidizing the Hf/Zr/Hf films deposited directly on the Si substrate. The subsequent N2 annealing at high temperature (>= 700 °C) not only results in the polycrystallization of the multilayered high-k films, but also causes the diffusion of Zr. The latter transforms the HfSixOy/HfO2/IL/ZrO2/IL/HfO2 film into the Zr-doped HfO2 film, and improves electrical properties in general. However, the thin SiOx interfacial layer starts to form if annealing temperature increases over 700 °C, deteriorating the equivalent oxide thickness. .

125Te NMR shielding and optoelectronic spectra in XTe3O8 (X = Ti, Zr, Sn and Hf) compounds: Ab initio calculations

NASA Astrophysics Data System (ADS)

Bashi, M.; Rahnamaye Aliabad, H. A.; Mowlavi, A. A.; Ahmad, Iftikhar

2017-11-01

We have calculated the NMR shielding, structural properties and optoelectronic spectra of XTe3O8 (X = Ti, Zr, Sn and Hf) compounds. The full potential linearized augmented plane wave (FP-LAPW) method and the modified Becke-Johnson (mBJ) are used by density functional theory schemes. The calculated shielding and measured shifts are arranged in a straight line and the tensors of magnetic shielding have a low symmetry and the shielding along the x direction is greater than the y and z directions. Obtained results show that the X ions have the most important influence on the 125Te chemical shift. Calculated chemical shielding components (σii) decrease from Ti to Sn then increases from Sn to Hf so that these behaviors are vice versa for 125Te isotropic chemical shift (δiso). Density of states spectra show that the X-p and d states play key role in the optical and NMR calculations. Optical results illustrate that there is a direct relation between the chemical shielding components for Te atom and the static dielectric function, refractive index and Plasmon energies.

Large ferroelectric polarization of TiN/Hf0.5Zr0.5O2/TiN capacitors due to stress-induced crystallization at low thermal budget

NASA Astrophysics Data System (ADS)

Kim, Si Joon; Narayan, Dushyant; Lee, Jae-Gil; Mohan, Jaidah; Lee, Joy S.; Lee, Jaebeom; Kim, Harrison S.; Byun, Young-Chul; Lucero, Antonio T.; Young, Chadwin D.; Summerfelt, Scott R.; San, Tamer; Colombo, Luigi; Kim, Jiyoung

2017-12-01

We report on atomic layer deposited Hf0.5Zr0.5O2 (HZO)-based capacitors which exhibit excellent ferroelectric (FE) characteristics featuring a large switching polarization (45 μC/cm2) and a low FE saturation voltage (˜1.5 V) as extracted from pulse write/read measurements. The large FE polarization in HZO is achieved by the formation of a non-centrosymmetric orthorhombic phase, which is enabled by the TiN top electrode (TE) having a thickness of at least 90 nm. The TiN films are deposited at room temperature and annealed at 400 °C in an inert environment for at least 1 min in a rapid thermal annealing system. The room-temperature deposited TiN TE acts as a tensile stressor on the HZO film during the annealing process. The stress-inducing TiN TE is shown to inhibit the formation of the monoclinic phase during HZO crystallization, forming an orthorhombic phase that generates a large FE polarization, even at low process temperatures.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

PubMed Central

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-01-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials. PMID:27803330

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor.

PubMed

von Rohr, Fabian; Winiarski, Michał J; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-11-15

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

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

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

DOE PAGES

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; ...

2016-11-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Strength design of Zr(x)Ti(x)Hf(x)Nb(x)Mo(x) alloys based on empirical electron theory of solids and molecules

NASA Astrophysics Data System (ADS)

Li, Y. K.; Chen, Y. W.; Cheng, X. W.; Wu, C.; Cheng, B.

2018-05-01

In this paper, the valence electron structure parameters of Zr(x)Ti(x)Hf(x)Nb(x)Mo(x) alloys were calculated based on the empirical electron theory of solids and molecules (EET), and their performance through these parameters were predicted. Subsequently, the alloys with special valence electron structure parameters were prepared byarc melting. The hardness and high-temperature mechanical properties were analyzed to verify the prediction. Research shows that the influence of shared electron number nA on the strongest bond determines the strength of these alloys and the experiments are consistent with the theoretical prediction.

Statistical Modeling of Zr/Hf Extraction using TBP-D2EHPA Mixtures

NASA Astrophysics Data System (ADS)

Rezaeinejhad Jirandehi, Vahid; Haghshenas Fatmehsari, Davoud; Firoozi, Sadegh; Taghizadeh, Mohammad; Keshavarz Alamdari, Eskandar

2012-12-01

In the present work, response surface methodology was employed for the study and prediction of Zr/Hf extraction curves in a solvent extraction system using D2EHPA-TBP mixtures. The effect of change in the levels of temperature, nitric acid concentration, and TBP/D2EHPA ratio (T/D) on the Zr/Hf extraction/separation was studied by the use of central composite design. The results showed a statistically significant effect of T/D, nitric acid concentration, and temperature on the extraction percentage of Zr and Hf. In the case of Zr, a statistically significant interaction was found between T/D and nitric acid, whereas for Hf, both interactive terms between temperature and T/D and nitric acid were significant. Additionally, the extraction curves were profitably predicted applying the developed statistical regression equations; this approach is faster and more economical compared with experimentally obtained curves.

Oxidation behavior of FeAl+Hf,Zr,B

NASA Technical Reports Server (NTRS)

Smialek, James L.; Doychak, Joseph

1988-01-01

The oxidation behavior of Fe-40Al-1Hf, Fe-40Al-1Hf-0.4B, and Fe-40Al-0.1Zr-0.4B (at. percent) alloys was characterized after 900, 1000, and 100 C exposures. Isothermal tests revealed parabolic kinetics after a period of transitional theta-alumina scale growth. The parabolic growth rates for the subsequent alpha-alumina scales were about five times higher than those for NiAl+0.1Zr alloys. The isothermally grown scales showed a propensity toward massive scale spallation due to both extensive rumpling from growth stresses and to an inner layer of HfO2. Cyclic oxidation for 200 1-hr cycles produced little degradation at 900 or 1000 C, but caused significant spallation at 1100 C in the form of small segments of the outer scale. The major difference in the cyclic oxidation of the three FeAl alloys was increased initial spallation for FeAl+Zr,B. Although these FeAl alloys showed many similarities to NiAl alloys, they were generally less oxidation resistant. It is believed that this resulted from nonoptimal levels of dopants and larger thermal expansion mismatch stresses.

Ferroelectric HfZrOx-based MoS2 negative capacitance transistor with ITO capping layers for steep-slope device application

NASA Astrophysics Data System (ADS)

Xu, Jing; Jiang, Shu-Ye; Zhang, Min; Zhu, Hao; Chen, Lin; Sun, Qing-Qing; Zhang, David Wei

2018-03-01

A negative capacitance field-effect transistor (NCFET) built with hafnium-based oxide is one of the most promising candidates for low power-density devices due to the extremely steep subthreshold swing (SS) and high on-state current induced by incorporating the ferroelectric material in the gate stack. Here, we demonstrated a two-dimensional (2D) back-gate NCFET with the integration of ferroelectric HfZrOx in the gate stack and few-layer MoS2 as the channel. Instead of using the conventional TiN capping metal to form ferroelectricity in HfZrOx, the NCFET was fabricated on a thickness-optimized Al2O3/indium tin oxide (ITO)/HfZrOx/ITO/SiO2/Si stack, in which the two ITO layers sandwiching the HfZrOx film acted as the control back gate and ferroelectric gate, respectively. The thickness of each layer in the stack was engineered for distinguishable optical identification of the exfoliated 2D flakes on the surface. The NCFET exhibited small off-state current and steep switching behavior with minimum SS as low as 47 mV/dec. Such a steep-slope transistor is compatible with the standard CMOS fabrication process and is very attractive for 2D logic and sensor applications and future energy-efficient nanoelectronic devices with scaling power supply.

(Zr,Ti)O2 interface structure in ZrO2-TiO2 nanolaminates with ultrathin periodicity

NASA Astrophysics Data System (ADS)

Aita, C. R.; DeLoach, J. D.; Yakovlev, V. V.

2002-07-01

A mixed cation interfacial structure in ZrO2-TiO2 nanolaminate films with ultrathin bilayer periodicity grown by sputter deposition at 297 K was identified by x-ray diffraction and nonresonant Raman spectroscopy. This structure consists of an amorphous phase at a ZrO2-on-TiO2 bilayer interface, followed by an extensive crystalline monoclinic (Zr,Ti)O2 solid solution predicted by Vegard's law. Monoclinic (Zr,Ti)O2 has previously been reported only once, in bulk powder of a single composition (ZrTiO4) at high pressure. Its stabilization in the nanolaminates is explained by the Gibbs-Thomson effect. This complex interfacial structure is shown to be a means of accommodating chemical mixing in the absence of a driving force for heteroepitaxy.

Atomistic study of the electronic contact resistivity between the half-Heusler alloys (HfCoSb, HfZrCoSb, HfZrNiSn) and the metal Ag

NASA Astrophysics Data System (ADS)

He, Yuping; Léonard, François; Spataru, Catalin D.

2018-06-01

Half-Heusler (HH) alloys have shown promising thermoelectric properties in the medium- and high-temperature range. To harness these material properties for thermoelectric applications, it is important to realize electrical contacts with low electrical contact resistivity. However, little is known about the detailed structural and electronic properties of such contacts and the expected values of contact resistivity. Here, we employ atomistic ab initio calculations to study electrical contacts in a subclass of HH alloys consisting of the compounds HfCoSb, HfZrCoSb, and HfZrNiSn. By using Ag as a prototypical metal, we show that the termination of the HH material critically determines the presence or absence of strong deformations at the interface. Our study includes contacts to doped materials, and the results indicate that the p -type materials generally form ohmic contacts while the n -type materials have a small Schottky barrier. We calculate the temperature dependence of the contact resistivity in the low- to medium-temperature range and provide quantitative values that set lower limits for these systems.

The behaviour of REE and Zr-Hf fractionation in the volcanic waters of Nevado del Ruiz system (Colombia)

NASA Astrophysics Data System (ADS)

Inguaggiato, Claudio; Censi, Paolo; Zuddas, Pierpaolo; Makario Londoño, John; Chacón, Zoraida; Alzate, Diego; Brusca, Lorenzo; D'Alessandro, Walter

2015-04-01

The geochemical behaviour of Rare Earth Element (REE), Zr and Hf have been investigated in the thermal waters of Nevado del Ruiz volcanic system. These fluids are characterised by a wide range of pH ranging between 1.0 and 8.8. The acidic waters are sulphate dominated with different Cl/SO4 ratios. The Nevado del Ruiz waters allowed to investigate the behaviour of investigated elements in a wide spectrum of pH and chemical composition of water. The important role of the pH and the ionic complexes have been evidenced in the distribution of REE, Zr and Hf in the aqueous phase. The pH rules the precipitation of authigenic oxyhydroxides of Fe, Al producing changes in REE, Zr, Hf amount and strong anomalies of Cerium and Europium. Y-Ho and Zr-Hf (twin pairs) have different behaviour in strong acidic waters with respect to the water with higher pH. Yttrium and Ho have the same behaviour of Zr and Hf in waters with pH near neutral-to-neutral, showing super-chondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate suggesting an enhanced scavenging of Ho and Hf respect to Y and Zr, leading to super-chondritic ratios. In acidic waters a different behaviour of twin pairs occurs with chondritic Y/Ho ratios (reflecting the Y/Ho ratio of average local rock) and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf have been investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anions chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH<3.6. In strong acidic waters, a different fractionation of Zr and Hf have been recognised as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

Structure, mechanical properties, and grindability of dental Ti-Zr alloys.

PubMed

Ho, Wen-Fu; Chen, Wei-Kai; Wu, Shih-Ching; Hsu, Hsueh-Chuan

2008-10-01

Structure, mechanical properties and grindability of a series of binary Ti-Zr alloys with zirconium contents ranging from 10 to 40 wt% have been investigated. Commercially pure titanium (c.p. Ti) was used as a control. Experimental results indicated that the diffraction peaks of all the Ti-Zr alloys matched those for alpha Ti. No beta-phase peaks were found. The hardness of the Ti-Zr alloys increased as the Zr contents increased, and ranged from 266 HV (Ti-10Zr) to 350 HV (Ti-40Zr). As the concentration of zirconium in the alloys increased, the strength, elastic recovery angles and hardness increased. Moreover, the elastically recoverable angle of Ti-40Zr was higher than of c.p. Ti by as much as 550%. The grindability of each metal was found to be largely dependent on the grinding conditions. The Ti-40Zr alloy had a higher grinding rate and grinding ratio than c.p. Ti at low speed. The grinding rate of the Ti-40Zr alloy at 500 m/min was about 1.8 times larger than that of c.p. Ti, and the grinding ratio was about 1.6 times larger than that of c.p. Ti. Our research suggested that the Ti-40Zr alloy has better mechanical properties, excellent elastic recovery capability and improved grindability at low grinding speed. The Ti-40Zr alloy has a great potential for use as a dental machining alloy.

Design lateral heterostructure of monolayer ZrS2 and HfS2 from first principles calculations

NASA Astrophysics Data System (ADS)

Yuan, Junhui; Yu, Niannian; Wang, Jiafu; Xue, Kan-Hao; Miao, Xiangshui

2018-04-01

The successful fabrication of two-dimensional lateral heterostructures (LHS's) has opened up unprecedented opportunities in material science and device physics. It is therefore highly desirable to search for more suitable materials to create such heterostructures for next-generation devices. Here, we investigate a novel lateral heterostructure composed of monolayer ZrS2 and HfS2 based on density functional theory. The phonon dispersion and ab initio molecular dynamics analysis indicate its good kinetic and thermodynamic stability. Remarkably, we find that these lateral heterostructures exhibit an indirect to direct bandgap transition, in contrast to the intrinsic indirect bandgap nature of ZrS2 and HfS2. The type-II alignment and chemical bonding across the interline have also been revealed. The tensile strain is proved to be an efficient way to modulate the band structure. Finally, we further discuss other three stable lateral heterostructures: (ZrSe2)2(HfSe2)2 LHS, (ZrS2)2(ZrSe2)2 LHS and (HfS2)2(HfSe2)2 LHS. Generally, the lateral heterostructures of monolayer ZrS2 and HfS2 are of excellent electrical properties, and may find potential applications for future electronic devices.

Simulation of Zr content in TiZrCuNi brazing filler metal for Ti6Al4V alloy

NASA Astrophysics Data System (ADS)

Yue, Xishan; Xie, Zonghong; Jing, Yongjuan

2017-07-01

To optimize the Zr content in Ti-based filler metal, the covalent electron on the nearest atoms bond in unit cell ( n A u-v ) with Ti-based BCC structure was calculated, in which the brazing temperature was considered due to its influence on the lattice parameter. Based on EET theory (The Empirical Electron Theory for solid and molecules), n_{{A}}^{{u - v}} represents the strength of the unit cell with defined element composition and structure, which reflects the effect from solid solution strengthening on the strength of the unit cell. For Ti-Zr-15Cu-10Ni wt% filler metal, it kept constant as 0.3476 with Zr as 37.5˜45 wt% and decreased to 0.333 with Zr decreasing from 37.5 to 25 wt%. Finally, it increased up to 0.3406 with Zr as 2˜10 wt%. Thus, Ti-based filler metal with Zr content being 2˜10 wt% is suggested based on the simulation results. Moreover, the calculated covalent electron of n A u-v showed good agreement with the hardness of the joint by filler 37.5Zr and 10Zr. The composition of Ti-10Zr-15Cu-10Ni wt% was verified in this study with higher tensile strength of the brazing joint and uniform microstructure of the interface.

Characterization of Ceramic Plasma-Sprayed Coatings, and Interaction Studies Between U-Zr Fuel and Ceramic Coated Interface at an Elevated Temperature

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

Ki Hwan Kim; Chong Tak Lee; R. S. Fielding

2011-08-01

Candidate coating materials for re-usable metallic nuclear fuel crucibles, HfN, TiC, ZrC, and Y2O3, were plasma-sprayed onto niobium substrates. The coating microstructure and the thermal cycling behavior were characterized, and U-Zr melt interaction studies carried out. The Y2O3 coating layer had a uniform thickness and was well consolidated with a few small pores scattered throughout. While the HfN coating was not well consolidated with a considerable amount of porosity, but showed somewhat uniform thickness. Thermal cycling tests on the HfN, TiC, ZrC, and Y2O3 coatings showed good cycling characteristics with no interconnected cracks forming even after 20 cycles. Interaction studiesmore » done on the coated samples by dipping into a U-20wt.%Zr melt indicated that HfN and Y2O3 did not form significant reaction layers between the melt and the coating while the TiC and the ZrC coatings were significantly degraded. Y2O3 exhibited the most promising performance among HfN, TiC, ZrC, and Y2O3 coatings.« less

Toward optimizing dental implant performance: Surface characterization of Ti and TiZr implant materials.

PubMed

Murphy, M; Walczak, M S; Thomas, A G; Silikas, N; Berner, S; Lindsay, R

2017-01-01

Targeting understanding enhanced osseointegration kinetics, the goal of this study was to characterize the surface morphology and composition of Ti and TiZr dental implant substrates subjected to one of two surface treatments developed by Straumann. These two treatments are typically known as SLA and SLActive, with the latter resulting in more rapid osseointegration. A range of techniques was applied to characterize four different substrate/surface treatment combinations (Ti SLA , Ti SLActive , TiZr SLA , and TiZr SLActive ). Contact angle measurements established their hydrophilic/hydrophobic nature. Surface morphology was probed with scanning electron microscopy. X-ray diffraction, Raman μ-spectroscopy, and X-ray photoelectron spectroscopy were used to elucidate the composition of the near-surface region. Consistent with previous work, surface morphology was found to differ only at the nanoscale, with both SLActive substrates displaying nano-protrusions. Spectroscopic data indicate that all substrates exhibit surface films of titanium oxide displaying near TiO 2 stoichiometry. Raman μ-spectroscopy reveals that amorphous TiO 2 is most likely the only phase present on Ti SL A , whilst rutile-TiO 2 is also evidenced on Ti SLActive , TiZr SLA , and TiZr SLActive . For TiZr alloy substrates, there is no evidence of discrete phases of oxidized Zr. X-ray photoelectron spectra demonstrate that all samples are terminated by adventitious carbon, with it being somewhat thicker (∼1nm) on Ti SL A and TiZr SLA . Given previous in vivo studies, acquired data suggest that both nanoscale protrusions, and a thinner layer of adventitious carbon contribute to the more rapid osseointegration of SLActive dental implants. Composition of the surface oxide layer is apparently less important in determining osseointegration kinetics. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Microstructure, Tensile and Creep Properties of Ta20Nb20Hf20Zr20Ti20 High Entropy Alloy

PubMed Central

Larianovsky, Natalya; Katz-Demyanetz, Alexander; Eshed, Eyal; Regev, Michael

2017-01-01

This paper examines the microstructure and mechanical properties of Ta20Nb20Hf20Zr20Ti20. Two casting processes, namely, gravity casting and suction-assisted casting, were applied, both followed by Hot Isostatic Pressing (HIP). The aim of the current study was to investigate the creep and tensile properties of the material, since the literature review revealed no data whatsoever regarding these properties. The main findings are that the HIP process is responsible for the appearance of a Hexagonal Close Packed (HCP) phase that is dispersed differently in these two castings. The HIP process also led to a considerable increase in the mechanical properties of both materials under compression, with values found to be higher than those reported in the literature. Contrary to the compression properties, both materials were found to be highly brittle under tension, either during room temperature tension tests or creep tests conducted at 282 °C. Fractography yielded brittle fracture without any evidence of plastic deformation prior to fracture. PMID:28773245

Microstructure and Phase Stability of Single Crystal NiAl Alloyed with Hf and Zr

NASA Technical Reports Server (NTRS)

Locci, I. E.; Dickerson, R. M.; Garg, A.; Noebe, R. D.; Whittenberger, J. D.; Nathal, M. V.; Darolia, R.

1996-01-01

Six near stoichiometric, NiAl single-crystal alloys, with 0.05-1.5 at.% of Hf and Zr additions plus Si impurities, were microstructurally analyzed in the as-cast, homogenized, and aged conditions. Hafnium-rich interdendritic regions, containing the Heusler phase (Ni2AlHf), were found in all the as-cast alloys containing Hf. Homogenization heat treatments partially reduced these interdendritic segregated regions. Transmission electron microscopy (TEM) observations of the as-cast and homogenized microstructures revealed the presence of a high density of fine Hf (or Zr) and Si-rich precipitates. These were identified as G-phase, Nil6X6Si7, or as an orthorhombic NiXSi phase, where X is Hf or Zr. Under these conditions the expected Heusler phase (beta') was almost completely absent. The Si responsible for the formation of the G and NiHfSi phases is the result of molten metal reacting with the Si-containing crucible used during the casting process. Varying the cooling rates after homogenization resulted in the refinement or complete suppression of the G and NiHfSi phases. In some of the alloys studied, long-term aging heat treatments resulted in the formation of Heusler precipitates, which were more stable at the aging temperature and coarsened at the expense of the G-phase. In other alloys, long-term aging resulted in the formation of the NiXSi phase. The stability of the Heusler or NiXSi phases can be traced to the reactive element (Hf or Zr) to silicon ratio. If the ratio is high, then the Heusler phase appears stable after long time aging. If the ratio is low, then the NiHfSi phase appears to be the stable phase.

Thermoelectric and Structural Properties of Zr-/Hf-Based Half-Heusler Compounds Produced at a Large Scale

NASA Astrophysics Data System (ADS)

Zillmann, D.; Waag, A.; Peiner, E.; Feyand, M.-H.; Wolyniec, A.

2018-02-01

The half-Heusler (HH) systems are promising candidates for thermoelectric (TE) applications since they have shown high figures of merit ( zT) of ˜ 1, which are directly related to the energy conversion efficiency. To use HH compounds for TE devices, the materials must be phase-stable at operating temperatures up to 600°C. Currently, only a few HH compositions are available in large quantities. Hence, we focus on the TE and structural properties of three commercially available Zr-/Hf-based HH compounds in this publication. In particular, we evaluate the thermal conductivities and the figures of merit and critically discuss uncertainties and propagation error in the measurements. We find thermal conductivities of less than 6.0 W K^{-1}m^{-1} for all investigated materials and notably high figures of merit of 0.93 and 0.60 for n- and p-type compounds, respectively, at 600°C. Additionally, our investigations reveal that the grain structures of all materials also contain secondary phases like HfO2, Sn-Ni and Ti-Zr-Sn rich phases while an additional SnO_2 phase was found following several hours of harsh heat treatment at 800°C.

Effects of interfacial layer on characteristics of TiN/ZrO2 structures.

PubMed

Kim, Younsoo; Kang, Sang Yeol; Choi, Jae Hyoung; Lim, Jae Soon; Park, Min Young; Chung, Suk-Jin; Chung, Jaegwan; Lee, Hyung Ik; Kim, Ki Hong; Kyoung, Yong Koo; Heo, Sung; Yoo, Cha Young; Kang, Ho-Kyu

2011-09-01

To minimize the formation of unwanted interfacial layers, thin interfacial layer (ZrCN layer) was deposited between TiN bottom electrode and ZrO2 dielectric in TiN/ZrO2/TiN capacitor. Carbon and nitrogen were also involved in the layer because ZrCN layer was thermally deposited using TEMAZ without any reactant. Electrical characteristics of TiN/ZrO2/TiN capacitor were improved by insertion of ZrCN layer. The oxidation of TiN bottom electrode was largely inhibited at TiN/ZrCN/ZrO2 structure compared to TiN/ZrO2 structure. While the sheet resistance of TiN/ZrCN/ZrO2 structure was constantly sustained with increasing ZrO2 thickness, the large increase of sheet resistance was observed in TiN/ZrO2 structure after 6 nm ZrO2 deposition. When ZrO2 films were deposited on ZrCN layer, the deposition rate of ZrO2 also increased. It is believed that ZrCN layer acted both as a protection layer of TiN oxidation and a seed layer of ZrO2 growth.

Effect of Cold Deformation and Annealing on the Microstructure and Tensile Properties of a HfNbTaTiZr Refractory High Entropy Alloy

NASA Astrophysics Data System (ADS)

Senkov, O. N.; Pilchak, A. L.; Semiatin, S. L.

2018-07-01

The microstructure and tensile properties of HfNbTaTiZr after cold working and annealing were investigated. Cold work was introduced by axial compression followed by rolling resulting in a total thickness reduction of 89 pct without any evidence of cracking. The cold-worked material retained a single-phase microstructure and had a room temperature tensile yield stress σ 0.2 = 1438 MPa, peak true stress σ p = 1495 MPa, and true fracture strain ɛ f = 5 pct. Annealing at 800 °C for up to 256 hours resulted in the precipitation of Nb and Ta rich particles with a BCC crystal structure inside a Hf-and-Zr-enriched BCC matrix. The second phase particles nucleated heterogeneously inside deformation bands and slip lines and coarsened during annealing. Analysis of the coarsening behavior suggested that kinetics were controlled by the diffusion of Nb and Ta. In the two-phase material, σ 0.2 and σ p decreased from 1159 to 1071 MPa and from 1174 to 1074 MPa, respectively, with an increase in particle diameter from 0.18 to 0.72 μm, while ɛ f remained between 5 and 8 pct. Full recrystallization and normal grain growth, with the activation energy of 238 kJ/mol and activation volume of 5.3 to 9.6 m3/mol, occurred during annealing above 1000 °C. After heat treatment at this temperature, the alloy was characterized by a single-phase BCC structure with σ 0.2 = 1110 to 1115 MPa, σ p = 1160 to 1195 MPa, and ɛ f = 12 to 19 pct with the maximum values attained after annealing for 1 hour.

Effect of Cold Deformation and Annealing on the Microstructure and Tensile Properties of a HfNbTaTiZr Refractory High Entropy Alloy

NASA Astrophysics Data System (ADS)

Senkov, O. N.; Pilchak, A. L.; Semiatin, S. L.

2018-05-01

The microstructure and tensile properties of HfNbTaTiZr after cold working and annealing were investigated. Cold work was introduced by axial compression followed by rolling resulting in a total thickness reduction of 89 pct without any evidence of cracking. The cold-worked material retained a single-phase microstructure and had a room temperature tensile yield stress σ 0.2 = 1438 MPa, peak true stress σ p = 1495 MPa, and true fracture strain ɛ f = 5 pct. Annealing at 800 °C for up to 256 hours resulted in the precipitation of Nb and Ta rich particles with a BCC crystal structure inside a Hf-and-Zr-enriched BCC matrix. The second phase particles nucleated heterogeneously inside deformation bands and slip lines and coarsened during annealing. Analysis of the coarsening behavior suggested that kinetics were controlled by the diffusion of Nb and Ta. In the two-phase material, σ 0.2 and σ p decreased from 1159 to 1071 MPa and from 1174 to 1074 MPa, respectively, with an increase in particle diameter from 0.18 to 0.72 μm, while ɛ f remained between 5 and 8 pct. Full recrystallization and normal grain growth, with the activation energy of 238 kJ/mol and activation volume of 5.3 to 9.6 m3/mol, occurred during annealing above 1000 °C. After heat treatment at this temperature, the alloy was characterized by a single-phase BCC structure with σ 0.2 = 1110 to 1115 MPa, σ p = 1160 to 1195 MPa, and ɛ f = 12 to 19 pct with the maximum values attained after annealing for 1 hour.

Discovery of ferromagnetism with large magnetic anisotropy in ZrMnP and HfMnP

DOE PAGES

Lamichhane, Tej N.; Taufour, Valentin; Masters, Morgan W.; ...

2016-08-29

Here, ZrMnP and HfMnP single crystals are grown by a self-flux growth technique, and structural as well as temperature dependent magnetic and transport properties are studied. Both compounds have an orthorhombic crystal structure. ZrMnP and HfMnP are ferromagnetic with Curie temperatures around 370 K and 320 K, respectively. The spontaneous magnetizations of ZrMnP and HfMnP are determined to be 1.9 μ B/f.u. and 2.1 μ B/f.u., respectively, at 50 K. The magnetocaloric effect of ZrMnP in terms of entropy change (Δ S) is estimated to be –6.7 kJ m –3 K –1 around 369 K. The easy axis of magnetizationmore » is [100] for both compounds, with a small anisotropy relative to the [010] axis. At 50 K, the anisotropy field along the [001] axis is ~4.6 T for ZrMnP and ~10 T for HfMnP. Such large magnetic anisotropy is remarkable considering the absence of rare-earth elements in these compounds. The first principle calculation correctly predicts the magnetization and hard axis orientation for both compounds, and predicts the experimental HfMnP anisotropy field within 25%. More importantly, our calculations suggest that the large magnetic anisotropy comes primarily from the Mn atoms, suggesting that similarly large anisotropies may be found in other 3d transition metal compounds.« less

Synthesis of MAX Phases in the Zr-Ti-Al-C System.

PubMed

Tunca, Bensu; Lapauw, Thomas; Karakulina, Olesia M; Batuk, Maria; Cabioc'h, Thierry; Hadermann, Joke; Delville, Rémi; Lambrinou, Konstantina; Vleugels, Jozef

2017-03-20

This study reports on the synthesis and characterization of MAX phases in the (Zr,Ti) n+1 AlC n system. The MAX phases were synthesized by reactive hot pressing and pressureless sintering in the 1350-1700 °C temperature range. The produced ceramics contained large fractions of 211 and 312 (n = 1, 2) MAX phases, while strong evidence of a 413 (n = 3) stacking was found. Moreover, (Zr,Ti)C, ZrAl 2 , ZrAl 3 , and Zr 2 Al 3 were present as secondary phases. In general, the lattice parameters of the hexagonal 211 and 312 phases followed Vegard's law over the complete Zr-Ti solid solution range, but the 312 phase showed a non-negligible deviation from Vegard's law around the (Zr 0.33 ,Ti 0.67 ) 3 Al 1.2 C 1.6 stoichiometry. High-resolution scanning transmission electron microscopy combined with X-ray diffraction demonstrated ordering of the Zr and Ti atoms in the 312 phase, whereby Zr atoms occupied preferentially the central position in the close-packed M 6 X octahedral layers. The same ordering was also observed in 413 stackings present within the 312 phase. The decomposition of the secondary (Zr,Ti)C phase was attributed to the miscibility gap in the ZrC-TiC system.

Microstructural investigation of plastically deformed Ti{sub 20}Zr{sub 20}Hf{sub 20}Nb{sub 20}Ta{sub 20} high entropy alloy by X-ray diffraction and transmission electron microscopy

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

Dirras, G., E-mail: dirras@univ-paris13.fr; Gubicza, J.; Heczel, A.

2015-10-15

The microstructure evolution in body-centered cubic (bcc) Ti{sub 20}Zr{sub 20}Hf{sub 20}Nb{sub 20}Ta{sub 20} high entropy alloy during quasi-static compression test was studied by X-ray line profile analysis (XLPA) and transmission electron microscopy (TEM). The average lattice constant and other important parameters of the microstructure such as the mean crystallite size, the dislocation density and the edge/screw character of dislocations were determined by XLPA. The elastic anisotropy factor required for XLPA procedure was determined by nanoindentation. XLPA shows that the crystallite size decreased while the dislocation density increased with strain during compression, and their values reached about 39 nm and 15more » × 10{sup 14} m{sup −2}, respectively, at a plastic strain of ~ 20%. It was revealed that with increasing strain the dislocation character became more screw. This can be explained by the reduced mobility of screw dislocations compared to edge dislocations in bcc structures. These observations are in line with TEM investigations. The development of dislocation density during compression was related to the yield strength evolution. - Highlights: • Ti{sub 20}Zr{sub 20}Hf{sub 20}Nb{sub 20}Ta{sub 20} high entropy alloy was processed by arc-melting. • The mechanical was evaluated by RT compression test. • The microstructure evolution was studied by XLPA and TEM. • With increasing strain the dislocation character became more screw. • The yield strength was related to the development of the dislocation density.« less

Lattice Thermal Conductivity from Atomistic Simulations: ZrB2 and HfB2

NASA Technical Reports Server (NTRS)

Lawson, John W.; Daw, Murray S.; Bauschlicher, Charles W.

2012-01-01

Ultra high temperature ceramics (UHTC) including ZrB2 and HfB2 have a number of properties that make them attractive for applications in extreme environments. One such property is their high thermal conductivity. Computational modeling of these materials will facilitate understanding of fundamental mechanisms, elucidate structure-property relationships, and ultimately accelerate the materials design cycle. Progress in computational modeling of UHTCs however has been limited in part due to the absence of suitable interatomic potentials. Recently, we developed Tersoff style parameterizations of such potentials for both ZrB2 and HfB2 appropriate for atomistic simulations. As an application, Green-Kubo molecular dynamics simulations were performed to evaluate the lattice thermal conductivity for single crystals of ZrB2 and HfB2. The atomic mass difference in these binary compounds leads to oscillations in the time correlation function of the heat current, in contrast to the more typical monotonic decay seen in monoatomic materials such as Silicon, for example. Results at room temperature and at elevated temperatures will be reported.

Fluorite transition metal hydride induced destabilization of the MgH2 system in MgH2/TMH2 multilayers ( TM=Sc , Ti, V, Cr, Y, Zr, Nb, La, Hf)

NASA Astrophysics Data System (ADS)

Tao, S. X.; Notten, P. H. L.; van Santen, R. A.; Jansen, A. P. J.

2010-09-01

The structural changes in MgH2 induced by contact with fluorite transition metal hydrides ( TMH2 , TM=Sc , Ti, V, Cr, Y, Zr, Nb, La, Hf) have been studied using density-functional theory calculations. Models of MgH2(rutile)/TiH2(fluorite) and MgH2(fluorite)/TiH2(fluorite) multilayers with different Mg:TM ratios have been designed. With a fixed thickness of the TMH2 layer, structure transformation of MgH2 from rutile to fluorite occurs with a decrease in thickness of the MgH2 layer. The hydrogen desorption energy from the fluorite MgH2 layer in the multilayers is significantly lower than that of the bulk rutile MgH2 . The structural deformation of the MgH2 layer due to the strain induced by TMH2 is found to be responsible for the destabilization of the Mg-H bond: the more structural deformation, the more destabilization of the Mg-H. Our results provide an important insight for the development of new hydrogen-storage materials with desirable thermodynamic properties.

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2.

PubMed

Perevalov, T V; Islamov, D R; Gritsenko, V A; Prosvirin, I P

2018-05-11

The electronic structure of oxygen-deficient Hf 0.5 Zr 0.5 O 2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf 0.5 Zr 0.5 O 2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf 0.5 Zr 0.5 O 2 : an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf 0.5 Zr 0.5 O 2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2

NASA Astrophysics Data System (ADS)

Perevalov, T. V.; Islamov, D. R.; Gritsenko, V. A.; Prosvirin, I. P.

2018-05-01

The electronic structure of oxygen-deficient Hf0.5Zr0.5O2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf0.5Zr0.5O2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf0.5Zr0.5O2: an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf0.5Zr0.5O2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Effects of HfB2 and HfN Additions on the Microstructures and Mechanical Properties of TiB2-Based Ceramic Tool Materials

PubMed Central

An, Jing; Song, Jinpeng; Liang, Guoxing; Gao, Jiaojiao; Xie, Juncai; Cao, Lei; Wang, Shiying; Lv, Ming

2017-01-01

The effects of HfB2 and HfN additions on the microstructures and mechanical properties of TiB2-based ceramic tool materials were investigated. The results showed that the HfB2 additive not only can inhibit the TiB2 grain growth but can also change the morphology of some TiB2 grains from bigger polygons to smaller polygons or longer ovals that are advantageous for forming a relatively fine microstructure, and that the HfN additive had a tendency toward agglomeration. The improvement of flexural strength and Vickers hardness of the TiB2-HfB2 ceramics was due to the relatively fine microstructure; the decrease of fracture toughness was ascribed to the formation of a weaker grain boundary strength due to the brittle rim phase and the poor wettability between HfB2 and Ni. The decrease of the flexural strength and Vickers hardness of the TiB2-HfN ceramics was due to the increase of defects such as TiB2 coarse grains and HfN agglomeration; the enhancement of fracture toughness was mainly attributed to the decrease of the pore number and the increase of the rim phase and TiB2 coarse grains. The toughening mechanisms of TiB2-HfB2 ceramics mainly included crack bridging and transgranular fracture, while the toughening mechanisms of TiB2-HfN ceramics mainly included crack deflection, crack bridging, transgranular fracture, and the core-rim structure. PMID:28772821

Solution treatment-delayed zirconium-strengthening behavior in Ti-7.5Mo-xZr alloy system

NASA Astrophysics Data System (ADS)

Chern Lin, Jiin-Huey; Fu, Yen-Han; Chen, Yen-Chun; Peng, Yu-Po; Ju, Chien-Ping

2018-01-01

The present study was devoted to investigate and compare the Zr-strengthening behavior in as-cast (AC) and solution-treated (ST) Ti-7.5Mo-xZr alloys. The experimental results indicated that AC Ti-7.5Mo and AC Ti-7.5Mo-1Zr alloys substantially had an orthorhombic {α }\\prime\\prime phase with a fine, acicular morphology. The content of equi-axed β phase continued to increase with increased Zr content at the expense of {α }\\prime\\prime phase. The threshold Zr content for the formation of β phase in the ST Ti-7.5Mo-xZr alloys was apparently higher than that in the AC Ti-7.5Mo-xZr alloys. The β granular structure was revealed in ST Ti-7.5Mo-5Zr alloy, which increased with increased Zr content. Unlike AC Ti-7.5Mo-9Zr alloy, within each grain of ST Ti-7.5Mo-9Zr alloy were still observed a significant portion of {α }\\prime\\prime morphology. AC Ti-7.5Mo alloy had the lowest YS, lowest tensile modulus and highest elongation among all AC Ti-7.5Mo-xZr alloys. When Zr content increased, both YS and modulus significantly increased while the elongation significantly decreased. Compared to AC Ti-7.5Mo alloy, AC Ti-7.5Mo-9Zr alloy had almost double YS, indicating the effectiveness of Zr-induced strengthening in the AC Ti-7.5Mo-xZr alloys. Compared to AC Ti-7.5Mo, ST Ti-7.5Mo alloys had lower YS, UTS and tensile modulus with almost the same elongation. All the XRD, metallography and tensile test results consistently indicated that the presence of Zr could accelerate the formation of β phase and effectively strengthen the AC Ti-7.5Mo-xZr alloys. A phenomenon of delayed β formation and delayed strengthening was noted in the ST Ti-7.5Mo-xZr alloys, compared to the AC Ti-7.5Mo-xZr alloys.

Chlorine mobility during annealing in N2 in ZrO2 and HfO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Ferrari, S.; Scarel, G.; Wiemer, C.; Fanciulli, M.

2002-12-01

Atomic layer deposition (ALD) growth of high-κ dielectric films (ZrO2 and HfO2) was performed using ZrCl4, HfCl4, and H2O as precursors. In this work, we use time of flight secondary ion mass spectrometry to investigate the chlorine distribution in ALD grown ZrO2 and HfO2 films, and its evolution during rapid thermal processes in nitrogen atmosphere. Chlorine outdiffusion is found to depend strongly upon annealing temperature and weakly upon the annealing time. While in ZrO2 chlorine concentration is significantly decreased already at 900 °C, in HfO2 it is extremely stable, even at temperatures as high as 1050 °C.

Color tone and interfacial microstructure of white oxide layer on commercially pure Ti and Ti-Nb-Ta-Zr alloys

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Mizushima, Keisuke; Watanabe, Yoshimi; Kasuga, Toshihiro; Niinomi, Mitsuo

2014-11-01

In this study, the relationships among oxidation condition, color tone, and the cross-sectional microstructure of the oxide layer on commercially pure (CP) Ti and Ti-36Nb-2Ta-3Zr-0.3O were investigated. “White metals” are ideal metallic materials having a white color with sufficient strength and ductility like a metal. Such materials have long been sought for in dentistry. We have found that the specific biomedical Ti alloys, such as CP Ti, Ti-36Nb-2Ta-3Zr-0.3O, and Ti-29Nb-13Ta-4.6Zr, form a bright yellowish-white oxide layer after a particular oxidation heat treatment. The brightness L* and yellowness +b* of the oxide layer on CP Ti and Ti-36Nb-2Ta-3Zr-0.3O increased with heating time and temperature. Microstructural observations indicated that the oxide layer on Ti-29Nb-13Ta-4.6Zr and Ti-36Nb-2Ta-3Zr-0.3O was dense and firm, whereas a piecrust-like layer was formed on CP Ti. The results obtained in this study suggest that oxide layer coating on Ti-36Nb-2Ta-3Zr-0.3O is an excellent technique for dental applications.

The mechanical, optoelectronic and thermoelectric properties of NiYSn (Y = Zr and Hf) alloys

NASA Astrophysics Data System (ADS)

Hamioud, Farida; Mubarak, A. A.

2017-09-01

First-principle calculations are performed using DFT as implemented in Wien2k code to compute the mechanical, electronic, optical and thermoelectric properties of NiYSn (Y = Zr and Hf) alloys. The computed lattice constants, bulk modulus and cohesive energy of these alloys at 0 K and 0 GPa are performed. NiZrSn and NiHfSn are found to be anisotropic and elastically stable. Furthermore, both alloys are confirmed to be thermodynamically stable by the calculated values of the standard enthalpy of formation. The Young’s and shear moduli values show that NiZrSn seems to be stiffer than NiHfSn. The optical properties are performed using the dielectric function. Some beneficial optoelectronic applications are found as exposed in the optical spectra. Moreover, the alloys are classified as good insulators for solar heating. The thermoelectric properties as a function of temperature are computed utilizing BoltzTrap code. The major charge carriers are found to be electrons and the alloys are classified as p-type doping alloys.

High-field superconductivity in the Nb-Ti-Zr ternary system

NASA Astrophysics Data System (ADS)

Ralls, K. M.; Rose, R. M.; Wulff, J.

1980-06-01

Resistive critical current densities, critical fields, and normal-state electrical resistivities were obtained at 4.2 °K for 55 alloys in the Nb-Ti-Zr ternary alloy system, excepting Ti-Zr binary compositions. The resistive critical field as a function of ternary composition has a saddle point between the Nb-Ti and Nb-Zr binaries, so that ternary alloying in this system is not expected to result in higher critical fields than the binary alloys.

The Effect of Element Substitution on Ti-in-Zircon Geothermometry in Volcanic Zircons from Mount Pinatubo, Philippines

NASA Astrophysics Data System (ADS)

Lee, S. L.; Hattori, K.

2017-12-01

Despite the extensive application of the Ti-in-zircon geothermometer, its accuracy in natural systems remains uncertain. In order to investigate the parameters contributing to Ti in zircon, we examined zircons from dacitic eruption products of Mount Pinatubo, Philippines, from the Pliocene (>2.5-2.7 Ma), 35000BP and 1991AD. All samples are unaltered and quenched from magmas at 790-825°C (Fe-Ti-oxide thermometry). Furthermore, the magma conditions of 1991 samples are well characterized: 780°C (cummingtonite rims on hornblende, Fe-Ti-oxide thermometry), 2 kbar pressure, 5.5-6.5 wt.% H2O and fO2 of NNO+1.6. Calculated zircon saturation temperatures are 760, 744 and 738°C (oldest to youngest). Zircon Ti concentrations are low (2.0-8.8 ppm), show positive covariation with U (35.6-639 ppm), Th (18.7-696 ppm), ∑REE (237-1310 ppm) and Y (247-1770 ppm), and negative covariation with Hf (7610-12000 ppm). The Ti-in-zircon geothermometer by Ferry and Watson (2007) yields mean temperatures of 690, 666 and 663°C (oldest to youngest), using TiO2 activity=0.6, SiO2 activity=1 and -40°C pressure correction. Therefore, temperatures calculated using this method are underestimated by >100°C. We suggest that elements in the Zr site impact the substitution of Ti in the Si site of zircon. Ti shows a positive covariation with Zr/Hf (37.0-57.3, r2=0.551). The ionic radius of Hf4+ is smaller than Zr4+, whereas cations like U4+, Th4+, REE3+ and Y3+ are larger. The departure from the ideal crystal configuration is evaluated using the parameter Zr/(Hf-x), whereby x=U4+, Th4+, ∑REE and Y3+. Ti contents are more strongly correlated with the parameter than Zr/Hf (r2=0.559, 0.565, 0.608, 0.616; respectively). This suggests that large cations replacing Zr strain the lattice, reducing the amount of Ti incorporated into zircon. This further suggests that ZrSiO4 activity is less than 1 in natural rocks, resulting in the systematic underestimation of Ti-in-zircon temperatures.

A novel process for preparation of titanium dioxide from Ti-bearing electric furnace slag: NH4HF2-HF leaching and hydrolyzing process.

PubMed

Zheng, Fuqiang; Guo, Yufeng; Qiu, Guanzhou; Chen, Feng; Wang, Shuai; Sui, Yulei; Jiang, Tao; Yang, Lingzhi

2018-02-15

A novel process to prepare titanium dioxide from Ti-bearing electric furnace slag by NH 4 HF 2 -HF leaching and hydrolyzing process has been developed. In this present study, the effects of [NH 4 + ]/[F] mXolar ratio, leaching temperature, [F] concentration, liquid/solid mass ratio, leaching time on the Ti extraction, and the phase transformations have been investigated to reveal the leaching mechanism of Ti-bearing electric furnace slag in NH 4 HF 2 -HF solution. In the NH 4 HF 2 -HF leaching process, the MgTi 2 O 5 and Al 2 TiO 5 are converted to TiF 6 2- and Mg-Al-bearing precipitate. Ti extraction rate reached 98.84% under the optimal conditions. In addition, 98.25% iron ions can be removed in the presence of NaCl prior to hydrolysis process. The effects of pH and temperature on the selective hydrolysis of TiF 6 2- during hydrolysis process were also studied. In the hydrolysis process, the TiF 6 2- is converted to (NH 4 ) 2 TiOF 4 . By calcination, high grade TiO 2 powder with its purity of 99.88% was obtained, using which the products, well crystallized anatase and rutile, were obtained through roasting at 800°C and 1000°C, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

First-principles study of lattice thermal conductivity in ZrTe5 and HfTe5

NASA Astrophysics Data System (ADS)

Wang, Cong; Wang, Haifeng; Chen, Y. B.; Yao, Shu-Hua; Zhou, Jian

2018-05-01

Recently, the layered transition-metal pentatellurides ZrTe5 and HfTe5 have attracted increasing attention because of their interesting topological electronic properties. Nevertheless, some of their other good physical properties seem to be ignored now. Actually, both ZrTe5 and HfTe5 have high electric conductivities (>105 Ω-1 m-1) and Seebeck coefficients (> 100 μV/K) at room temperature, thus making them promising thermoelectric materials. However, the disadvantage is that the thermal conductivities of the two materials are relatively high according to the few available experiments; meanwhile, the detailed mechanism of the intrinsic thermal conductivity has not been studied yet. Based on the density functional theory and the Boltzmann transport theory, we present here the theoretical study of the intrinsic lattice thermal conductivities of ZrTe5 and HfTe5, which are found to be in the range of 5-8 W/mṡK at room temperature and well consistent with the experimental results. We also find that the thermal conductivities of the two materials are anisotropic, which are mainly caused by their anisotropic crystal structures. Based on the detailed analysis, we proposed that the thermal conductivities of the two materials could possibly be reduced by different kinds of structural engineering at the atomic and mesoscopic scales, such as alloying, doping, nano-structuring, and polycrystalline structuring, which could make ZrTe5 and HfTe5 good thermoelectric materials for room temperature thermoelectric applications.

Electronic structure study of Ce1-xAxO2 (A = Zr & Hf) nanoparticles: NEXAFS and EXAFS investigations.

PubMed

Sharma, Aditya; Varshney, Mayora; Shin, Hyun-Joon; Park, Yong Jun; Kim, Min-Gyu; Ha, Tae-Kyun; Chae, Keun Hwa; Gautam, Sanjeev

2014-10-07

Single phase nanoparticles (NPs) of CeO2, Ce0.5Zr0.5O2, Ce0.5Hf0.5O2 and Ce0.5Hf0.25Zr0.25O2 were successfully synthesized by co-precipitation method at constant pH and temperature. The X-ray diffraction results revealed that the additive atoms did not segregate to form secondary phases but led to grain size variation in the NPs. The 10 Dq values in the near edge X-ray absorption fine structure (NEXAFS) spectra at the O K-edge did not vary in the same way as the average grain size was changed for the doped CeO2 NPs. The deconvolution of Ce M5-edge and detailed analysis of O K pre-edge peak have shown the higher Ce(+3)/(Ce(+3) + Ce(+4)) ratio in the Zr- and Hf-doped samples. The local atomic structure around the Ce, Zr and Hf atoms was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at Ce K-edge, Zr K-edge and Hf L3-edge, respectively, and the EXAFS data were fitted with the theoretical calculations. The 4f occupancy, Ce(+3)/(Ce(+3) + Ce(+4)) ratio of Ce ions, coordination number of Ce and Ce-Ce/Ce-O bond distances were sensitive to the additive atoms but not explicitly changed according to the grain size variation in the NPs.

Effects of TiN coating on the corrosion of nanostructured Ti-30Ta-xZr alloys for dental implants

NASA Astrophysics Data System (ADS)

Kim, Won-Gi; Choe, Han-Cheol

2012-01-01

Electrochemical characteristics of a titanium nitride (TiN)-coated/nanotube-formed Ti-Ta-Zr alloy for biomaterials have been researched by using the magnetic sputter and electrochemical methods. Ti-30Ta-xZr (x = 3, 7 and 15 wt%) alloys were prepared by arc melting and heat treated for 24 h at 1000 °C in an argon atmosphere and then water quenching. The formation of oxide nanotubes was achieved by anodizing a Ti-30Ta-xZr alloy in H3PO4 electrolytes containing small amounts of fluoride ions at room temperature. Anodization was carried out using a scanning potentiostat, and all experiments were conducted at room temperature. The microstructure and morphology of nanotube arrays were characterized by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The TiN coatings were obtained by the radio-frequency (RF) magnetron sputtering technique. The depositions were performed from pure Ti targets on Ti-30Ta-xZr alloys substrates. The corrosion properties of the specimens were examined using potentiodynamic test in a 0.9% NaCl solution by using potentiostat. The microstructures of Ti-30Ta-xZr alloys were changed from an equiaxed to a needle-like structure with increasing Zr content. The interspace between the nanotubes was approximately 20, 80 and 200 nm for Zr contents of 3, 7 and 15 wt%, respectively. The corrosion resistance of the TiN-coated on the anodized Ti-30Ta-xZr alloys was higher than that of the untreated Ti alloys, indicating a better protective effect.

Oxidation of ZrB2-and HfB2-Based Ultra-High Temperature Ceramics: Effects of Ta Additions

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Levine, Stanley; Lorinez, Jonathan

2003-01-01

Several compositions of ZrB2- and HfB2-based Ultra-High Temperature Ceramics (UHTC) were oxidized in stagnant air at 1627 C in ten minute cycles for times up to 100 minutes. These compositions include: ZrB2 - 20v% SiC, HfB2 - 20v% SiC, ZrB2 - 20v% SiC - 20v% TaSi2, ZrB2 - 33v% SiC, HfB2 - 20v% SiC - 20v% TaSi2, and ZrB2 - 20v% SiC - 20v% TaC. The weight change due to oxidation was recorded. The ZrB2 - 20v% SiC - 20v% TaSi2 composition was also oxidized in stagnant air at 1927 C and in an arc jet atmosphere. Samples were analyzed after oxidation by x-ray diffraction, field emission scanning electron microscopy, and energy dispersive spectroscopy to determine the reaction products and to observe the microstructure. The ZrB2 - 20v% SiC - 20v% TaSi2 showed the lowest oxidation rate at 1627 C, but performed poorly under the more extreme tests due to liquid phase formation. Effects of Ta-additions on the oxidation of the diboride-based UHTC are discussed.

Empirical Study of the Multiaxial, Thermomechanical Behavior of NiTiHf Shape Memory Alloys

NASA Technical Reports Server (NTRS)

Shukla, Dhwanil; Noebe, Ronald D.; Stebner Aaron P.

2013-01-01

An empirical study was conducted to characterize the multiaxial, thermomechanical responses of new high temperature NiTiHf alloys. The experimentation included loading thin walled tube Ni(sub 50.3)Ti(sub 29.7)Hf(sub 20) alloy samples along both proportional and nonproportional axial-torsion paths at different temperatures while measuring surface strains using stereo digital image correlation. A Ni(sub 50.3)Ti(sub 33.7)Hf(sub 16) alloy was also studied in tension and compression to document the effect of slightly depleting the Hf content on the constitutive responses of NiTiHf alloys. Samples of both alloys were made from nearly texture free polycrystalline material processed by hot extrusion. Analysis of the data shows that very small changes in composition significantly alter NiTiHf alloy properties, as the austenite finish (Af) temperature of the 16-at Hf alloy was found to be approximately 60 C less than the 20-at Hf alloy (approximately 120 C vs. 180 C). In addition, the 16-at Hf alloy exhibited smaller compressive transformation strains (2 vs. 2.5 percent). Multi-axial characterization of the 20-at % Hf alloy showed that while the random polycrystal transformation strains in tension (4 percent) and compression (2.5 percent) are modest in comparison with binary NiTi (6 percent, 4 percent), the torsion performance is superior (7 vs. 4 shear strain width to the pseudoelastic plateau).

The effect of Al segregation on Schottky barrier height and effective work function in TiAl/TiN/HfO2 gate stacks

NASA Astrophysics Data System (ADS)

Kim, Geun-Myeong; Oh, Young Jun; Chang, K. J.

2016-07-01

We perform first-principles density functional calculations to investigate the effects of Al incorporation on the p-type Schottky barrier height ≤ft({φ\\text{p}}\\right) and the effective work function for various high-k/metal gate stacks, such as TiN/HfO2 with interface Al impurities, Ti1-x Al x N/HfO2, and TiAl/TiN/HfO2. When Al atoms substitute for the interface Ti atoms at TiN/HfO2 interface, interface dipole fields become stronger, leading to the increase of {φ\\text{p}} and thereby the n-type shift of effective work function. In Ti1-x Al x N/HfO2 interface, {φ\\text{p}} linearly increases with the Al content, attributed to the presence of interface Al atoms. On the other hand, in TiAl/TiN/HfO2 interface, where Al is assumed not to segregate from TiAl to TiN, {φ\\text{p}} is nearly independent of the thickness of TiAl. Our results indicate that Al impurities at the metal/dielectric interface play an important role in controlling the effective work function, and provide a clue to understanding the n-type shift of the effective work function observed in TiAl/TiN/HfO2 gate stacks fabricated by using thegate-last process.

Fractionation of Zr and Hf during the differentiation of peralkaline magmatic system (Lovozero rare metal deposit, Kola Peninsula)

NASA Astrophysics Data System (ADS)

Kogarko, Liya

2016-04-01

Zirconium and hafnium are valuable strategic metals. We assessed principal features of the distribution of these elements in peralkaline rocks, ores and rock-forming and accessory minerals of Lovozero complex. The accumulation of these elements during the evolution of alkaline magma of Lovozero deposit up to extremely high concentrations in eudialyte ores (5-8% ZrO2 and 1200-1800 ppm Hf) has been established. These ores represent valuable complex raw material not only for Zr and Hf, but for REE as well. We evaluated partition coefficients of these elements in alkaline pyroxenes (aegirines) from porphyry-like agpaitic lujavrites of Lovozero massif which are 0.40 for zirconium and 0.58 for hafnium. We assessed variations of Zr/Hf ratio for all the rocks of Lovozero alkaline massif. The growth of this ratio in the course of the evolution of alkaline magma has been observed from 38 in the earliest magmatic phase, to 44 in the second phase and to 51-53 in the latest manifestation of alkaline magmatsm. On the basis of the obtained data and equations of equilibrium and fractional crystallization the model of the fractionation of zirconium and hafnium during the evolution of Lovozero intrusion has been constructed. We have demonstrated that the source of strongly enriched magmatic systems similar to Lovozero rare metal deposit is short-lived enriched reservoir - metasomatized and carbonatized mantle substrate. We investigated the fractionation of zirconium and hafnium in carbonatized mantle xenoliths from East Antarctica. The elevated Zr/Hf ratios (up to 125) in metasomatized xenoliths by comparison with the chondritic value have been found. The main reactions of carbonate metasomatism lead to the replacement of primary orthopyroxene by clinopyroxene 2Mg2Si2O6 + CaMg(CO3)2 = 2Mg2SiO4 + CaMgSi2O6 + 2CO2 3CaMg(CO3)2 + CaMgSi2O6 = 4CaCO3 + 2Mg2SiO4 + 2CO2 The substantial expansion of the clinopyroxene crystallization field results in increase of Zr/Hf ratio in equilibrium

Bone response to a novel Ti-Ta-Nb-Zr alloy.

PubMed

Stenlund, Patrik; Omar, Omar; Brohede, Ulrika; Norgren, Susanne; Norlindh, Birgitta; Johansson, Anna; Lausmaa, Jukka; Thomsen, Peter; Palmquist, Anders

2015-07-01

Commercially pure titanium (cp-Ti) is regarded as the state-of-the-art material for bone-anchored dental devices, whereas the mechanically stronger alloy (Ti-6Al-4V), made of titanium, aluminum (Al) and vanadium (V), is regarded as the material of choice for high-load applications. There is a call for the development of new alloys, not only to eliminate the potential toxic effect of Al and V but also to meet the challenges imposed on dental and maxillofacial reconstructive devices, for example. The present work evaluates a novel, dual-stage, acid-etched, Ti-Ta-Nb-Zr alloy implant, consisting of elements that create low toxicity, with the potential to promote osseointegration in vivo. The alloy implants (denoted Ti-Ta-Nb-Zr) were evaluated after 7 days and 28 days in a rat tibia model, with reference to commercially pure titanium grade 4 (denoted Ti). Analyses were performed with respect to removal torque, histomorphometry and gene expression. The Ti-Ta-Nb-Zr showed a significant increase in implant stability over time in contrast to the Ti. Further, the histological and gene expression analyses suggested faster healing around the Ti-Ta-Nb-Zr, as judged by the enhanced remodeling, and mineralization, of the early-formed woven bone and the multiple positive correlations between genes denoting inflammation, bone formation and remodeling. Based on the present experiments, it is concluded that the Ti-Ta-Nb-Zr alloy becomes osseointegrated to at least a similar degree to that of pure titanium implants. This alloy is therefore emerging as a novel implant material for clinical evaluation. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Microstructure research for ferroelectric origin in the strained Hf0.5Zr0.5O2 thin film via geometric phase analysis

NASA Astrophysics Data System (ADS)

Bi, Han; Sun, Qingqing; Zhao, Xuebing; You, Wenbin; Zhang, David Wei; Che, Renchao

2018-04-01

Recently, non-volatile semiconductor memory devices using a ferroelectric Hf0.5Zr0.5O2 film have been attracting extensive attention. However, at the nano-scale, the phase structure remains unclear in a thin Hf0.5Zr0.5O2 film, which stands in the way of the sustained development of ferroelectric memory nano-devices. Here, a series of electron microscopy evidences have illustrated that the interfacial strain played a key role in inducing the orthorhombic phase and the distorted tetragonal phase, which was the origin of the ferroelectricity in the Hf0.5Zr0.5O2 film. Our results provide insight into understanding the association between ferroelectric performances and microstructures of Hf0.5Zr0.5O2-based systems.

Refining As-cast β-Ti Grains Through ZrN Inoculation

NASA Astrophysics Data System (ADS)

Qiu, Dong; Zhang, Duyao; Easton, Mark A.; St John, David H.; Gibson, Mark A.

2018-03-01

The columnar-to-equiaxed transition and remarkable refinement of β-Ti grains occur in an as-cast Ti-13Mo alloy when a new grain refiner, ZrN, was inoculated at a nitrogen level as low as 0.4 wt pct. The grain refining effect is attributed to in situ-formed TiN particles that provide active nucleation sites and solute Zr that promotes constitutional supercooling. Reproducible orientation relationships were identified between TiN nucleants and β-Ti matrix, and well explained by the edge-to-edge matching model.

As-Cast Icosashedral Quasicrystals in Ti-Zr-Ni Alloys

NASA Astrophysics Data System (ADS)

Lee, Geun Woo; Gangopadhyay, Anup K.; Kelton, Kenneth F.

2002-03-01

Most Ti-based icosahedral quasicrystals (i-phase) obtained by rapid quenching from the melt are metastable and disordered. In contrast, the Ti-Zr-Ni i-phase prepared by low temperature annealing is stable and better ordered. This i-phase is formed by a solid-state transformation from C14 Laves phase and α (Ti/Zr) solid-solution phase. It has not been possible previously to grow this i-phase directly from the liquid. Here, the nucleation and growth of the i-phase from the liquid in as-cast Ti-Zr-Ni alloys is reported. Pentagonal growth ledges in as-cast Ti-Zr-Ni ingots are clearly observed. Transmission electron microscopy and x-ray diffraction studies confirm the phase identity. Differential scanning calorimetry measurements show an endothermic transformation from the i-phase to a phase mixture of the C14 Laves and solid-solution phases, demonstrating that this i-phase is also stable. The short time that the liquid remains in the Laves phase-forming-field and the higher nucleation rate of the i-phase, owing to the presumed similarity between the local atomic structures of the i-phase and liquid, allows the i-phase to nucleate and grow directly from the liquid. Container-less solidification studies using electrostatic levitation (ESL) techniques support this conclusion.

Friction and Wear of Unlubricated NiTiHf with Nitriding Surface Treatments

NASA Technical Reports Server (NTRS)

Stanford, Malcolm K.

2018-01-01

The unlubricated friction and wear properties of the superelastic materials NiTi and NiTiHf, treated by either gas nitriding or plasma nitriding, have been investigated. Pin on disk testing of the studied materials was performed at sliding speeds from 0.01 to 1m/s at normal loads of 1, 5 or 10N. For all of the studied friction pairs (NiTiHf pins vs. NiTi and NiTiHf disks) over the given parameters, the steady-state coefficients of friction varied from 0.22 to 1.6. Pin wear factors ranged from approximately 1E-6 against the NiTiHf and plasma nitrided disks to approximately 1E-4 for the gas nitrided disks. The plasma nitrided disks provided wear protection in several cases and tended to wear by adhesion. The gas nitrided treatment generated the most pin wear but had essentially no disk wear except at the most severe of the studied conditions (1N load and 1m/s sliding speed). The results of this study are expected to provide guidance for design of components such as gears and fasteners.

Reactive magnetron cosputtering of hard and conductive ternary nitride thin films: Ti-Zr-N and Ti-Ta-N

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

Abadias, G.; Koutsokeras, L. E.; Dub, S. N.

2010-07-15

Ternary transition metal nitride thin films, with thickness up to 300 nm, were deposited by dc reactive magnetron cosputtering in Ar-N{sub 2} plasma discharges at 300 deg. C on Si substrates. Two systems were comparatively studied, Ti-Zr-N and Ti-Ta-N, as representative of isostructural and nonisostructural prototypes, with the aim of characterizing their structural, mechanical, and electrical properties. While phase-separated TiN-ZrN and TiN-TaN are the bulk equilibrium states, Ti{sub 1-x}Zr{sub x}N and Ti{sub 1-y}Ta{sub y}N solid solutions with the Na-Cl (B1-type) structure could be stabilized in a large compositional range (up to x=1 and y=0.75, respectively). Substituting Ti atoms by eithermore » Zr or Ta atoms led to significant changes in film texture, microstructure, grain size, and surface morphology, as evidenced by x-ray diffraction, x-ray reflectivity, and scanning electron and atomic force microscopies. The ternary Ti{sub 1-y}Ta{sub y}N films exhibited superior mechanical properties to Ti{sub 1-x}Zr{sub x}N films as well as binary compounds, with hardness as high as 42 GPa for y=0.69. All films were metallic, the lowest electrical resistivity {rho}{approx}65 {mu}{Omega} cm being obtained for pure ZrN, while for Ti{sub 1-y}Ta{sub y}N films a minimum was observed at y{approx}0.3. The evolution of the different film properties is discussed based on microstructrural investigations.« less

Atom probe tomographic studies of precipitation in Al-0.1Zr-0.1Ti (at.%) alloys.

PubMed

Knipling, Keith E; Dunand, David C; Seidman, David N

2007-12-01

Atom probe tomography was utilized to measure directly the chemical compositions of Al(3)(Zr(1)-(x)Ti(x)) precipitates with a metastable L1(2) structure formed in Al-0.1Zr-0.1Ti (at.%) alloys upon aging at 375 degrees C or 425 degrees C. The alloys exhibit an inhomogeneous distribution of Al(3)(Zr(1)-(x)Ti(x)) precipitates, as a result of a nonuniform dendritic distribution of solute atoms after casting. At these aging temperatures, the Zr:Ti atomic ratio in the precipitates is about 10 and 5, respectively, indicating that Ti remains mainly in solid solution rather than partitioning to the Al(3)(Zr(1)-(x)Ti(x)) precipitates. This is interpreted as being due to the very small diffusivity of Ti in alpha-Al, consistent with prior studies on Al-Sc-Ti and Al-Sc-Zr alloys, where the slower diffusing Zr and Ti atoms make up a small fraction of the Al(3)(Zr(1)-(x)Ti(x)) precipitates. Unlike those alloys, however, the present Al-Zr-Ti alloys exhibit no interfacial segregation of Ti at the matrix/precipitate heterophase interface, a result that may be affected by a significant disparity in the evaporation fields of the alpha-Al matrix and Al(3)(Zr(1)-(x)Ti(x)) precipitates and/or a lack of local thermodynamic equilibrium at the interface.

Intense visible light emission from stress-activated ZrO2:Ti

NASA Astrophysics Data System (ADS)

Akiyama, Morito; Xu, Chao-Nan; Nonaka, Kazuhiro

2002-07-01

We have investigated the luminescence phenomena from stress-activated ZrO2:Ti. The luminescence is clearly visible to the naked eye in the atmosphere. The luminescence center has been identified as the Ti4+ ion from spectra of the mechanoluminescence and also from photoluminescence studies of ZrO2:Ti. The mechanoluminescence intensity decreases on repetitive application of stress but recovers completely on irradiation with ultraviolet light. ZrO2 is an n-type semiconductor and has electron traps. It is suggested that the mechanoluminescence mechanism arises from the movement of dislocations and recombination between electrons and holes released from these traps which are associated with the Ti4+ centers.

Effects of high pressure nitrogen annealing on ferroelectric Hf0.5Zr0.5O2 films

NASA Astrophysics Data System (ADS)

Kim, Taeho; Park, Jinsung; Cheong, Byoung-Ho; Jeon, Sanghun

2018-02-01

The effect of high-pressure nitrogen annealing at up to 50 atmospheres (atm) on Hf0.5Zr0.5O2 films at relatively low temperatures (450 °C) is analyzed using polarization-electric field curves, bipolar switching endurance measurements, grazing angle incidence X-ray diffraction, and piezoelectric force microscopy. Hf0.5Zr0.5O2 films annealed at 450 °C/50 atm have excellent characteristics, including remanent polarizations greater than 20 μC/cm2, a switching speed of 200 ns, and reliability, measured by sustained performance after 1010 bipolar switching cycles. The enhanced device features are attributed to the transition to the orthorhombic-phase from the tetragonal-phase of Hf0.5Zr0.5O2 at high pressure, which is also consistent with the results of "wake-up" analysis, and the variations of the pure polarization curves, extracted from the total displacement field under pressure.

Effects of Ti doping on the dielectric properties of HfO{sub 2} nanoparticles

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

Pokhriyal, S.; Biswas, S., E-mail: drsomnathbiswas@gmail.com

2016-05-06

We report the effects of Ti doping on the dielectric properties of HfO{sub 2} [Hf{sub 1-x}Ti{sub x}O{sub 2} (x = 0.2-0.8)] nanoparticles at room temperature. The Hf{sub 1-x}Ti{sub x}O{sub 2} nanoparticles were synthesized by a wet chemical process. The structural and morphological properties of the derived samples were analyzed with X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission electron microscopy (HRTEM). Impedance analysis was performed in pelletized samples in the frequency range of 1 MHz to 1 GHz. The obtained results were analyzed in correlation with microstructure and doping concentration in the derived samples. The averagemore » size of the Hf{sub 1-x}Ti{sub x}O{sub 2} nanoparticles is typically in the range of 4-8 nm depending on the processing temperature. The Hf{sub 1−x}Ti{sub x}O{sub 2} nanoparticles show reduction in crystallinity with the increase in Ti doping. The dielectric constants of the derived samples decrease with the increase in frequency. The ac-conductivity in the samples increases with the increase in frequency irrespective of Ti concentration and shows significant drop with the increase in Ti concentration at all frequencies.« less

Modeling of NiTiHf using finite difference method

NASA Astrophysics Data System (ADS)

Farjam, Nazanin; Mehrabi, Reza; Karaca, Haluk; Mirzaeifar, Reza; Elahinia, Mohammad

2018-03-01

NiTiHf is a high temperature and high strength shape memory alloy with transformation temperatures above 100oC. A constitutive model based on Gibbs free energy is developed to predict the behavior of this material. Two different irrecoverable strains including transformation induced plastic strain (TRIP) and viscoplastic strain (VP) are considered when using high temperature shape memory alloys (HTSMAs). The first one happens during transformation at high levels of stress and the second one is related to the creep which is rate-dependent. The developed model is implemented for NiTiHf under uniaxial loading. Finite difference method is utilized to solve the proposed equations. The material parameters in the equations are calibrated from experimental data. Simulation results are captured to investigate the superelastic behavior of NiTiHf. The extracted results are compared with experimental tests of isobaric heating and cooling at different levels of stress and also superelastic tests at different levels of temperature. More results are generated to investigate the capability of the proposed model in the prediction of the irrecoverable strain after full transformation in HTSMAs.

Investigating the Structural, Thermal, and Electronic Properties of the Zircon-Type ZrSiO4, ZrGeO4 and HfSiO4 Compounds

NASA Astrophysics Data System (ADS)

Chiker, Fafa; Boukabrine, Fatiha; Khachai, H.; Khenata, R.; Mathieu, C.; Bin Omran, S.; Syrotyuk, S. V.; Ahmed, W. K.; Murtaza, G.

2016-11-01

In the present study, the structural, thermal, and electronic properties of some important orthosilicate dielectrics, such as the ZrSiO4, ZrGeO4, and HfSiO4 compounds, have been investigated theoretically with the use of first-principle calculations. We attribute the application of the modified Becke-Johnson exchange potential, which is basically an improvement over the local density approximation and the Perdew-Burke-Ernzerhof exchange-correlation functional, for a better description of the band gaps of the compounds. This resulted in a good agreement with our estimated values in comparison with the reported experimental data, specifically for the ZrSiO4, and HfSiO4 compounds. Conversely, for the ZrGeO4 compound, the calculated electronic band structure shows a direct band gap at the Γ point with the value of 5.79 eV. Furthermore, our evaluated thermal properties that are calculated by using the quasi-harmonic Debye model indicated that the volume variation with temperature is higher in the ZrGeO4 compound as compared to both the ZrSiO4 and HfSiO4 compounds, which is ascribed to the difference between the electron shells of the Si and Ge atoms. Therefore, these results also indicate that while the entropy ( S) and enthalpy ( U) parameters increase monotonically, the free energy ( G), in contrast, decreases monotonically with increasing temperature, respectively. Moreover, the pressure and temperature dependencies of the Debye temperature Θ, thermal expansion coefficient, and heat capacities C V were also predicted in our study.

Lattice Thermal Conductivity of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2 from Atomistic Simulations

NASA Technical Reports Server (NTRS)

Lawson, JOhn W.; Daw, Murray S.; Bauschlicher, Charles W.

2011-01-01

Ultra high temperature ceramics (UHTC) including ZrB2 and HfB2 are candidate materials for applications in extreme environments because of their high melting point, good mechanical properties and reasonable oxidation resistance. Unlike many ceramics, these materials have high thermal conductivity which can be advantageous, for example, to reduce thermal shock. Recently, we developed Tersoff style interatomic potentials for both ZrB2 and HfB2 appropriate for atomistic simulations. As an application, Green-Kubo molecular dynamics simulations were performed to evaluate the lattice thermal conductivity for single crystals of ZrB2 and HfB2. The atomic mass difference in these binary compounds leads to oscillations in the time correlation function of the heat current. Results at room temperature and at elevated temperatures will be reported.

New FCC Mg–Zr and Mg–Zr–ti deuterides obtained by reactive milling

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

Guzik, Matylda N., E-mail: matylda.guzik@ife.no; Deledda, Stefano; Sørby, Magnus H.

2015-03-15

Results for binary Mg–Zr and ternary Mg–Zr–Ti mixtures ball milled at room temperature under reactive deuterium atmosphere (5.6–6.7 MPa) are reported. X-ray and neutron powder diffraction combined with Rietveld refinements show that two new cubic phases were formed during milling. Mg{sub 0.40}Zr{sub 0.60}D{sub 1.78} and Mg{sub 0.40}Zr{sub 0.26}Ti{sub 0.34}D{sub 1.98} crystallize with disordered face centered cubic metal atom arrangements. Results of differential scanning calorimetry and termogravimetric measurements demonstrate that both deuterides desorb deuterium at lower temperatures than MgD{sub 2}, ZrD{sub 2} or TiD{sub 2}; 528 and 575 K in the Mg–Zr–D and Mg–Zr–Ti–D system, respectively. Interestingly, Mg{sub 0.40}Zr{sub 0.26}Ti{sub 0.34}D{submore » 1.98} stores deuterium reversibly at 673 K and 10 MPa of D{sub 2}. - Graphical abstract: High resolution SR-PXD patterns obtained for Mg{sub 0.40}Zr{sub 0.60}D{sub 1.78} and first time reported Mg{sub 0.40}Zr{sub 0.26}Ti{sub 0.34}D{sub 1.98}. - Highlights: • Synthesis and characterization of Mg{sub 0.40}Zr{sub 0.60}D{sub 1.78} and Mg{sub 0.40}Zr{sub 0.26}Ti{sub 0.34}D{sub 1.98}. • New deuterides obtained by milling under H{sub 2} gas pressure in the order of a few MPa. • Phases desorb deuterium at temperature lower than corresponding binary deuterides. • Mg{sub 0.40}Zr{sub 0.26}Ti{sub 0.34}D{sub 1.98} stores hydrogen reversibly at 673 K and 10 MPa of D{sub 2}.« less

Hardness and Second Phase Percentage of Ni-Ti-Hf Compounds After Heat Treatment at 700C

NASA Technical Reports Server (NTRS)

Stanford, Malcolm K.

2017-01-01

The Vickers hardness and second phase precipitation of three ternary intermetallic Ni-Ti-Hf compounds containing either 1, 3 or 5 at.% Hf were compared to 60-Nitinol (55 at.% Ni - 45 at.% Ti). Heat treatment either at 700 C or with a subsequent aging step, hardened the 3 and 5 at.% Hf-containing ternaries to approximately 620 HV (56 HRC). Heat treatment increased the hardness of the 1 at.% Hf compound by more than 25 percent. Average hardness of the 3 and 5 at.% Hf ternaries, though higher than that of the binary Ni-Ti or the Ni-Ti-Hf compound containing 1 at.% Hf, appeared to be fairly insensitive to the different heat treatments. There was a drastic reduction of fatigue-enhancing second phase precipitates for the 5 at.% Hf ternaries compared to the other compounds. These results should guide materials selection for development of aerospace componentry.

Hf layer thickness dependence of resistive switching characteristics of Ti/Hf/HfO2/Au resistive random access memory device

NASA Astrophysics Data System (ADS)

Nakajima, Ryo; Azuma, Atsushi; Yoshida, Hayato; Shimizu, Tomohiro; Ito, Takeshi; Shingubara, Shoso

2018-06-01

Resistive random access memory (ReRAM) devices with a HfO2 dielectric layer have been studied extensively owing to the good reproducibility of their SET/RESET switching properties. Furthermore, it was reported that a thin Hf layer next to a HfO2 layer stabilized switching properties because of the oxygen scavenging effect. In this work, we studied the Hf thickness dependence of the resistance switching characteristics of a Ti/Hf/HfO2/Au ReRAM device. It is found that the optimum Hf thickness is approximately 10 nm to obtain good reproducibility of SET/RESET voltages with a small RESET current. However, when the Hf thickness was very small (∼2 nm), the device failed after the first RESET process owing to the very large RESET current. In the case of a very thick Hf layer (∼20 nm), RESET did not occur owing to the formation of a leaky dielectric layer. We observed the occurrence of multiple resistance states in the RESET process of the device with a Hf thickness of 10 nm by increasing the RESET voltage stepwise.

Composition dependences of crystal structure and electrical properties of epitaxial Pb(Zr,Ti)O3 films grown on Si and SrTiO3 substrates

NASA Astrophysics Data System (ADS)

Okamoto, Shoji; Okamoto, Satoshi; Yokoyama, Shintaro; Akiyama, Kensuke; Funakubo, Hiroshi

2016-10-01

{100}-oriented Pb(Zr x ,Ti1- x )O3 (PZT) thin films of approximately 2 µm thickness and Zr/(Zr + Ti) ratios of 0.39-0.65 were epitaxially grown on (100)cSrRuO3//(100)SrTiO3 (STO) and (100)cSrRuO3//(100)cLaNiO3//(100)CeO2//(100)YSZ//(100)Si (Si) substrates having different thermal expansion coefficients by pulsed metal-organic chemical vapor deposition (MOCVD). The effects of Zr/(Zr + Ti) ratio and type of substrate on the crystal structure and dielectric, ferroelectric and piezoelectric properties of the films were systematically investigated. The X-ray diffraction measurement showed that both films changed from having a tetragonal symmetry to rhombohedral symmetry through the coexisting region with increasing Zr/(Zr + Ti) ratio. This region showed the Zr/(Zr + Ti) ratios of 0.45-0.59 for the films on the STO substrates that were wider than the films on the Si substrates. Saturation polarization values were minimum at approximately Zr/(Zr + Ti) = 0.50 for the films on the STO substrates, and no obvious Zr/(Zr + Ti) ratio dependence was detected in the films on the Si substrates. On the other hand, the maximum field-induced strain values measured by scanning force microscopy at approximately Zr/(Zr + Ti) = 0.50 at 100 kV/cm were about 0.5 and 0.1% in the films on the Si and STO, respectively.

Properties and Degradation of Polarization Reversal of Soft BaTiO3 Ceramics for Ferroelectric Thin-Film Devices

NASA Astrophysics Data System (ADS)

Thongrueng, Jirawat; Tsuchiya, Toshio; Masuda, Yoichiro; Fujita, Shigetaka; Nagata, Kunihiro

1999-09-01

Soft BaTiO3 ceramics having a very low coercive field of 65 V/mm were prepared by substituting 9 mol% Hf Zr for the Ti-site of BaTiO3, for applications to ferroelectric thin-film devices. Electrical properties of the soft BaTiO3 ceramics were measured and compared with those of normal BaTiO3 ceramics. By substituting Hf Zr for Ti-site, the phase transition temperatures were controlled, and we could select the preferred crystal structure from the tetragonal, orthorhombic and rhombohedral phases at room temperature. In addition, the preparation and characterization of the soft BaTiO3 thin-films using a sol-gel process were carried out.

Experimental and theoretical determination of the dipole-quadrupole and dipole-octopole polarizabilities of the group IV tetrachlorides TiCl4, ZrCl4, and HfCl4

NASA Astrophysics Data System (ADS)

Hohm, Uwe; Maroulis, G.

2006-03-01

The dipole-quadrupole and dipole-octopole polarizabilities A and E of TiCl4, ZrCl4, and HfCl4 have been determined from collision-induced light-scattering experiments. Our respective experimental results for ∣A ∣ are (165±10), (110±30), and (140±20) e2a03Eh-1, whereas ∣E∣ is determined to be (675±125), (750±200), and (670±400) e2a04Eh-1. Theory predicts values convincingly close to experiment, as A =(181.4±9.1), (167.6±8.4), and (139.8±7.0) e2a03Eh-1, and E =(-671±67), (-688±69), and (-574±57) e2a04Eh-1. In addition our quantum chemical ab initio calculations give reliable values for the dipole polarizability α, as well as for the octopole and hexadecapole moments Ω and Φ for all three substances.

Increasing Ti-6Al-4V brazed joint strength equal to the base metal by Ti and Zr amorphous filler alloys

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

Ganjeh, E., E-mail: navidganjehie@sina.kntu.ac.ir; Sarkhosh, H.; Bajgholi, M.E.

Microstructural features developed along with mechanical properties in furnace brazing of Ti-6Al-4V alloy using STEMET 1228 (Ti-26.8Zr-13Ni-13.9Cu, wt.%) and STEMET 1406 (Zr-9.7Ti-12.4Ni-11.2Cu, wt.%) amorphous filler alloys. Brazing temperatures employed were 900-950 Degree-Sign C for the titanium-based filler and 900-990 Degree-Sign C for the zirconium-based filler alloys, respectively. The brazing time durations were 600, 1200 and 1800 s. The brazed joints were evaluated by ultrasonic test, and their microstructures and phase constitutions analyzed by metallography, scanning electron microscopy and X-ray diffraction analysis. Since microstructural evolution across the furnace brazed joints primarily depends on their alloying elements such as Cu, Ni andmore » Zr along the joint. Accordingly, existence of Zr{sub 2}Cu, Ti{sub 2}Cu and (Ti,Zr){sub 2}Ni intermetallic compounds was identified in the brazed joints. The chemical composition of segregation region in the center of brazed joints was identical to virgin filler alloy content which greatly deteriorated the shear strength of the joints. Adequate brazing time (1800 s) and/or temperature (950 Degree-Sign C for Ti-based and 990 Degree-Sign C for Zr-based) resulted in an acicular Widmanstaetten microstructure throughout the entire joint section due to eutectoid reaction. This microstructure increased the shear strength of the brazed joints up to the Ti-6Al-4V tensile strength level. Consequently, Ti-6Al-4V can be furnace brazed by Ti and Zr base foils produced excellent joint strengths. - Highlights: Black-Right-Pointing-Pointer Temperature or time was the main factors of controlling braze joint strength. Black-Right-Pointing-Pointer Developing a Widmanstaetten microstructure generates equal strength to base metal. Black-Right-Pointing-Pointer Brittle intermetallic compounds like (Ti,Zr){sub 2}Ni/Cu deteriorate shear strength. Black-Right-Pointing-Pointer Ti and Zr base filler alloys were the best choice for

Grain Refinement and Mechanical Properties of Cu–Cr–Zr Alloys with Different Nano-Sized TiCp Addition

PubMed Central

Zhang, Dongdong; Bai, Fang; Wang, Yong; Wang, Jinguo; Wang, Wenquan

2017-01-01

The TiCp/Cu master alloy was prepared via thermal explosion reaction. Afterwards, the nano-sized TiCp/Cu master alloy was dispersed by electromagnetic stirring casting into the melting Cu–Cr–Zr alloys to fabricate the nano-sized TiCp-reinforced Cu–Cr–Zr composites. Results show that nano-sized TiCp can effectively refine the grain size of Cu–Cr–Zr alloys. The morphologies of grain in Cu–Cr–Zr composites changed from dendritic grain to equiaxed crystal because of the addition and dispersion of nano-sized TiCp. The grain size decreased from 82 to 28 μm with the nano-sized TiCp content. Compared with Cu–Cr–Zr alloys, the ultimate compressive strength (σUCS) and yield strength (σ0.2) of 4 wt% TiCp-reinforced Cu–Cr–Zr composites increased by 6.7% and 9.4%, respectively. The wear resistance of the nano-sized TiCp-reinforced Cu–Cr–Zr composites increased with the increasing nano-sized TiCp content. The wear loss of the nano-sized TiCp-reinforced Cu–Cr–Zr composites decreased with the increasing TiCp content under abrasive particles. The eletrical conductivity of Cu–Cr–Zr alloys, 2% and 4% nano-sized TiCp-reinforced Cu–Cr–Zr composites are 64.71% IACS, 56.77% IACS and 52.93% IACS, respectively. PMID:28786937

XAFS atomistic insight of the oxygen gettering in Ti/HfO 2 based OxRRAM

NASA Astrophysics Data System (ADS)

Viennet, R.; Roussel, H.; Rapenne, L.; Deschanvres, J. L.; Renevier, H.; Jousseaume, V.; Jalaguier, E.; Proietti, M. G.

2018-05-01

Hafnia-based resistive memories technology has come to maturation and acceded to the market of nonvolatile memories. Nevertheless, the physical mechanisms involved in resistive switching are not yet fully understood and the numerous ab initio simulations studies have few many atomic-scale experimental counterparts. In this study we investigate the oxygen migration mechanism from an amorphous HfO2 layer to the Ti cap layer at a local scale before and after a thermal treatment. X-ray absorption spectroscopy at the Ti K edge and Hf LIII edge has been performed on samples as-deposited and annealed in Ar at 400 ∘C to mimic the back-end-of-line thermal budget (BEOL) of CMOS technology. The short-range Ti and Hf environments have been determined, showing that annealing promotes the migration of O from HfO2 to Ti, the amount of which is quantified. This provokes an expansion and an increase of atomic disorder in the Ti lattice. The nature of the oxygen gettering mechanism by the Ti metal is understood by comparing samples with increasing Ti-capping thickness. We show that the Ti getter effect has to be activated by thermal treatment and that the O diffusion takes place in a region of a few nanometers close to the Ti /HfO2 interface. Therefore, the thermal budget history and the Ti cap-layer thickness determine the oxygen vacancy content in the HfO2 layer, which in turn controls the electrical properties, especially the forming operation.

SYNTHESIS OF ZrI$sub 4$ AND HfI$sub 4$ BY HALOID EXCHANGE (in Russian)

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

Nisel'son, L.A.; Teslitskaya, M.V.; Shvedova, T.A.

1962-05-01

Syntheses of ZrI/sub 4/ and Hfl/sub 4/ by reactions of ZrCl/sub 4/ with SiI/sub 4/, Al/sub 2/I/sub 6/, HI, and Al/sub 2/Br and HfCl/sub 4/ with Al/sub 2 / I/sub 6/ are analyzed. The highest exchange yield was reached with /sub 4/ from ZrCl/sub 4/ and other admixtures was achieved by distillation. (R.V.J.)

Grain Refinement and Mechanical Properties of Cu-Cr-Zr Alloys with Different Nano-Sized TiCp Addition.

PubMed

Zhang, Dongdong; Bai, Fang; Wang, Yong; Wang, Jinguo; Wang, Wenquan

2017-08-08

The TiC p /Cu master alloy was prepared via thermal explosion reaction. Afterwards, the nano-sized TiC p /Cu master alloy was dispersed by electromagnetic stirring casting into the melting Cu-Cr-Zr alloys to fabricate the nano-sized TiC p -reinforced Cu-Cr-Zr composites. Results show that nano-sized TiC p can effectively refine the grain size of Cu-Cr-Zr alloys. The morphologies of grain in Cu-Cr-Zr composites changed from dendritic grain to equiaxed crystal because of the addition and dispersion of nano-sized TiC p . The grain size decreased from 82 to 28 μm with the nano-sized TiC p content. Compared with Cu-Cr-Zr alloys, the ultimate compressive strength (σ UCS ) and yield strength (σ 0.2 ) of 4 wt% TiC p -reinforced Cu-Cr-Zr composites increased by 6.7% and 9.4%, respectively. The wear resistance of the nano-sized TiCp-reinforced Cu-Cr-Zr composites increased with the increasing nano-sized TiCp content. The wear loss of the nano-sized TiC p -reinforced Cu-Cr-Zr composites decreased with the increasing TiC p content under abrasive particles. The eletrical conductivity of Cu-Cr-Zr alloys, 2% and 4% nano-sized TiCp-reinforced Cu-Cr-Zr composites are 64.71% IACS, 56.77% IACS and 52.93% IACS, respectively.

ZnO/(Hf,Zr)O2/ZnO-trilayered nanowire capacitor structure fabricated solely by metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Fujisawa, Hironori; Kuwamoto, Kei; Nakashima, Seiji; Shimizu, Masaru

2016-02-01

HfO2-based thin films are one of the key dielectric and ferroelectric materials in Si-CMOS LSIs as well as in oxide electronic nanodevices. In this study, we demonstrated the fabrication of a ZnO/(Hf,Zr)O2/ZnO-trilayered nanowire (NW) capacitor structure solely by metalorganic chemical vapor deposition (MOCVD). 15-nm-thick dielectric (Hf,Zr)O2 and 40-nm-thick top ZnO electrode layers were uniformly grown by MOCVD on a ZnO NW template with average diameter, length, and aspect ratio of 110 nm, 10 µm, and ˜90, respectively. The diameter and aspect ratio of the resultant trilayerd NWs are 200-300 nm and above 30, respectively. The crystalline phase of HfO2 and stacked the structure are also discussed.

Electrochemical studies on zirconium and its biocompatible alloys Ti-50Zr at.% and Zr-2.5Nb wt.% in simulated physiologic media.

PubMed

Oliveira, Nilson T C; Biaggio, Sonia R; Rocha-Filho, Romeu C; Bocchi, Nerilso

2005-09-01

Different electrochemical studies were carried out for Zr and its biocompatible alloys Ti-50Zr at.% and Zr-2.5Nb wt.% in solutions simulating physiologic media, Ringer and PBS (phosphate buffered saline) solutions. The results from rest-potential measurements showed that the three materials are spontaneously passivated in both solutions and that the Ti-50Zr alloy has the greatest tendency for spontaneous oxide formation. Some corrosion parameters (such as the pitting and repassivation potentials) were obtained via cyclic voltammetry in both solutions, revealing that the Ti-50Zr has the best corrosion protection while Zr has the worst. On the other hand, the pre-anodization (up to 8 V vs. SCE) of the alloys in a 0.15 mol/L Na2SO4 solution led to a significant improvement in their protection against pitting corrosion when exposed to the Ringer solution. Elemental analyses by EDX showed that during pitting corrosion, there is no preferential corrosion of any of the alloying elements (Zr, Ti, Nb). Copyright (c) 2005 Wiley Periodicals, Inc.

Hydrolysis of ZrCl4 and HfCl4: The Initial Steps in the High-Temperature Oxidation of Metal Chlorides to Produce ZrO2 and HfO2

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

Fang, Zongtang; Dixon, David A.

2013-03-08

The gas-phase hydrolysis of MCl4 (M = Zr, Hf) to produce the initial particles on the way to zirconia and hafnia nanoparticles has been studied with electronic structure theory. The potential energy surfaces, the themochemistry of the reaction species, and the reaction paths for the initial steps of MCl4 reacting with H2O have been calculated. The hydrolysis of MCl4 at higher temperatures begins with the formation of oxychlorohydroxides followed by the elimination of HCl instead of the direct production of MOCl2 and HCl or MO2 and HCl due to the substantial endothermicities associated with the formation of gas-phase MO2. Themore » structural properties and heats of formation of the reactants and products are consistent with the available experimental results. A number of metal oxychlorides (oxychlorohydroxides) intermediate clusters have been studied to assess their role in the production of MO2 nanoparticles. The calculated clustering reaction energies of those intermediates are highly exothermic, so they could be readily formed in the hydrolysis process. These intermediate clusters can be formed exothermically from metal oxychlorohydroxides by the elimination of one HCl or H2O molecule. Our calculations show that the mechanisms leading to the formation of MO2 nanoparticles are complicated and are accompanied by the potential production of a wide range of intermediates, as found for the production of TiO2 particles from the high-temperature oxidation of TiCl4.« less

First-principles study of (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 solid solutions

NASA Astrophysics Data System (ADS)

Amoroso, Danila; Cano, Andrés; Ghosez, Philippe

2018-05-01

(Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 solid solutions are the building blocks of lead-free piezoelectric materials that attract a renewed interest. We investigate the properties of these systems by means of first-principles calculations, with a focus on the lattice dynamics and the competition between different ferroelectric phases. We first analyze the four parent compounds in order to compare their properties and their different tendency towards ferroelectricity. The core of our study is systematic characterization of the binary systems (Ba ,Ca ) TiO3 and Ba (Ti ,Zr ) O3 within both the virtual crystal approximation and direct supercell calculations. In the case of Ca doping, we find a gradual transformation from B -site to A -site ferroelectricity due to steric effects that largely determines the behavior of the system. In the case of Zr doping, in contrast, the behavior is eventually dominated by cooperative Zr-Ti motions and the local electrostatics. In addition, our comparative study reveals that the specific microscopic physics of these solids sets severe limits to the applicability of the virtual crystal approximation for these systems.

Experimental Determination of Impurity and Interdiffusion Coefficients in Seven Ti and Zr Binary Systems Using Diffusion Multiples

NASA Astrophysics Data System (ADS)

Chen, Zhangqi; Liu, Zi-Kui; Zhao, Ji-Cheng

2018-05-01

Diffusion coefficients of seven binary systems (Ti-Mo, Ti-Nb, Ti-Ta, Ti-Zr, Zr-Mo, Zr-Nb, and Zr-Ta) at 1200 °C, 1000 °C, and 800 °C were experimentally determined using three Ti-Mo-Nb-Ta-Zr diffusion multiples. Electron probe microanalysis (EPMA) was performed to collect concentration profiles at the binary diffusion regions. Forward simulation analysis (FSA) was then applied to extract both impurity and interdiffusion coefficients in Ti-rich and Zr-rich part of the bcc phase. Excellent agreements between our results and most of the literature data validate the high-throughput approach combining FSA with diffusion multiples to obtain a large amount of systematic diffusion data, which will help establish the diffusion (mobility) databases for the design and development of biomedical and structural Ti alloys.

Experimental Determination of Impurity and Interdiffusion Coefficients in Seven Ti and Zr Binary Systems Using Diffusion Multiples

NASA Astrophysics Data System (ADS)

Chen, Zhangqi; Liu, Zi-Kui; Zhao, Ji-Cheng

2018-07-01

Diffusion coefficients of seven binary systems (Ti-Mo, Ti-Nb, Ti-Ta, Ti-Zr, Zr-Mo, Zr-Nb, and Zr-Ta) at 1200 °C, 1000 °C, and 800 °C were experimentally determined using three Ti-Mo-Nb-Ta-Zr diffusion multiples. Electron probe microanalysis (EPMA) was performed to collect concentration profiles at the binary diffusion regions. Forward simulation analysis (FSA) was then applied to extract both impurity and interdiffusion coefficients in Ti-rich and Zr-rich part of the bcc phase. Excellent agreements between our results and most of the literature data validate the high-throughput approach combining FSA with diffusion multiples to obtain a large amount of systematic diffusion data, which will help establish the diffusion (mobility) databases for the design and development of biomedical and structural Ti alloys.

Dehydriding properties of Ti or/and Zr-doped sodium aluminum hydride prepared by ball-milling

NASA Astrophysics Data System (ADS)

Xiao, Xue-Zhang; Chen, Li-Xin; Wang, Xin-Hua; Li, Shou-Quan; Hang, Zhou-Ming; Chen, Chang-Pin; Wang, Qi-Dong

2007-12-01

The NaAlH4 complex is attracting great attention for its potential applications in hydrogen-powered fuel-cell vehicles due to its high hydrogen storage capacity and suitable thermodynamic properties. However, its practicable hydrogen storage capacity presently obtained is less than the theoretical capacity (5.6 wt.%). To improve the hydrogen capacity, we chose metallic Ti or/and Zr powder as catalyst dopants, and prepared the sodium aluminum hydride by hydrogenation of ball-milled NaH/Al mixture containing 10 mol% dopants with different proportions of Ti and Zr, and then investigated the effects on their hydrogen storage (dehydriding) properties. The results showed that different catalyst dopants affected the dehydriding properties greatly. The catalysis of metal Ti as a catalyst dopant alone on dehydriding kinetics for the entire dehydrogenation process of ball-milled (NaH/Al) composite was higher than that of adopting Zr alone. The synergistic catalytic effect of Ti and Zr together as co-dopants on the dehydrogenation process of (NaH/Al) composite was higher than that using only Ti or Zr as dopant individually. The composite doped with proper proportion of Ti and Zr together (8 mol% Ti+ 2 mol% Zr) as co-dopants exhibited the highest dehydriding kinetic property and desorption capacity.

Are new TiNbZr alloys potential substitutes of the Ti6Al4V alloy for dental applications? An electrochemical corrosion study.

PubMed

Ribeiro, Ana Lúcia Roselino; Hammer, Peter; Vaz, Luís Geraldo; Rocha, Luís Augusto

2013-12-01

The main aim of this work was to assess the electrochemical behavior of new Ti35Nb5Zr and Ti35Nb10Zr alloys in artificial saliva at 37 °C to verify if they are indicated to be used as biomaterials in dentistry as alternatives to Ti6Al4V alloys in terms of corrosion protection efficiency of the material. Electrochemical impedance spectroscopy (EIS) experiments were carried out for different periods of time (0.5-216 h) in a three-electrode cell, where the working electrode (Ti alloys) was exposed to artificial saliva at 37 °C. The near-surface region of the alloys was investigated using x-ray photoelectron spectroscopy (XPS). All alloys exhibited an increase in corrosion potential with the immersion time, indicating the growth and stabilization of the passive film. Ti35Nb5Zr and Ti6Al4V alloys had their EIS results interpreted by a double-layer circuit, while the Ti35Nb10Zr alloy was modeled by a one-layer circuit. In general, the new TiNbZr alloys showed similar behavior to that observed for the Ti6Al4V. XPS results suggest, in the case of the TiNbZr alloys, the presence of a thicker passive layer containing a lower fraction of TiO2 phase than that of Ti6Al4V. After long-term immersion, all alloys develop a calcium phosphate phase on the surface. The new TiNbZr alloys appear as potential candidates to be used as a substitute to Ti6Al4V in the manufacturing of dental implant-abutment sets.

Effect of heat treatment on morphology evolution of Ti2Ni phase in Ti-Ni-Al-Zr alloy

NASA Astrophysics Data System (ADS)

Sheng, Liyuan; Yang, Yang; Xi, Tingfei

2018-03-01

The Ti6Al2Zr alloy with 15 wt.% Ni addition was prepared and then heat treated in the research. The microstructure of the alloy and evolution of Ti2Ni precipitate were investigated. The microstructure observations demonstrate that the Ni addition could promote the formation of eutectoid and eutectic structures in Ti-Al-Zr alloy. In the eutectoid structure, the ultrafine Ti2Ni fiber precipitates in the α-Ti matrix, but in the eutectic structure, the fine α-Ti phases precipitate in the Ti2Ni matrix. The heat treatment could change the morphology of Ti2Ni precipitates by thinning, fragmenting, merging and spherizing. In the alloy heat treated at and below 1073K, the coarsening of α-Ti precipitates in eutectic structure and Ti2Ni precipitates in eutectoid structure is the mainly characteristic. In the alloy heat treated above 1073K, the phase transformation of α to β phase is the main characteristic, which changes the morphology and amount of Ti2Ni phase by the solid solution of Ni. The phase transformation temperature of Ti-Ni-Al-Zr alloy is between 1073-1123K, which is increased compared with that of the Ti-Ni binary phase diagram.

First principles study of structural, electronic and optical properties of perovskites CaZrO3 and CaHfO3 in cubic phase

NASA Astrophysics Data System (ADS)

Hoat, D. M.; Silva, J. F. Rivas; Blas, A. Méndez

2018-07-01

In this work, we present the first principles calculations for structural, electronic and optical properties of perovskites CaZrO3 and CaHfO3 using the full-potential linearized augmented plane wave method (FP-LAPW) within the framework of density functional theory (DFT) as implemented in WIEN2k package. The exchange-correlation potential is treated with local density approximation (LDA) and generalized gradient approximation (GGA-PBE and PBESol). Additionally, the Tran Blaha modified Becke-Johnson exchange potential (mBJ) also is employed for electronic and optical calculations due to that it gives very accurate band gap of solids. Our obtained structural parameters are in good agreement with experimental datas and other theoretical results. The energy band gap obtained with mBJ is 4.56 eV for CaZrO3 and 5.27 eV for CaHfO3. The hybridization of states of O atom with those of Zr and Hf atoms in CaZrO3 and CaHfO3, respectively, is observed. The spin-orbit coupling effect on electronic properties of considered compounds also is investigated. Finally, the linear optical properties of CaZrO3 and CaHfO3 are derived from their complex dielectric function calculated with mBJ potential for wide energy range up to 45 eV, and all of them analyzed in details.

Biocorrosion Evaluation on a Zr-Cu-Ag-Ti Metallic Glass

NASA Astrophysics Data System (ADS)

Kumar, Shresh; Anwar, Rebin; Ryu, Wookha; Park, E. S.; Vincent, S.

2018-04-01

Metallic glasses are in high demand for fabrication of variety of innovative products, in particular surgical and biomedical tools and devices owing to its excellent biocompatible properties. In the present investigation, a novel Zr39.5Cu50.5Ag4Ti6 metallic glass composition was synthesized using melt spinning technique. Potentiodynamic polarization studies were conducted to investigate bio-corrosion behaviour of Zr39.5Cu50.5Ag4Ti6 metallic glass. The test were conducted in various simulated artificial body conditions such as artificial saliva solution, phosphate-buffered saline solution, artificial blood plasma solution, and Hank’s balanced saline solution. The bio-corrosion results of metallic glass were compared with traditional biomaterials. The study aims to provide bio-compatible properties of Zr39.5Cu50.5Ag4Ti6 metallic glass.

Mechanical Characterisation and Biomechanical and Biological Behaviours of Ti-Zr Binary-Alloy Dental Implants

PubMed Central

Jiménez-Garrudo, Antonio; Gil-Mur, Francisco Javier; Manero, José María; Punset-Fuste, Miquel; Chávarri-Prado, David; Diéguez-Pereira, Markel; Monticelli, Francesca

2017-01-01

The objective of the study is to characterise the mechanical properties of Ti-15Zr binary alloy dental implants and to describe their biomechanical behaviour as well as their osseointegration capacity compared with the conventional Ti-6Al-4V (TAV) alloy implants. The mechanical properties of Ti-15Zr binary alloy were characterised using Roxolid© implants (Straumann, Basel, Switzerland) via ultrasound. Their biomechanical behaviour was described via finite element analysis. Their osseointegration capacity was compared via an in vivo study performed on 12 adult rabbits. Young's modulus of the Roxolid© implant was around 103 GPa, and the Poisson coefficient was around 0.33. There were no significant differences in terms of Von Mises stress values at the implant and bone level between both alloys. Regarding deformation, the highest value was observed for Ti-15Zr implant, and the lowest value was observed for the cortical bone surrounding TAV implant, with no deformation differences at the bone level between both alloys. Histological analysis of the implants inserted in rabbits demonstrated higher BIC percentage for Ti-15Zr implants at 3 and 6 weeks. Ti-15Zr alloy showed elastic properties and biomechanical behaviours similar to TAV alloy, although Ti-15Zr implant had a greater BIC percentage after 3 and 6 weeks of osseointegration. PMID:29318142

Engineering of the chemical reactivity of the Ti/HfO₂ interface for RRAM: experiment and theory.

PubMed

Calka, Pauline; Sowinska, Malgorzata; Bertaud, Thomas; Walczyk, Damian; Dabrowski, Jarek; Zaumseil, Peter; Walczyk, Christian; Gloskovskii, Andrei; Cartoixà, Xavier; Suñé, Jordi; Schroeder, Thomas

2014-04-09

The Ti/HfO2 interface plays a major role for resistance switching performances. However, clear interface engineering strategies to achieve reliable and reproducible switching have been poorly investigated. For this purpose, we present a comprehensive study of the Ti/HfO2 interface by a combined experimental-theoretical approach. Based on the use of oxygen-isotope marked Hf*O2, the oxygen scavenging capability of the Ti layer is clearly proven. More importantly, in line with ab initio theory, the combined HAXPES-Tof-SIMS study of the thin films deposited by MBE clearly establishes a strong impact of the HfO2 thin film morphology on the Ti/HfO2 interface reactivity. Low-temperature deposition is thus seen as a RRAM processing compatible way to establish the critical amount of oxygen vacancies to achieve reproducible and reliable resistance switching performances.

Geochemistry of Zr, Hf, and REE in a wide spectrum of Eh and water composition: The case of Dead Sea Fault system (Israel)

NASA Astrophysics Data System (ADS)

Censi, P.; Raso, M.; Yechieli, Y.; Ginat, H.; Saiano, F.; Zuddas, P.; Brusca, L.; D'Alessandro, W.; Inguaggiato, C.

2017-03-01

Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh < 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu2+ concentration relative to Eu3+ in these waters suggested by model calculations. The higher stability of Eu2+ with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.

In Situ Synchrotron Radiation X-ray Diffraction Study on Phase and Oxide Growth during a High Temperature Cycle of a NiTi-20 at.% Zr High Temperature Shape Memory Alloy

NASA Astrophysics Data System (ADS)

Carl, Matthew; Van Doren, Brian; Young, Marcus L.

2018-03-01

Ternary additions to binary NiTi shape memory alloys are known to significantly affect the characteristic martensite-to-austenite phase transformation, i.e., decrease or increase transformation temperatures. High temperature shape memory alloys can be created by adding Au, Pt, Pd, Hf, or Zr to binary NiTi in appropriate amounts; however, the majority of these ternary additions are exceedingly expensive, unfortunately making them impractical for most commercial applications. Zr is the exception of the group, but it is often disregarded because of its poor workability and thermal stability. In an effort to find a temperature range that allows for the potential workability of NiTiZr alloys in normal atmosphere environments and to gain understanding as to the cause of failure during processing, a NiTi-20 at.% Zr was subjected to a thermal cycle ranging from RT to 1000 °C with short 15 min holds at select temperatures during both heating and cooling while simultaneously collecting high-energy synchrotron radiation X-ray diffraction measurements. This study provides valuable insight into the kinetics of precipitation and oxide formation and its relationship to processing. In addition, scanning electron microscopy was performed on five samples, each isothermally held to examine precipitation and oxide structure and growth.

In Situ Synchrotron Radiation X-ray Diffraction Study on Phase and Oxide Growth during a High Temperature Cycle of a NiTi-20 at.% Zr High Temperature Shape Memory Alloy

NASA Astrophysics Data System (ADS)

Carl, Matthew; Van Doren, Brian; Young, Marcus L.

2018-02-01

Ternary additions to binary NiTi shape memory alloys are known to significantly affect the characteristic martensite-to-austenite phase transformation, i.e., decrease or increase transformation temperatures. High temperature shape memory alloys can be created by adding Au, Pt, Pd, Hf, or Zr to binary NiTi in appropriate amounts; however, the majority of these ternary additions are exceedingly expensive, unfortunately making them impractical for most commercial applications. Zr is the exception of the group, but it is often disregarded because of its poor workability and thermal stability. In an effort to find a temperature range that allows for the potential workability of NiTiZr alloys in normal atmosphere environments and to gain understanding as to the cause of failure during processing, a NiTi-20 at.% Zr was subjected to a thermal cycle ranging from RT to 1000 °C with short 15 min holds at select temperatures during both heating and cooling while simultaneously collecting high-energy synchrotron radiation X-ray diffraction measurements. This study provides valuable insight into the kinetics of precipitation and oxide formation and its relationship to processing. In addition, scanning electron microscopy was performed on five samples, each isothermally held to examine precipitation and oxide structure and growth.

Microstructures, Martensitic Transformation, and Mechanical Behavior of Rapidly Solidified Ti-Ni-Hf and Ti-Ni-Si Shape Memory Alloys

NASA Astrophysics Data System (ADS)

Han, X. L.; Song, K. K.; Zhang, L. M.; Xing, H.; Sarac, B.; Spieckermann, F.; Maity, T.; Mühlbacher, M.; Wang, L.; Kaban, I.; Eckert, J.

2018-03-01

In this work, the microstructure and mechanical properties of rapidly solidified Ti50- x/2Ni50- x/2Hf x ( x = 0, 2, 4, 6, 8, 10, and 12 at.%) and Ti50- y/2Ni50- y/2Si y ( y = 1, 2, 3, 5, 7, and 10 at.%) shape memory alloys (SMAs) were investigated. The sequence of the phase formation and transformations in dependence on the chemical composition is established. Rapidly solidified Ti-Ni-Hf or Ti-Ni-Si SMAs are found to show relatively high yield strength and large ductility for specific Hf or Si concentrations, which is due to the gradual disappearance of the phase transformation from austenite to twinned martensite and the predominance of the phase transformation from twinned martensite to detwinned martensite during deformation as well as to the refinement of dendrites and the precipitation of brittle intermetallic compounds.

Investigation of (Ti-Zr-Hf-V-Nb)N Multicomponent Nanostructured Coatings before and after Thermal Annealing by Nuclear Physics Methods of Analysis

NASA Astrophysics Data System (ADS)

Pogrebnjak, A. D.; Beresnev, V. M.; Bondar', A. V.; Kaverin, M. V.; Ponomarev, A. G.

2013-10-01

(Ti-Zr-Hf-V-Nb)N multicomponent nanostructured coatings with thickness of 1.0-1.4 μm synthesized by the method of cathode arc-vapor deposition at temperatures of 250-300°С are investigated by various mutually complementary methods of elemental structural analysis using slow positron beams (SPB), proton microbeam based particle-induced x-ray emission (μ-PIXE), energy-dispersive x-ray spectroscopy (EDS) and scanning electron microscopy (SEM) analyses based on electron micro- and nanobeams, x-ray diffraction (XRD) method of phase structural analysis, and the "a-sin2φ" method of measuring a stressed-strained state (x-ray tensometry). The elemental composition, microstructure, residual stress in nanograins, profiles of defect and atom distributions with depth and over the coating surface in 3D-representation are studied for these coatings, and their phase composition, severely strained state, and composition of coatings before and after annealing at Tann = 600°С for annealing time τ = 30 min are investigated. It is demonstrated that the oxidation resistance of the examined coatings can be significantly increased by high-temperature annealing that leads to the formation of elastic severely strained compression state of the coating. Redistribution of elements and defects, their segregation near the interface boundaries and around grains and subgrains in the process of thermostimulated diffusion, and termination of spinodal segregation without considerable change of the average nanograin size are revealed.

Effect of photocatalytic reduction of carbon dioxide by N-Zr co-doped nano TiO2.

PubMed

Zhang, Ru; Wang, Li; Kang, Zhuo; Li, Qiang; Pan, Huixian

2017-11-01

Modified sol-gel method was adopted to prepare TiO 2 , Zr-TiO 2 and N/Zr-TiO 2 composite catalyst. The as-synthesized photocatalysts were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Brunner- Emmet- Teller measurement and UV-Vis diffuse reflectance spectroscopy. And the photocatalytic performance toward CO 2 reduction was evaluated under ultraviolet light. The catalyst particles were demonstrated in the nanometer level size. When N and Zr are co-doped, on the one hand, Ti 4+ can be replaced by Zr 4  +, which leads to lattice distortion and inhibits electron-hole recombination. On the other hand, N enters into TiO 2 lattice gap to form O-Ti-N bond structure, and partial Ti 4+ are reduced to Ti 3+ . Compared with pristine TiO 2 , the specific surface area and the band gap of N/Zr-TiO 2 were improved and reduced, respectively. The N and Zr synergistically contribute to the obviously strengthened absorption intensity in visible region, as well as significantly improved photocatalytic activity. In the gas phase reactor, when the calcination temperature was 550°C, 0.125N/0.25Zr-TiO 2 composite performed the highest photocatalytic activity UV irradiation for 8 h, and the corresponding CH 4 yield was 11.837 µmol/g, which was 87.8% higher than that of pristine TiO 2 . For the visible light, the CH 4 yield was 9.003 µmol/g after 8 h irradiation, which was 83.9% higher than that of pristine TiO 2 .

Vacuum Brazing TC4 Titanium Alloy to 304 Stainless Steel with Cu-Ti-Ni-Zr-V Amorphous Alloy Foil

NASA Astrophysics Data System (ADS)

Dong, Honggang; Yang, Zhonglin; Wang, Zengrui; Deng, Dewei; Dong, Chuang

2014-10-01

Dissimilar metal vacuum brazing between TC4 titanium alloy and 304 stainless steel was conducted with newly designed Cu-Ti-Ni-Zr-V amorphous alloy foils as filler metals. Solid joints were obtained due to excellent compatibility between the filler metal and stainless steel substrate. Partial dissolution of stainless steel substrate occurred during brazing. The shear strength of the joint brazed with Cu43.75Ti37.5Ni6.25Zr6.25V6.25 foil was 105 MPa and that with Cu37.5Ti25Ni12.5Zr12.5V12.5 was 116 MPa. All the joints fractured through the gray layer in the brazed seam, revealing brittle fracture features. Cr4Ti, Cu0.8FeTi, Fe8TiZr3 and Al2NiTi3C compounds were found in the fractured joint brazed with Cu43.75Ti37.5Ni6.25Zr6.25V6.25 foil, and Fe2Ti, TiCu, Fe8TiZr3 and NiTi0.8Zr0.3 compounds were detected in the joint brazed with Cu37.5Ti25Ni12.5Zr12.5V12.5 foil. The existence of Cr-Ti, Fe-Ti, Cu-Fe-Ti, and Fe-Ti-V intermetallic compounds in the brazed seam caused fracture of the resultant joints.

Bio-corrosion and cytotoxicity studies on novel Zr 55Co 30Ti 15 and Cu 60Zr 20Ti 20 metallic glasses

DOE PAGES

Vincent, S.; Daiwile, A.; Devi, S. S.; ...

2014-09-26

Metallic glasses are a potential and compatible implant candidate for biomedical applications. In the present investigation, a comparative study between novel Zr 55Co 30Ti 15 and Cu 60Zr 20Ti 20 metallic glasses is carried out to evaluate in vitro biocompatibility using simulated body fluids. The bio-corrosion behavior of Zr- and Cu-based metallic glasses in different types of artificial body fluids such as artificial saliva solution, phosphate-buffered saline solution, artificial blood plasma solution, and Hank’s balanced saline solution is evaluated using potentiodynamic polarization studies at a constant body temperature of 310.15 K (37 °C). Surface morphology of samples after bio-corrosion experimentsmore » was observed by scanning electron microscopy. In vitro cytotoxicity test on glassy alloys were performed using human osteosarcoma cell line as per 10993-5 guidelines from International Organization for Standardization. As a result, the comparative study between Zr- and Cu-based glassy alloys provides vital information about the effect of elemental composition on biocompatibility of metallic glasses.« less

Surface Characterization, Corrosion Resistance and in Vitro Biocompatibility of a New Ti-Hf-Mo-Sn Alloy

PubMed Central

Ion, Raluca; Drob, Silviu Iulian; Ijaz, Muhammad Farzik; Vasilescu, Cora; Osiceanu, Petre; Gordin, Doina-Margareta; Cimpean, Anisoara; Gloriant, Thierry

2016-01-01

A new superelastic Ti-23Hf-3Mo-4Sn biomedical alloy displaying a particularly large recovery strain was synthesized and characterized in this study. Its native passive film is very thick (18 nm) and contains very protective TiO2, Ti2O3, HfO2, MoO2, and SnO2 oxides (XPS analysis). This alloy revealed nobler electrochemical behavior, more favorable values of the corrosion parameters and open circuit potentials in simulated body fluid in comparison with commercially pure titanium (CP-Ti) and Ti-6Al-4V alloy taken as reference biomaterials in this study. This is due to the favorable influence of the alloying elements Hf, Sn, Mo, which enhance the protective properties of the native passive film on alloy surface. Impedance spectra showed a passive film with two layers, an inner, capacitive, barrier, dense layer and an outer, less insulating, porous layer that confer both high corrosion resistance and bioactivity to the alloy. In vitro tests were carried out in order to evaluate the response of Human Umbilical Vein Endothelial Cells (HUVECs) to Ti-23Hf-3Mo-4Sn alloy in terms of cell viability, cell proliferation, phenotypic marker expression and nitric oxide release. The results indicate a similar level of cytocompatibility with HUVEC cells cultured on Ti-23Hf-3Mo-4Sn substrate and those cultured on the conventional CP-Ti and Ti-6Al-4V metallic materials. PMID:28773939

Nanostructured Ti-Zr-Pd-Si-(Nb) bulk metallic composites: Novel biocompatible materials with superior mechanical strength and elastic recovery.

PubMed

Hynowska, A; Blanquer, A; Pellicer, E; Fornell, J; Suriñach, S; Baró, M D; Gebert, A; Calin, M; Eckert, J; Nogués, C; Ibáñez, E; Barrios, L; Sort, J

2015-11-01

The microstructure, mechanical behaviour, and biocompatibility (cell culture, morphology, and cell adhesion) of nanostructured Ti45 Zr15 Pd35- x Si5 Nbx with x = 0, 5 (at. %) alloys, synthesized by arc melting and subsequent Cu mould suction casting, in the form of rods with 3 mm in diameter, are investigated. Both Ti-Zr-Pd-Si-(Nb) materials show a multi-phase (composite-like) microstructure. The main phase is cubic β-Ti phase (Im3m) but hexagonal α-Ti (P63/mmc), cubic TiPd (Pm3m), cubic PdZr (Fm3m), and hexagonal (Ti, Zr)5 Si3 (P63/mmc) phases are also present. Nanoindentation experiments show that the Ti45 Zr15 Pd30 Si5 Nb5 sample exhibits lower Young's modulus than Ti45 Zr15 Pd35 Si5 . Conversely, Ti45 Zr15 Pd35 Si5 is mechanically harder. Actually, both alloys exhibit larger values of hardness when compared with commercial Ti-40Nb, (HTi-Zr-Pd-Si ≈ 14 GPa, HTi-Zr-Pd-Si-Nb ≈ 10 GPa and HTi-40Nb ≈ 2.7 GPa). Concerning the biological behaviour, preliminary results of cell viability performed on several Ti-Zr-Pd-Si-(Nb) discs indicate that the number of live cells is superior to 94% in both cases. The studied Ti-Zr-Pd-Si-(Nb) bulk metallic system is thus interesting for biomedical applications because of the outstanding mechanical properties (relatively low Young's modulus combined with large hardness), together with the excellent biocompatibility. © 2014 Wiley Periodicals, Inc.

Effect of TiO2, ZrO2, and TiO2-ZrO2 on the performance of CuO-ZnO catalyst for CO2 hydrogenation to methanol

NASA Astrophysics Data System (ADS)

Xiao, Jie; Mao, Dongsen; Guo, Xiaoming; Yu, Jun

2015-05-01

The influence of TiO2, ZrO2, and TiO2-ZrO2 mixed oxide on the catalytic performance of CuO-ZnO catalyst in the methanol synthesis from CO2 hydrogenation was studied. The catalysts were prepared by oxalate co-precipitation method and characterized by TGA, N2 adsorption, XRD, reactive N2O adsorption, XPS, H2-TPR, H2-TPD, and CO2-TPD techniques. Characterization results reveal that all the additives improve the CuO dispersion in the catalyst body and increase the Cu surface area and adsorption capacities of CO2 and H2. The results of catalytic test reveal that the additives increase both the CO2 conversion and methanol selectivity, and TiO2-ZrO2 mixed oxide is more effective than single components of TiO2 or ZrO2. Moreover, the activity of methanol synthesis is correlated directly with CO2 adsorption capacity over the catalysts.

Ferroelectric performances and crystal structures of (Pb, La)(Zr, Ti, Nb)O{sub 3}

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

Kitamura, Naoto; Division of Ecosystem Research, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510; Mizoguchi, Takuma

2014-02-15

In this study, we focused on Nb and La substituted Pb(Zr, Ti)O{sub 3}: i.e., (Pb, La)(Zr, Ti, Nb)O{sub 3}. As for the samples, dependences of ferroelectric properties on La and Nb compositions were examined. In addition, the crystal structures were analyzed by the Rietveld method, and then a relationship between the metal compositions and the crystal structures were discussed. From P–E hysteresis loop measurements, it was found that the remanant polarization of Pb(Zr, Ti)O{sub 3} was increased by both the La and Nb substitutions although the heavy substitution of La had an undesirable effect. It was also indicated that themore » Curie temperature decreased with increasing La content. The Rietveld analysis using synchrotron X-ray diffraction patterns demonstrated that the structure distortion was relaxed by the La and Nb substitutions. Such a change in the crystals was well consistent with the harmful effects on the Curie temperature and the remanent polarization by the heavy La substitution. - Graphical abstract: Rietveld refinement pattern of 2 mol% PbSiO{sub 3}-added Pb{sub 0.95}La{sub 0.05}Zr{sub 0.50}Ti{sub 0.45}Nb{sub 0.05}O{sub 3} (synchrotron X-ray diffraction). Display Omitted - Highlights: • (Pb,La)(Zr,Ti,Nb)O{sub 3} were successfully synthesized. • Remanant polarization of Pb(Zr,Ti)O{sub 3} was improved by substitutions of La and Nb. • Crystal structures of (Pb,La)(Zr,Ti,Nb)O{sub 3} were refined and the distortions were estimated.« less

Effects of Zr and Si on the Glass Forming Ability and Compressive Properties of Ti-Cu-Co-Sn Alloys

NASA Astrophysics Data System (ADS)

Wang, Tan; Wu, Yidong; Si, Jiajia; Hui, Xidong

2015-06-01

To succeed in finding novel Ti-based bulk metallic glasses, which are free from Be, Ni, and noble metallic elements, a comprehensive study was performed on the effects of Zr and Si on the microstructural evolution, glass-forming ability (GFA), and mechanical properties of Ti46Cu44- x Zr x Co7Sn3 ( x = 0, 5, 10, 12.5, and 16 at. pct) and Ti46Cu31.5Zr12.5- x Co7Sn3Si x ( x = 0.5, 1, and 1.5 at. pct) alloys. It is shown that with the increase of Zr, the sequence of phase formation is β-Ti + α-Ti + (Ti, Zr)3Cu4 ⇒ β-Ti + α-Ti + TiCu ⇒ β-Ti + Ti2Cu + glass ⇒ glass ⇒ β-Ti + Ti2Cu + TiCuSn. The quinary Ti-Zr-Cu-Co-Sn alloy with 12.5 pct Zr exhibits the best GFA. The addition of 1 pct Si results in the improvement of the critical size of glassy rods up to 3 mm in diameter. The yield stress and Young's modulus of Z-series alloys increases, and the plastic strain decreases with the addition of Zr. The yield stress and ultimate compression stress of Ti46Zr11.5Cu31.5Co7Sn3Si1 glassy alloy reach 2477.9 and 2623.3 MPa, respectively. It was found that the addition of Si promotes the generation and multiplication of shear bands, resulting in certain plasticity in these kinds of glassy alloys.

Lattice Thermal Conductivity of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2 from Atomistic Simulations

NASA Technical Reports Server (NTRS)

Lawson, John W.; Daw, Murray S.; Bauschlicher, Charles W.

2012-01-01

Ultra high temperature ceramics (UHTC) including ZrB2 and HfB2 have a number of properties that make them attractive for applications in extreme environments. One such property is their high thermal conductivity. Computational modeling of these materials will facilitate understanding of fundamental mechanisms, elucidate structure-property relationships, and ultimately accelerate the materials design cycle. Progress in computational modeling of UHTCs however has been limited in part due to the absence of suitable interatomic potentials. Recently, we developed Tersoff style parameterizations of such potentials for both ZrB2 and HfB2 appropriate for atomistic simulations. As an application, Green-Kubo molecular dynamics simulations were performed to evaluate the lattice thermal conductivity for single crystals of ZrB2 and HfB2. The atomic mass difference in these binary compounds leads to oscillations in the time correlation function of the heat current, in contrast to the more typical monotonic decay seen in monoatomic materials such as Silicon, for example. Results at room temperature and at elevated temperatures will be reported.

Growth of Pb(Ti,Zr)O 3 thin films by metal-organic molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Avrutin, V.; Liu, H. Y.; Izyumskaya, N.; Xiao, B.; Özgür, Ü.; Morkoç, H.

2009-02-01

Single-crystal Pb(Zr xTi 1-x)O 3 thin films have been grown on (0 0 1) SrTiO 3 and SrTiO 3:Nb substrates by molecular beam epitaxy using metal-organic source of Zr and two different sources of reactive oxygen—RF plasma and hydrogen-peroxide sources. The same growth modes and comparable structural properties were observed for the films grown with both oxygen sources, while the plasma source allowed higher growth rates. The films with x up to 0.4 were single phase, while attempts to increase x beyond gave rise to the ZrO 2 second phase. The effects of growth conditions on growth modes, Zr incorporation, and phase composition of the Pb(Zr xTi 1-x)O 3 films are discussed. Electrical and ferroelectric properties of the Pb(Zr xTi 1-x)O 3 films of ~100 nm in thickness grown on SrTiO 3:Nb were studied using current-voltage, capacitance-voltage, and polarization-field measurements. The single-phase films show low leakage currents and large breakdown fields, while the values of remanent polarization are low (around 5 μC/cm 2). It was found that, at high sweep fields, the contribution of the leakage current to the apparent values of remanent polarization can be large, even for the films with large electrical resistivity (˜10 8-10 9 Ω cm at an electric filed of 1 MV/cm). The measured dielectric constant ranges from 410 to 260 for Pb(Zr 0.33Ti 0.67)O 3 and from 313 to 213 for Pb(Zr 0.2Ti 0.8)O 3 in the frequency range from 100 to 1 MHz.

Ternary ceramic alloys of Zr-Ce-Hf oxides

DOEpatents

Becher, P.F.; Funkenbusch, E.F.

1990-11-20

A ternary ceramic alloy is described which produces toughening of zirconia and zirconia composites through the stress transformation from tetragonal phase to monoclinic phase. This alloy, having the general formula Ce[sub x]Hf[sub y]Zr[sub 1[minus]x[minus]y]O[sub 2], is produced through the addition of appropriate amounts of ceria and hafnia to the zirconia. Typically, improved toughness is achieved with about 5 to about 15 mol % ceria and up to about 40 mol % hafnia. The preparation of alloys of these compositions are given together with data as to the densities, tetragonal phase content, hardness and fracture toughness. The alloys are useful in preparing zirconia bodies as well as reinforcing ceramic composites. 1 fig.

Mn-coatings on the micro-pore formed Ti-29Nb-xHf alloys by RF-magnetron sputtering for dental applications

NASA Astrophysics Data System (ADS)

Park, Seon-Yeong; Choe, Han-Cheol

2018-02-01

In this study, Mn-coatings on the micro-pore formed Ti-29Nb-xHf alloys by RF-magnetrons sputtering for dental applications were studied using different experimental techniques. Mn coating films were formed on Ti-29Nb-xHf alloys by a radio frequency magnetron sputtering technique for 0, 1, 3, and 5 min at 45 W. The microstructure, composition, and phase structure of the coated alloys were examined by optical microscopy, field emission scanning electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The microstructure of Ti-29Nb alloy showed α" phase in the needle-like structure and Ti-29Nb-15Hf alloy showed β phase in the equiaxed structure. As the sputtering time increased, the circular particles of Mn coatings on the Ti-29Nb alloy increased at inside and outside surfaces. As the sputtering time increased, [Mn + Ca/P] ratio of the plasma electrolytic oxidized films in Ti- 29Nb-xHf alloys increased. The corrosion potential (Ecorr) of Mn coatings on the Ti-29Nb alloy showed higher than that of Mn coatings on the Ti-29Nb-15Hf alloy. The passive current density (Ipass) of the Mn coating on the Ti-29Nb alloy and Mn coatings on the Ti-29Nb-15Hf alloy was less noble than the non-Mn coated Ti-29Nb and Ti-29Nb-15Hf alloys surface.

Hydrogenation behavior of Ti-implanted Zr-1Nb alloy with TiN films deposited using filtered vacuum arc and magnetron sputtering

NASA Astrophysics Data System (ADS)

Kashkarov, E. B.; Nikitenkov, N. N.; Sutygina, A. N.; Bezmaternykh, A. O.; Kudiiarov, V. N.; Syrtanov, M. S.; Pryamushko, T. S.

2018-02-01

More than 60 years of operation of water-cooled reactors have shown that local or general critical hydrogen concentration is one of the basic limiting criteria of zirconium-based fuel element claddings. During the coolant radiolysis, released hydrogen penetrates and accumulates in zirconium alloys. Hydrogenation of zirconium alloys leads to degradation of their mechanical properties, hydride cracking and stress corrosion cracking. In this research the effect of titanium nitride (TiN) deposition on hydrogenation behavior of Ti-implanted Zr-1Nb alloy was described. Ti-implanted interlayer was fabricated by plasma immersion ion implantation (PIII) at the pulsed bias voltage of 1500 V to improve the adhesion of TiN and reduce hydrogen penetration into Zr-1Nb alloy. We conducted the comparative analysis on hydrogenation behavior of the Ti-implanted alloy with sputtered and evaporated TiN films by reactive dc magnetron sputtering (dcMS) and filtered cathodic vacuum arc deposition (FVAD), respectively. The crystalline structure and surface morphology were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The elemental distribution was analyzed using glow-discharge optical emission spectroscopy (GD-OES). Hydrogenation was performed from gas atmosphere at 350 °C and 2 atm hydrogen pressure. The results revealed that TiN films as well as Ti implantation significantly reduce hydrogen absorption rate of Zr-1Nb alloy. The best performance to reduce the rate of hydrogen absorption is Ti-implanted layer with evaporated TiN film. Morphology of the films impacted hydrogen permeation through TiN films: the denser film the lower hydrogen permeation. The Ti-implanted interface plays an important role of hydrogen accumulation layer for trapping the penetrated hydrogen. No deterioration of adhesive properties of TiN films on Zr-1Nb alloy with Ti-implanted interface occurs under high-temperature hydrogen exposure. Thus, the fabrication of Ti

Constraints on Hf and Zr mobility in high-sulfidation epithermal systems: formation of kosnarite, KZr2(PO4)3, in the Chaquicocha gold deposit, Yanacocha district, Peru

NASA Astrophysics Data System (ADS)

Deditius, Artur P.; Utsunomiya, Satoshi; Sanchez-Alfaro, Pablo; Reich, Martin; Ewing, Rodney C.; Kesler, Stephen E.

2015-04-01

We report the first occurrence of Hf-rich kosnarite [K(Hf,Zr)2(PO4)3], space group R- 3c, Z = 6, in the giant Chaquicocha high-sulfidation epithermal gold deposit in the Yanacocha mining district, Peru. Kosnarite crystals are small (<100 μm) and occur in 2-3-mm-thick veins that cut intensively silicified rocks. The paragenesis includes a first stage of As-free pyrite and quartz (plus gratonite and rutile), followed by trace metal-rich pyrite [(Fe,As,Pb,Au)S2] and secondary Fe sulfates. Kosnarite is associated with quartz and is clearly late within the paragenetic sequence. Electron microprobe analyses (EMPA) of kosnarite show relatively high concentrations of HfO2 and Rb2O (7.61 and 1.05 wt.%, respectively). The re-calculated chemical formulas of kosnarite vary from KΣ1.00(Zr1.93Na0.01Hf0.01Mn0.01)Σ1.96(P3.04O4)Σ3 to (K0.92Rb0.05Na0.03)Σ1.00(Zr1.81Hf0.19)Σ2.00 [(P2.98Si0.02As0.01)Σ3.01O4]Σ3, where Hf and Rb are most likely incorporated according to a coupled substitution of Hf4+ + Rb+ ⇔ Zr4+ + K+. Back-scattered electron (BSE) images and elemental mapping of kosnarite reveal that Hf and Rb are enriched in 2-10-μm-wide oscillatory and/or sector zones. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observations of such zones reveal a pattern of alternating, 5-50-nm-thick, Hf-rich and Zr-rich nanozones. These high-resolution observations indicate that the incorporation of Hf does not appear to cause significant distortion in the kosnarite structure. Semiquantitative TEM-energy-dispersive X-ray spectrometry (EDS) analyses of the nano-layers show up to 22 wt.% of HfO2, which corresponds to 31 mol% of the hypothetical, KHf2(PO4)3, end-member. The presence of kosnarite in the advanced argillic alteration zone at Yanacocha is indicative of Hf and Zr mobility under highly acidic conditions and points towards an unforeseen role of phosphates as sinks of Zr and Hf in high-sulfidation epithermal environments. Finally

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Brazing characteristics of a Zr-Ti-Cu-Fe eutectic alloy filler metal for Zircaloy-4

NASA Astrophysics Data System (ADS)

Lee, Jung G.; Lim, C. H.; Kim, K. H.; Park, S. S.; Lee, M. K.; Rhee, C. K.

2013-10-01

A Zr-Ti-Cu-Fe quaternary eutectic alloy was employed as a new Be-free brazing filler metal for Zircaloy-4 to supersede physically vapor-deposited Be coatings used conventionally with several disadvantages. The quaternary eutectic composition of Zr58Ti16Cu10Fe16 (at.%) showing a low melting temperature range from 832 °C to 853 °C was designed by a partial substitution of Zr with Ti based on a Zr-Cu-Fe ternary eutectic system. By applying an alloy ribbon with the determined composition, a highly reliable joint was obtained with a homogeneous formation of predominantly grown α-Zr phases owing to a complete isothermal solidification, exhibiting strength higher than that of Zircaloy-4. The homogenization of the joint was rate-controlled by the diffusion of the filler elements (Ti, Cu, and Fe) into the Zircaloy-4 base metal, and the detrimental segregation of the Zr2Fe phase in the central zone was completely eliminated by an isothermal holding at a brazing temperature of 920 °C for 10 min.

A comparative study of the mechanical and thermal properties of defective ZrC, TiC and SiC.

PubMed

Jiang, M; Zheng, J W; Xiao, H Y; Liu, Z J; Zu, X T

2017-08-24

ZrC and TiC have been proposed to be alternatives to SiC as fuel-cladding and structural materials in nuclear reactors due to their strong radiation tolerance and high thermal conductivity at high temperatures. To unravel how the presence of defects affects the thermo-physical properties under irradiation, first-principles calculations based on density function theory were carried out to investigate the mechanical and thermal properties of defective ZrC, TiC and SiC. As compared with the defective SiC, the ZrC and TiC always exhibit larger bulk modulus, smaller changes in the Young's and shear moduli, as well as better ductility. The total thermal conductivity of ZrC and TiC are much larger than that of SiC, implying that under radiation environment the ZrC and TiC will exhibit superior heat conduction ability than the SiC. One disadvantage for ZrC and TiC is that their Debye temperatures are generally lower than that of SiC. These results suggest that further improving the Debye temperature of ZrC and TiC will be more beneficial for their applications as fuel-cladding and structural materials in nuclear reactors.

Surface Characterization of ZrO2/Zr Coating on Ti6Al4V and IN VITRO Evaluation of Corrosion Behavior and Biocompatibility

NASA Astrophysics Data System (ADS)

Wang, Ruoyun; Sun, Yonghua; He, Xiaojing; Gao, Yuee; Yao, Xiaohong

Biocompatibility is crucial for implants. In recent years, numerous researches were conducted aiming to modify titanium alloys, which are the most extensively used materials in orthopedic fields. The application of zirconia in the biomedical field has recently been explored. In this study, the biological ZrO2 coating was synthesized on titaniumalloy (Ti6Al4V) substrates by a duplex-treatment technique combining magnetron sputtering with micro-arc oxidation (MAO) in order to further improve the corrosion resistance and biocompatibility of Ti6Al4V alloys. The microstructures and phase constituents of the coatings were characterized by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD), the surface wettability was evaluated by contact angle measurements. The results show that ZrO2 coatings are porous with pore sizes less than 2μm and consist predominantly of the tetragonal ZrO2 (t-ZrO2) and cubic ZrO2(c-ZrO2) phase. Electrochemical tests indicate that the corrosion rate of Ti6Al4V substrates is appreciably reduced after surface treatment in the phosphate buffer saline (PBS). In addition, significantly improved cell adhesion and growth were observed from the ZrO2/Zr surface. Therefore, the hybrid approach of magnetron sputtering and MAO provides a surface modification for Ti6Al4V to achieve acceptable corrosion resistance and biocompatibility.

Influence of oxygen vacancies in ALD HfO2-x thin films on non-volatile resistive switching phenomena with a Ti/HfO2-x/Pt structure

NASA Astrophysics Data System (ADS)

Sokolov, Andrey Sergeevich; Jeon, Yu-Rim; Kim, Sohyeon; Ku, Boncheol; Lim, Donghwan; Han, Hoonhee; Chae, Myeong Gyoon; Lee, Jaeho; Ha, Beom Gil; Choi, Changhwan

2018-03-01

We report a modulation of oxygen vacancies profile in atomic layer deposition (ALD) HfO2-x thin films by reducing oxidant pulse time (0.7 s-0.1 s) and study its effect on resistive switching behavior with a Ti/HfO2-x/Pt structure. Hf 4f spectra of x-ray photoelectron microscopy (XPS) and depth profile confirm varied oxygen vacancies profiles by shifts of binding energies of Hf 4f5/2 and Hf 4f7/2 main peaks and its according HfO2-x sub-oxides for each device. The ultraviolet photoelectron spectroscopy (UPS) confirms different electron affinity (χ) of HfO2 and HfO2-x thin films, implying that barrier height at Ti/oxide interface is reduced. Current transport mechanism is dictated by Ohmic conduction in fully oxidized HfO2 thin films - Device A (0.7 s) and by Trap Filled Space Charge Limited Conduction (TF-SCLC) in less oxidized HfO2-x thin films - Device B (0.3 s) and Device C (0.1 s). A switching mechanism related to the oxygen vacancies modulation in Ti/HfO2-x/Pt based resistive random access memory (RRAM) devices is used to explain carefully notified current transport mechanism variations from device-to-device. A proper endurance and long-time retention characteristics of the devices are also obtained.

Physical and electrical properties of SrTiO3 and SrZrO3

NASA Astrophysics Data System (ADS)

Fashren Muhamad, Norhizatol; Aina Maulat Osman, Rozana; Sobri Idris, Mohd; Yasin, Mohd Najib Mohd

2017-11-01

Perovskite type oxide strontium titanate (SrTiO3) and strontium zirconate (SrZrO3) ceramic powder has been synthesized using conventional solid state reaction method. The powders were mixed and ground undergone calcinations at 1400°C for 12 h and sintered at 1550°C for 5h. X-ray Diffraction exposes physical properties SrTiO3 which exhibit cubic phase (space group: pm-3m) at room temperature meanwhile SrZrO3 has Orthorhombic phase (space group: pnma). The electrical properties such as dielectric constant (ɛr), dielectric loss (tan δ), and conductivity (σ) were studied in variation temperature and frequency. High dielectric constant of SrTiO3 and SrZrO3 were observed at 10 kHz for both samples about 240 and 21 respectively at room temperature. The dielectric loss of SrTiO3 and SrZrO3 is very low loss value approximately 0.00076 and 0.67512 indicates very good dielectric.

Microstructure, Surface Characterization, and Electrochemical Behavior of New Ti-Zr-Ta-Ag Alloy in Simulated Human Electrolyte

NASA Astrophysics Data System (ADS)

Vasilescu, Cora; Drob, Silviu Iulian; Osiceanu, Petre; Moreno, Jose Maria Calderon; Prodana, Mariana; Ionita, Daniela; Demetrescu, Ioana; Marcu, Maria; Popovici, Ion Alexandru; Vasilescu, Ecaterina

2017-01-01

A new Ti-20Zr-5Ta-2Ag alloy was elaborated and characterized regarding its microstructure, its native passive film composition and thickness, its surface wettability, its electrochemical behavior in Ringer solution of different pH values, and its ion release. The new alloy has a bi-phase, α + β, acicular, homogeneous microstructure (scanning electron microscopy (SEM)). Its native passive film (12-nm thicknesses) consists of the protective TiO2, ZrO2, and Ta2O5 oxides, Ti and Ta suboxides, and metallic Ag (X-ray photoelectron spectroscopy (XPS) data). The alloy possesses high hydrophilic properties. The main electrochemical parameters of the new alloy are superior to those of Ti as a result of the beneficial influence of Zr, Ta, and Ag alloying elements, which reinforce its native passive film. Electrochemical impedance spectroscopy (EIS) spectra in Ringer solutions for the new alloy displayed better values of impedances and phase angles, proving a more insulate passive film than that on the Ti surface. The main corrosion parameters for the new Ti-20Zr-5Ta-2Ag alloy are more favorable by about 25 to 38 times than those of Ti, confirming extremely resistant passive film. The new Ti-20Zr-5Ta-2Ag alloy releases into Ringer solution low quantities of Ti4+, Zr4+ metallic ions (inductively coupled plasma-mass spectroscopy (ICP-MS)). The Ag+ ions are released in low quantity, conferring to this alloy's low antibacterial activity. All experimental results show that the new Ti-20Zr-5Ta-2Ag alloy fulfills the requirements for biocompatibility, corrosion resistance, and antibacterial protection.

Extraction chromatography of the Rf homologs, Zr and Hf, using TEVA and UTEVA resins in HCl, HNO3, and H2SO4 media

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

Alfonso, M. C.; Bennett, M. E.; Folden, C. M.

2015-06-20

The extraction behavior of the Rf homologs, Zr and Hf, has been studied in HCl, HNO3, and H2SO4 media using TEVA (R) (a trioctyl and tridecyl methyl ammonium-based resin) and UTEVA (R) (a diamyl amylphosphonate-based resin). All six systems were considered for the future chemical characterization of Rf. Batch uptake studies were first performed to determine which systems could separate Zr and Hf and these results were used to determine what acid concentration range to focus on for the column studies. The batch uptake studies showed that UTEVA separates Zr and Hf in all media, while the intergroup separation wasmore » only observed in HCl media with TEVA. Both HCl systems showed viability for potential extraction chromatographic studies of Rf.« less

Senary refractory high-entropy alloy HfNbTaTiVZr

DOE PAGES

Gao, Michael C.; Zhang, B.; Yang, S.; ...

2015-09-03

Discovery of new single-phase high-entropy alloys (HEAs) is important to understand HEA formation mechanisms. The present study reports computational design and experimental validation of a senary HEA, HfNbTaTiVZr, in a body-centered cubic structure. The phase diagrams and thermodynamic properties of this senary system were modeled using the CALPHAD method. Its atomic structure and diffusion constants were studied using ab initio molecular dynamics simulations. Here, the microstructure of the as-cast HfNbTaTiVZr alloy was studied using X-ray diffraction and scanning electron microscopy, and the microsegregation in the as-cast state was found to qualitatively agree with the solidification predictions from CALPHAD. Supported bymore » both simulation and experimental results, the HEA formation rules are discussed.« less

Shape memory behavior of single crystal and polycrystalline Ni-rich NiTiHf high temperature shape memory alloys

NASA Astrophysics Data System (ADS)

Saghaian, Sayed M.

NiTiHf shape memory alloys have been receiving considerable attention for high temperature and high strength applications since they could have transformation temperatures above 100 °C, shape memory effect under high stress (above 500 MPa) and superelasticity at high temperatures. Moreover, their shape memory properties can be tailored by microstructural engineering. However, NiTiHf alloys have some drawbacks such as low ductility and high work hardening in stress induced martensite transformation region. In order to overcome these limitations, studies have been focused on microstructural engineering by aging, alloying and processing. Shape memory properties and microstructure of four Ni-rich NiTiHf alloys (Ni50.3Ti29.7Hf20, Ni50.7Ti 29.3Hf20, Ni51.2Ti28.8Hf20, and Ni52Ti28Hf20 (at. %)) were systematically characterized in the furnace cooled condition. H-phase precipitates were formed during furnace cooling in compositions with greater than 50.3Ni and the driving force for nucleation increased with Ni content. Alloy strength increased while recoverable strain decreased with increasing Ni content due to changes in precipitate characteristics. The effects of the heat treatments on the transformation characteristics and microstructure of the Ni-rich NiTiHf shape memory alloys have been investigated. Transformation temperatures are found to be highly annealing temperature dependent. Generation of nanosize precipitates (˜20 nm in size) after three hours aging at 450 °C and 550 °C improved the strength of the material, resulting in a near perfect dimensional stability under high stress levels (> 1500 MPa) with a work output of 20-30 J cm- 3. Superelastic behavior with 4% recoverable strain was demonstrated at low and high temperatures where stress could reach to a maximum value of more than 2 GPa after three hours aging at 450 and 550 °C for alloys with Ni great than 50.3 at. %. Shape memory properties of polycrystalline Ni50.3Ti29.7 Hf20 alloys were studied via

Synthesis and characterisation of ionic liquids based on 1-butyl-3-methylimidazolium chloride and MCl(4), M = Hf and Zr.

PubMed

Campbell, Paul S; Santini, Catherine C; Bouchu, Denis; Fenet, Bernard; Rycerz, Leszek; Chauvin, Yves; Gaune-Escard, Marcelle; Bessada, Catherine; Rollet, Anne-Laure

2010-02-07

Dialkylimidazolium chlorometallate molten salts resulting from the combination of zirconium or hafnium tetrachloride and 1-butyl-3-methylimidazolium chloride, [C(1)C(4)Im][Cl], have been prepared with a molar fraction of MCl(4), R = n(MCl4)/n(MCl4) + n([C1C4IM][Cl]) equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. The structure and composition were studied by Differential Scanning Calorimetry (DSC), (35)Cl (263 to 333 K), (1)H and (13)C solid state and solution NMR spectroscopy, and electrospray ionisation (ESI) mass spectrometry. The primary anions of the MCl(4)-based ILs were [MCl(5)], [MCl(6)] and [M(2)Cl(9)], whose relative abundances varied with R. For R = 0.33, pure solid [C(1)C(4)Im](2)[MCl(6)], for both M = Zr and Hf are formed (m.p. = 366 and 385 K, respectively). For R = 0.67 pure ionic liquids [C(1)C(4)Im][M(2)Cl(9)] for both M = Zr and Hf are formed (T(g) = 224 and 220 K, respectively). The thermal dissociation has been attempted of [C(1)C(4)Im](2)[HfCl(6)], and [C(1)C(4)Im](2)[ZrCl(6)] monitored by (35)Cl and (91)Zr solid NMR (high temperature up to 551 K).

Improved conversion efficiency of dye sensitized solar cell using Zn doped TiO2-ZrO2 nanocomposite

NASA Astrophysics Data System (ADS)

Tomar, Laxmi J.; Bhatt, Piyush J.; Desai, Rahul K.; Chakrabarty, B. S.; Panchal, C. J.

2016-05-01

TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites were prepared by hydrothermal method for dye sensitized solar cell (DSSC) application. The structural and optical properties were investigated by X -ray diffraction (XRD) and UV-Visible spectroscopy respectively. XRD results revealed the formation of material in nano size. The average crystallite size is 22.32 nm, 17.41 nm and 6.31 nm for TiO2, TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites respectively. The optical bandgap varies from 2.04 eV to 3.75 eV. Dye sensitized solar cells were fabricated using the prepared material. Pomegranate juice was used as a sensitizer and graphite coated conducting glass plate was used as counter electrode. The I - V characteristics were recorded to measure photo response of DSSC. Photovoltaic parameter like open circuit voltage, power conversion efficiency, and fill factor were evaluated for fabricated solar cell. The power conversion efficiency of DSSC fabricated with TiO2, TiO2-ZrO2 and Zn doped TiO2-ZrO2 nanocomposites were found 0.71%, 1.97% and 4.58% respectively.

Polarization Rotation in Ferroelectric Tricolor PbTiO3/SrTiO3/PbZr0.2Ti0.8O3 Superlattices.

PubMed

Lemée, Nathalie; Infante, Ingrid C; Hubault, Cécile; Boulle, Alexandre; Blanc, Nils; Boudet, Nathalie; Demange, Valérie; Karkut, Michael G

2015-09-16

In ferroelectric thin films, controlling the orientation of the polarization is a key element to controlling their physical properties. We use laboratory and synchrotron X-ray diffraction to investigate ferroelectric bicolor PbTiO3/PbZr0.2Ti0.8O3 and tricolor PbTiO3/SrTiO3/PbZr0.2Ti0.8O3 superlattices and to study the role of the SrTiO3 layers on the domain structure. In the tricolor superlattices, we demonstrate the existence of 180° ferroelectric stripe nanodomains, induced by the depolarization field produced by the SrTiO3 layers. Each ultrathin SrTiO3 layer modifies the electrostatic boundary conditions between the ferroelectric layers compared to the corresponding bicolor structures, leading to the suppression of the a/c polydomain states. Combined with the electrostatic effect, the tensile strain induced by PbZr0.2Ti0.8O3 in the PbTiO3 layers leads to polarization rotation in the system as evidenced by grazing incidence X-ray measurements. This polarization rotation is associated with the monoclinic Mc phase as revealed by the splitting of the (HHL) and (H0L) reciprocal lattice points. This work demonstrates that the tricolor paraelectric/ferroelectric superlattices constitute a tunable system to investigate the concomitant effects of strains and depolarizing fields. Our studies provide a pathway to stabilize a monoclinic symmetry in ferroelectric layers, which is of particular interest for the enhancement of the piezoelectric properties.

The effect of C content on the mechanical properties of Ti-Zr coatings.

PubMed

Rodríguez-Hernández, M G; Jiménez, O; Alvarado-Hernández, F; Flores, M; Andrade, E; Canto, C E; Ávila, C; Espinoza-Beltrán, F

2015-09-01

In this study, Ti-Zr and Ti-Zr-C coatings were deposited at room temperature via pulsed-DC magnetron sputtering. A 70Ti-30Zr at% target and a 99.99% graphite plate were used to deposit samples. In order to modify C content, coatings were deposited at different target powers such as 50, 75 and 100 W. Changes on the structure, microstructure and mechanical properties due to C addition were studied. Results indicate that the as-deposited coatings were partly crystalline and that an increment on C content stabilized α' phase and inhibited the appearance of ω precipitates. Therefore, Ti-Zr-C alloys with C>1.9 at% showed only α' phase whereas the others alloys exhibited α'+ω structures. Hardness values from 12.94 to 34.31 GPa were obtained, whereas the elastic modulus was found between 181.84 and 298 GPa. Finally, a high elastic recovery ratio (0.69-0.87) was observed as a function of composition. The overall properties of these coatings were improved due to C content increment, martensitic α' phase and nanocrystalline grain size (10-16 nm). Copyright © 2015 Elsevier Ltd. All rights reserved.

Development of Ti-Nb-Zr alloys with high elastic admissible strain for temporary orthopedic devices.

PubMed

Ozan, Sertan; Lin, Jixing; Li, Yuncang; Ipek, Rasim; Wen, Cuie

2015-07-01

A new series of beta Ti-Nb-Zr (TNZ) alloys with considerable plastic deformation ability during compression test, high elastic admissible strain, and excellent cytocompatibility have been developed for removable bone tissue implant applications. TNZ alloys with nominal compositions of Ti-34Nb-25Zr, Ti-30Nb-32Zr, Ti-28Nb-35.4Zr and Ti-24.8Nb-40.7Zr (wt.% hereafter) were fabricated using the cold-crucible levitation technique, and the effects of alloying element content on their microstructures, mechanical properties (tensile strength, yield strength, compressive yield strength, Young's modulus, elastic energy, toughness, and micro-hardness), and cytocompatibilities were investigated and compared. Microstructural examinations revealed that the TNZ alloys consisted of β phase. The alloy samples displayed excellent ductility with no cracking, or fracturing during compression tests. Their tensile strength, Young's modulus, elongation at rupture, and elastic admissible strain were measured in the ranges of 704-839 MPa, 62-65 GPa, 9.9-14.8% and 1.08-1.31%, respectively. The tensile strength, Young's modulus and elongation at rupture of the Ti-34Nb-25Zr alloy were measured as 839 ± 31.8 MPa, 62 ± 3.6 GPa, and 14.8 ± 1.6%, respectively; this alloy exhibited the elastic admissible strain of approximately 1.31%. Cytocompatibility tests indicated that the cell viability ratios (CVR) of the alloys are greater than those of the control group; thus the TNZ alloys possess excellent cytocompatibility. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

High temperature phase decomposition in Ti{sub x}Zr{sub y}Al{sub z}N

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

Lind, Hans; Pilemalm, Robert; Rogström, Lina

2014-12-15

Through a combination of theoretical and experimental observations we study the high temperature decomposition behavior of c-(Ti{sub x}Zr{sub y}Al{sub z}N) alloys. We show that for most concentrations the high formation energy of (ZrAl)N causes a strong tendency for spinodal decomposition between ZrN and AlN while other decompositions tendencies are suppressed. In addition we observe that entropic effects due to configurational disorder favor a formation of a stable Zr-rich (TiZr)N phase with increasing temperature. Our calculations also predict that at high temperatures a Zr rich (TiZrAl)N disordered phase should become more resistant against the spinodal decomposition despite its high and positivemore » formation energy due to the specific topology of the free energy surface at the relevant concentrations. Our experimental observations confirm this prediction by showing strong tendency towards decomposition in a Zr-poor sample while a Zr-rich alloy shows a greatly reduced decomposition rate, which is mostly attributable to binodal decomposition processes. This result highlights the importance of considering the second derivative of the free energy, in addition to its absolute value in predicting decomposition trends of thermodynamically unstable alloys.« less

Corrosion-Resistant Ti- xNb- xZr Alloys for Nitric Acid Applications in Spent Nuclear Fuel Reprocessing Plants

NASA Astrophysics Data System (ADS)

Manivasagam, Geetha; Anbarasan, V.; Kamachi Mudali, U.; Raj, Baldev

2011-09-01

This article reports the development, microstructure, and corrosion behavior of two new alloys such as Ti-4Nb-4Zr and Ti-2Nb-2Zr in boiling nitric acid environment. The corrosion test was carried out in the liquid, vapor, and condensate phases of 11.5 M nitric acid, and the potentiodynamic anodic polarization studies were performed at room temperature for both alloys. The samples subjected to three-phase corrosion testing were characterized using scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDAX). As Ti-2Nb-2Zr alloy exhibited inferior corrosion behavior in comparison to Ti-4Nb-4Zr in all three phases, weldability and heat treatment studies were carried out only on Ti-4Nb-4Zr alloy. The weldability of the new alloy was evaluated using tungsten inert gas (TIG) welding processes, and the welded specimen was thereafter tested for its corrosion behavior in all three phases. The results of the present investigation revealed that the newly developed near alpha Ti-4Nb-4Zr alloy possessed superior corrosion resistance in all three phases and excellent weldability compared to conventional alloys used for nitric acid application in spent nuclear reprocessing plants. Further, the corrosion resistance of the beta heat-treated Ti-4Nb-4Zr alloy was superior when compared to the sample heat treated in the alpha + beta phase.

A flexible, high-performance magnetoelectric heterostructure of (001) oriented Pb(Zr0.52Ti0.48)O3 film grown on Ni foil

NASA Astrophysics Data System (ADS)

Palneedi, Haribabu; Yeo, Hong Goo; Hwang, Geon-Tae; Annapureddy, Venkateswarlu; Kim, Jong-Woo; Choi, Jong-Jin; Trolier-McKinstry, Susan; Ryu, Jungho

2017-09-01

In this study, a flexible magnetoelectric (ME) heterostructure of PZT/Ni was fabricated by depositing a (001) oriented Pb(Zr0.52Ti0.48)O3 (PZT) film on a thin, flexible Ni foil buffered with LaNiO3/HfO2. Excellent ferroelectric properties and large ME voltage coefficient of 3.2 V/cmṡOe were realized from the PZT/Ni heterostructure. The PZT/Ni composite's high performance was attributed to strong texturing of the PZT film, coupled with the compressive stress in the piezoelectric film. Besides, reduced substrate clamping in the PZT film due to the film on the foil structure and strong interfacial bonding in the PZT/LaNiO3/HfO2/Ni heterostructure could also have contributed to the high ME performance of PZT/Ni.

Work production using the two-way shape memory effect in NiTi and a Ni-rich NiTiHf high-temperature shape memory alloy

NASA Astrophysics Data System (ADS)

Atli, K. C.; Karaman, I.; Noebe, R. D.; Bigelow, G.; Gaydosh, D.

2015-12-01

The work output capacity of the two-way shape memory effect (TWSME) in a Ni50.3Ti29.7Hf20 (at%) high-temperature shape memory alloy (HTSMA) was investigated and compared to that of binary Ni49.9Ti50.1 (at%). TWSME was induced through a training procedure of 100 thermomechanical cycles under different tensile stresses. It was observed that TWSME in as-extruded and trained Ni50.3Ti29.7Hf20 could produce 0.7% strain against a compressive stress of 100 MPa, corresponding to a maximum work output of 0.08 J g-1, compared to a maximum value of 0.06 J g-1 for binary NiTi. A peak aging heat treatment of 3 h at 550 °C, which previously has been shown to result in near-perfect functional stability in Ni50.3Ti29.7Hf20 during isobaric thermal cycling, did not improve the TWSME and actually resulted in a decrease in the magnitude and stability of the TWSME and its work output capacity. Nevertheless, the magnitude of TWSM behavior of Ni50.3Ti29.7Hf20, in the absence of an aging heat treatment, renders it an attractive candidate for high-temperature TWSM actuation.

Electrochemical corrosion, wear and cell behavior of ZrO2/TiO2 alloyed layer on Ti-6Al-4V.

PubMed

Li, Jianfang; He, Xiaojing; Zhang, Guannan; Hang, Ruiqiang; Huang, Xiaobo; Tang, Bin; Zhang, Xiangyu

2018-06-01

Ti-6Al-4V (TC4) has received increasing attention as biomaterial but also raised concerns about the long-term safety of releasing of metal ions and poor wear resistance. In this work, an ZrO 2 /TiO 2 alloyed layer was prepared on TC4 by plasma surface alloying with Zr and subsequently annealed in the air for improved corrosion and wear resistant. To assess the corrosion performance of the alloyed layer, the specimens were measured by open circuit potential, electrochemical impedance spectroscopy and potentiodynamic polarization in simulated body fluid solution. The result shows that the ZrO 2 /TiO 2 alloyed layer exhibits strikingly high polarization resistance, wide passive region and very low current density, indicating the excellent corrosion resistance. The layer also displays significant improvement of wear resistance. Furthermore, the alloyed layer restricts cell adhesion and spreading. We infer that the ZrO 2 /TiO 2 alloyed layer might be potentially useful implanted devices such as biosensors, bioelectronics or drug delivery devices. Copyright © 2018 Elsevier B.V. All rights reserved.

Thermal stability, adhesion and electrical studies on (Ti,Zr)N x thin films as low resistive diffusion barriers between Cu and Si

NASA Astrophysics Data System (ADS)

Huang, Cheng-Lin; Lai, Chih-Huang; Tsai, Po-Hao; Kuo, Yu-Lin; Lin, Jing-Cheng; Lee, Chiapyng

2014-05-01

In this study, we investigated the thermal stability, wettability, adhesion and reliability of (Ti,Zr)N x films used as the diffusion barrier between Cu and Si. (Ti,Zr)N x films were prepared by DC reactive magnetron sputtering from a Ti-5 at. % Zr alloy target in N2/Ar gas mixtures. A minimum film resistivity of 59.3 µω cm was obtained at an N2/Ar flow ratio of 2.75, which corresponds to the near stoichiometric composition (N/(Ti,Zr) ratio ˜0.95). The sheet resistance of Cu/(Ti,Zr)N0.95/Si was not significantly increased until annealing above 750°C, indicating good thermal stability. On the other hand, the adhesion energy between Cu and the (Ti,Zr)Nx film was reduced as the N/Ti ratio was increased. To obtain reliable performance on stress-induced-voiding (SIV) and electromigration (EM) tests, we proposed to use (Ti,Zr)/(Ti,Zr)N x /(Ti,Zr) tri-layers. We suggest that the interfacial adhesion between barrier and Cu plays an important role in reliability. The proposed tri-layer structure may be a promising candidate for a barrier, as it exhibits excellent reliability without increasing resistance.

Additive Manufacturing of NiTiHf High Temperature Shape Memory Alloy

NASA Technical Reports Server (NTRS)

Benafan, Othmane; Bigelow, Glen S.; Elahinia, Mohammad; Moghaddam, Narges Shayesteh; Amerinatanzi, Amirhesam; Saedi, Soheil; Toker, Guher Pelin; Karaca, Haluk

2017-01-01

Additive manufacturing of a NiTi-20Hf high temperature shape memory alloy (HTSMA) was investigated. A selective laser melting (SLM) process by Phenix3D Systems was used to develop components from NiTiHf powder (of approximately 25-75 m particle fractions), and the thermomechanical response was compared to the conventionally vacuum induction skull melted counterpart. Transformation temperatures of the SLM material were found to be slightly lower due to the additional oxygen pick up from the gas atomization and melting process. The shape memory response in compression was measured for stresses up to 500 MPa, and transformation strains were found to be very comparable (Up to 1.26 for the as-extruded; up to 1.52 for SLM).

ZrO2-modified mesoporous nanocrystalline TiO2-xNx as efficient visible light photocatalysts.

PubMed

Wang, Xinchen; Yu, Jimmy C; Chen, Yilin; Wu, Ling; Fu, Xianzhi

2006-04-01

Mesoporous nanocrystalline TiO2-xNx and TiO2-xNx/ZrO2 visible-light photocatalysts have been prepared by a sol-gel method. The photocatalysts were characterized by XRD, N2 adsorption-desorption, TEM, XPS, UV/Vis, and IR spectroscopy. The photocatalytic activity of the samples was evaluated by the decomposition of ethylene in air under visible light (lambda > 450 nm) illumination. Results revealed that nitrogen was doped into the lattice of TiO2 by the thermal treatment of NH3-adsorbed TiO2 hydrous gels, converting the TiO2 into a visible-light responsive catalyst. The introduction of ZrO2 into TiO2-xNx considerably inhibits the undesirable crystal growth during calcination. Consequently, the ZrO2-modified TiO2-xNx displays higher porosity, higher specific surface area, and an improved thermal stability over the corresponding unmodified TiO2-xNx samples.

Cavitation resistance of surface composition "Steel-Ni-TiNi-TiNiZr-cBNCo", formed by High-Velocity Oxygen-Fuel spraying

NASA Astrophysics Data System (ADS)

Blednova, Zh. M.; Dmitrenko, D. V.; Balaev, E. U. O.

2018-01-01

The object of the study is a multilayered surface composition "Steel - a Multicomponent material with Shape Memory Effect - a wear-resistant layer" under conditions of cavitation effects in sea water. Multicomponent TiNi-based coatings with addition of alloying elements such as Zr in an amount up to 10% mass, allow to create a composite material with a gradient of properties at the interface of layers, which gives new properties to coatings and improves their performance significantly. The use of materials with shape memory effect (SME) as surface layers or in the composition of surface layered compositions allows to provide an effective reaction of materials to the influence of external factors and adaptation to external influences. The surface composite layer cBN-10%Co has high hardness and strength, which ensures its resistance to shock cyclic influences of collapsing caverns. The increased roughness of the surface of a solid surface composite in the form of strong columnar structures ensures the crushing of vacuum voids, redistributing their effect on the entire surface, and not concentrating them in certain zones. In addition, the gradient structure of the multilayer composite coating TiNi-Ti33Ni49Zr18-cBN-10%Co Co makes it possible to create conditions for the relaxation of stresses created by the variable impact load of cavitation caverns and the manifestation of compensating internal forces due to thermo-elastic martensitic transformations of SME materials. The cavitation resistance of the coating TiNi-Ti33Ni49Zr18-cBN-10%Co according to the criterion of mass wear is 15-20 times higher than that of the base material without coating and 10-12 times higher than that of the TiNi-TiNiZr coating. The proposed architecture of the multifunctional gradient composition, "steel-Ni-TiNi- Ti33Ni49Zr18-cBN-10%Co", each layer of which has its functional purpose, allows to increase the service life of parts operating under conditions of cavitation-fatigue loading in

Efficiency enhancement of dye-sensitized solar cells by use of ZrO2-doped TiO2 nanofibers photoanode.

PubMed

Mohamed, Ibrahim M A; Dao, Van-Duong; Barakat, Nasser A M; Yasin, Ahmed S; Yousef, Ahmed; Choi, Ho-Suk

2016-08-15

Due to the good stability and convenient optical properties, TiO2 nanostructures still the prominent photoanode materials in the Dye Sensitized Solar Cells (DSCs). However, the well-known low bandgap energy and weak adsorption affinity for the dye distinctly constrain the wide application. This work discusses the impact of Zr-doping and nanofibrous morphology on the performance and physicochemical properties of TiO2. Zr-doped TiO2 nanofibers (NFs), with various zirconia content (0, 0.5, 1, 1.5 and 2wt%) were prepared by calcination of electrospun mats composed of polyvinyl acetate, titanium isopropoxyl and zirconium n-propoxyl. For all formulations, the results have shown that the prepared materials are continuous, randomly oriented, and good morphology nanofibers. The average diameter decreased from 353.85nm to 210.78nm after calcination without a considerable influence on the nanofibrous structure regardless the zirconia content. XRD result shows that there is no Rutile nor Brookite phases in the obtained material and the average crystallite size of the sample is affected by the presence of Zr-doping and changed from 23.01nm to 37.63nm for TiO2 and Zr-doped TiO2, respectively. Optical studies have shown Zr-doped TiO2 NFs have more absorbance in the visible region than that of pristine TiO2 NFs; the maximum absorbance is corresponding to the NFs having 1wt% zirconia. The improved spectra of Zr-doped TiO2 in the visible region is attributed to the heterostructure composition resulting from Zr-doping. The absorption bandgaps were calculated using Tauc model as 3.202 and 3.217 for pristine and Zr (1wt%)-doped TiO2 NFs, respectively. Furthermore, in Dye-sensitized Solar Cells, utilizing Zr (1wt%)-doped TiO2 nanofibers achieved higher efficiency of 4.51% compared to the 1.61% obtained from the pristine TiO2 NFs. Copyright © 2016 Elsevier Inc. All rights reserved.

Unusual and Tunable Negative Linear Compressibility in the Metal-Organic Framework MFM-133(M) (M = Zr, Hf).

PubMed

Yan, Yong; O'Connor, Alice E; Kanthasamy, Gopikkaa; Atkinson, George; Allan, David R; Blake, Alexander J; Schröder, Martin

2018-03-21

High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB 4- [H 4 TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M 6 (μ 3 -OH) 8 (OH) 8 (COO) 8 } clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward a more elongated polyhedron under static compression. Despite the isomorphous nature of these two structures, MFM-133(Hf) shows a higher degree of NLC than the Zr(IV) analogue. Thus, for the first time, we demonstrate here that the NLC property can be effectively tuned in a framework material by simply varying the inorganic component of the frameworks without changing the network topology and structure.

3D surface topography study of the biofunctionalized nanocrystalline Ti-6Zr-4Nb/Ca-P

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

Jakubowicz, J., E-mail: jaroslaw.jakubowicz@put.poznan.pl; Adamek, G.; Jurczyk, M.U.

2012-08-15

In this work surface of the sintered Ti-6Zr-4Nb nanocrystalline alloy was electrochemically biofunctionalized. The porous surface was produced by anodic oxidation in 1 M H{sub 3}PO{sub 4} + 2%HF electrolyte at 10 V for 30 min. Next the calcium-phosphate (Ca-P) layer was deposited, onto the formed porous surface, using cathodic potential - 5 V kept for 60 min in 0.042 M Ca(NO{sub 3}){sub 2} + 0.025 M (NH{sub 4}){sub 2}HPO{sub 4} + 0.1 M HCl electrolyte. The deposited Ca-P layer anchored in the pores. The biofunctionalized surface was studied by XRD, SEM and EDS. In vitro tests culture of normalmore » human osteoblast (NHOst) cells showed very good cells proliferation, colonization and multilayering. Using optical profiler, roughness and hybrid 3D surface topography parameters were estimated. Correlation between surface composition, morphology, roughness and biocompatibility results was done. It has been shown by us that surface with appropriate chemical composition and topography, after combined electrochemical anodic and cathodic surface treatment, supports osteoblast adhesion and proliferation. 3D topography measurements using optical profiler play a key role in the biomaterials surface analysis. - Highlights: Black-Right-Pointing-Pointer Nanocrystalline Ti-6Zr-4Nb/Ca-P material was produced for hard tissue implant applications. Black-Right-Pointing-Pointer Calcium-phosphate results in surface biofunctionalization. Black-Right-Pointing-Pointer The biofunctionalized surface shows good in-vitro behavior.« less

New Intermetallic Ternary Phosphide Chalcogenide AP2-xXx (A = Zr, Hf; X = S, Se) Superconductors with PbFCl-Type Crystal Structure

NASA Astrophysics Data System (ADS)

Kitô, Hijiri; Yanagi, Yousuke; Ishida, Shigeyuki; Oka, Kunihiko; Gotoh, Yoshito; Fujihisa, Hiroshi; Yoshida, Yoshiyuki; Iyo, Akira; Eisaki, Hiroshi

2014-07-01

We have synthesized a series of intermetallic ternary phosphide chalcogenide superconductors, AP2-xXx (A = Zr, Hf; X = S, Se), using the high-pressure synthesis technique. These materials have a PbFCl-type crystal structure (space group P4/nmm) when x is greater than 0.3. The superconducting transition temperature Tc changes systematically with x, yielding dome-like phase diagrams. The maximum Tc is achieved at approximately x = 0.7, at which point the Tc is 6.3 K for ZrP2-xSex (x = 0.75), 5.5 K for HfP2-xSex (x = 0.7), 5.0 K for ZrP2-xSx (x = 0.675), and 4.6 K for Hfp2-xSx (x = 0.5). They are typical type-II superconductors and the upper and lower critical fields are estimated to be 2.92 T at 0 K and 0.021 T at 2 K for ZrP2-xSex (x = 0.75), respectively.

The influence of HF treatment on corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy

NASA Astrophysics Data System (ADS)

Ye, Xin-Yu; Chen, Min-Fang; You, Chen; Liu, De-Bao

2010-06-01

The samples made of a Mg-2.5wt.%Zn-0.5wt.%Zr alloy were immersed in the 20% hydrofluoric acid (HF) solution at room temperature for different time, with the aim of improving the properties of magnesium (Mg) alloy in applications as biomaterials. The corrosion resistance and in vitro biocompatibility of untreated and fluoride-coated samples were investigated. The results show that the optimum process is to immerse Mg alloys in the 20% HF solution for 6 h. After the immersion, a dense magnesium fluoride (MgF2) coating of 0.5 μm was synthesized on the surface of Mg-Zn-Zr alloy. Polarization tests recorded a reduction in the corrosion current density from 2.10 to 0.05 μA/cm2 due to the MgF2 protective coating. Immersion tests in the simulated body fluid (SBF) also reveal a much milder corrosion on the fluoride-coated samples, and its corrosion rate was calculated to be 0.05 mm/yr. Hemolysis test suggests that the conversion coated Mg alloy has no obvious hemolysis reaction. The hemolysis ratio (HR) of the samples decreases from 11.34% to 1.86% with the HF treatment, which meets the requirements of biomaterials (HR < 5%). The coculture of 3T3 fibroblasts with Mg alloy results in the adhesion and proliferation of cells on the surface of fluoride-coated samples. All the results show that the MgF2 conversion coating would markedly improve the corrosion resistance and in vitro biocompatibility of Mg-Zn-Zr alloy.

Ferroelectricity and antiferroelectricity of doped thin HfO2-based films.

PubMed

Park, Min Hyuk; Lee, Young Hwan; Kim, Han Joon; Kim, Yu Jin; Moon, Taehwan; Kim, Keum Do; Müller, Johannes; Kersch, Alfred; Schroeder, Uwe; Mikolajick, Thomas; Hwang, Cheol Seong

2015-03-18

The recent progress in ferroelectricity and antiferroelectricity in HfO2-based thin films is reported. Most ferroelectric thin film research focuses on perovskite structure materials, such as Pb(Zr,Ti)O3, BaTiO3, and SrBi2Ta2O9, which are considered to be feasible candidate materials for non-volatile semiconductor memory devices. However, these conventional ferroelectrics suffer from various problems including poor Si-compatibility, environmental issues related to Pb, large physical thickness, low resistance to hydrogen, and small bandgap. In 2011, ferroelectricity in Si-doped HfO2 thin films was first reported. Various dopants, such as Si, Zr, Al, Y, Gd, Sr, and La can induce ferro-electricity or antiferroelectricity in thin HfO2 films. They have large remanent polarization of up to 45 μC cm(-2), and their coercive field (≈1-2 MV cm(-1)) is larger than conventional ferroelectric films by approximately one order of magnitude. Furthermore, they can be extremely thin (<10 nm) and have a large bandgap (>5 eV). These differences are believed to overcome the barriers of conventional ferroelectrics in memory applications, including ferroelectric field-effect-transistors and three-dimensional capacitors. Moreover, the coupling of electric and thermal properties of the antiferroelectric thin films is expected to be useful for various applications, including energy harvesting/storage, solid-state-cooling, and infrared sensors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zr doping effect with low-cost solid-state reaction method to synthesize submicron Li4Ti5O12 anode material

NASA Astrophysics Data System (ADS)

Seo, Inseok; Lee, Cheul-Ro; Kim, Jae-Kwang

2017-09-01

To improve the electrochemical properties, fine Zr-doping Li4Ti5O12 anode materials for rechargeable lithium batteries with a uniform particle size distribution were synthesized by a modified solid-state reaction using fine Li2CO3 and TiO2 (anatase) powders as precursors with a Li:Ti molar ratio of 4:5. The use of fine Li2CO3 and TiO2 (anatase) powders as precursors prevented the formation of ZrO2 at 0.1 mol Zr-doping. XRD analysis revealed that the substitution of Zr for Ti leads to the increase of lattice parameters, allowing improved Li diffusion. The discharge capacity retention increased slightly with Zr-doping and the 0.1 mol Zr-doped Li4Ti5O12 electrode achieved 99% retention of discharge capacity.

Grain size engineering for ferroelectric Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films by an insertion of Al{sub 2}O{sub 3} interlayer

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

Kim, Han Joon; Park, Min Hyuk; Kim, Yu Jin

2014-11-10

The degradation of ferroelectric (FE) properties of atomic layer deposited Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films with increasing thickness was mitigated by inserting 1 nm-thick Al{sub 2}O{sub 3} interlayer at middle position of the thickness of the FE film. The large P{sub r} of 10 μC/cm{sup 2}, which is 11 times larger than that of single layer Hf{sub 0.5}Zr{sub 0.5}O{sub 2} film with equivalent thickness, was achieved from the films as thick as 40 nm. The Al{sub 2}O{sub 3} interlayer could interrupt the continual growth of Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films, and the resulting decrease of grain size prevented the formation of non-ferroelectricmore » monoclinic phase. The Al{sub 2}O{sub 3} interlayer also largely decreased the leakage current of the Hf{sub 0.5}Zr{sub 0.5}O{sub 2} films.« less

Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters.

PubMed

Yao, Yuan; Li, Gonghu; Gray, Kimberly A; Lueptow, Richard M

2008-07-15

We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.

Nanostructured multielement (TiHfZrNbVTa)N coatings before and after implantation of N+ ions (1018 cm-2): Their structure and mechanical properties

NASA Astrophysics Data System (ADS)

Pogrebnjak, A. D.; Bondar, O. V.; Borba, S. O.; Abadias, G.; Konarski, P.; Plotnikov, S. V.; Beresnev, V. M.; Kassenova, L. G.; Drodziel, P.

2016-10-01

Multielement high entropy alloy (HEA) nitride (TiHfZrNbVTa)N coatings were deposited by vacuum arc and their structural and mechanical stability after implantation of high doses of N+ ions, 1018 cm-2, were investigated. The crystal structure and phase composition were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy, while depth-resolved nanoindentation tests were used to determine the evolution of hardness and elastic modulus along the implantation depth. XRD patterns show that coatings exhibit a main phase with fcc structure, which preferred orientation varies from (1 1 1) to (2 0 0), depending on the deposition conditions. First-principles calculations reveal that the presence of Nb atoms could favor the formation of solid solution with fcc structure in multielement HEA nitride. TEM results showed that amorphous and nanostructured phases were formed in the implanted coating sub-surface layer (∼100 nm depth). Concentration of nitrogen reached 90 at% in the near-surface layer after implantation, and decreased at higher depth. Nanohardness of the as-deposited coatings varied from 27 to 38 GPa depending on the deposition conditions. Ion implantation led to a significant decrease of the nanohardness to 12 GPa in the implanted region, while it reaches 24 GPa at larger depths. However, the H/E ratio is ⩾0.1 in the sub-surface layer due to N+ implantation, which is expected to have beneficial effect on the wear properties.

Zirconium, hafnium, and rare earth element partition coefficients for ilmenite and other minerals in high-Ti lunar mare basalts - An experimental study

NASA Technical Reports Server (NTRS)

Mckay, G.; Wagstaff, J.; Yang, S.-R.

1986-01-01

Partition coefficients were determined for Gd, Lu, Hf and Zr among ilmenite, armalcolite, and synthetic high-Ti mare basaltic melts at temperatures from 1122 deg to 1150 deg, and at oxygen fugacities of IW x 10 exp 0.5, by in situ analysis with an electron microprobe, using samples doped to present concentration levels. Coefficients for Zr were also measured for samples containing 600-1600 ppm Zr using this microprobe. In addition, coefficients were determined for Hf and Zr between chromian ulvospinel and melt, for Hf between pigeonite and melt, and for Lu between olivine and melt by microprobe analysis of samples doped to present levels. Values measured using the microprobe were in agreement with the values measured by analyzing mineral separates from the same run products by isotope dilution. Coefficient values for ilmenite are less than 0.01 for the LREE, are around 0.1 for the HREE, and are several times greater than this for Zr and Hf.

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

NASA Astrophysics Data System (ADS)

Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

2003-07-01

The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

Study of Ti 4+ substitution in ZrW 2O 8 negative thermal expansion materials

NASA Astrophysics Data System (ADS)

De Buysser, Klaartje; Van Driessche, Isabel; Putte, Bart Vande; Schaubroeck, Joseph; Hoste, Serge

2007-08-01

Powder XRD-analysis and thermo-mechanical analysis on sintered TiO 2-WO 3-ZrO 2 mixtures revealed the formation of Zr 1-xTi xW 2O 8 solid solutions. A noticeable decrease in unit cell parameter ' a' and in the order-disorder transition temperature could be seen in the case of Zr 1-xTi xW 2O 8 solid solutions. Studies performed on other ZrW 2O 8 solid solutions have attributed an increase in phase transition temperature to a decrease in free lattice volume, whereas a decrease in phase transition temperature was suggested to be due to the presence of a more disordered state. Our studies indicate that the phase transition temperature in our materials is strongly influenced by the bond dissociation energy of the substituting ion-oxygen bond. A decrease in bond strength may compensate for the effect of a decrease in lattice free volume, lowering the phase transition temperature as the degree of substitution by Ti 4+ increases. This hypothesis is proved by differential scanning calorimetry.

Biomimetic Hydroxyapatite Growth on Functionalized Surfaces of Ti-6Al-4V and Ti-Zr-Nb Alloys

NASA Astrophysics Data System (ADS)

Pylypchuk, Ie V.; Petranovskaya, A. L.; Gorbyk, P. P.; Korduban, A. M.; Markovsky, P. E.; Ivasishin, O. M.

2015-08-01

A biomimetic approach for coating titanium-containing alloys with hydroxyapatite (HA) is reported in the article. Two types of Ti-containing alloys were chosen as an object for coating: Ti-6Al-4V (recommended for orthopedic application) and a novel highly biocompatible Ti-Zr-Nb alloy, with good mechanical compatibility due to a modulus that is more close to that of human bones (E ≈ 50 GPa instead of 110 GPa in Ti-6Al-4V). Coating process was carried out in a 10×-concentrated simulated body fluid (SBF)—synthetic analog of human body plasma. The effect of oxidized and carboxylated alloy surface on formation of biomimetic hydroxyapatite has been studied. By XRD, we found influence of thermal conditions on HA crystal formation and size. SEM images and Fourier transform infrared confirmed that hydroxyapatite with different morphology, crystallinity, and Ca/P ratio formed on metallic surfaces. X-ray photoelectron spectroscopy showed that in the Ti-6AL-4V sample the observed Ca/P ratio reach 0.97, whereas in the Ti-Zr-Nb sample the observed Ca/P ratio reach 1.15.

Improving the tribocorrosion resistance of Ti6Al4V surface by laser surface cladding with TiNiZrO2 composite coating

NASA Astrophysics Data System (ADS)

Obadele, Babatunde Abiodun; Andrews, Anthony; Mathew, Mathew T.; Olubambi, Peter Apata; Pityana, Sisa

2015-08-01

Ti6Al4V alloy was laser cladded with titanium, nickel and zirconia powders in different ratio using a 2 kW CW ytterbium laser system (YLS). The microstructures of the cladded layers were examined using field emission scanning electron microscopy (FESEM) equipped with energy dispersive X-ray spectroscopy (EDS) and X-ray diffractometry (XRD). Corrosion and tribocorrosion tests were performed on the cladded surface in 1 M H2SO4 solution. The microstructure revealed the transformation from a dense dendritic structure in TiNi coating to a flower-like structure observed in TiNiZrO2 cladded layers. There was a significant increase in surface microindentation hardness values of the cladded layers due to the present of hard phase ZrO2 particles. The results obtained show that addition of ZrO2 improves the corrosion resistance property of TiNi coating but decrease the tribocorrosion resistance property. The surface hardening effect induced by ZrO2 addition, combination of high hardness of Ti2Ni phase could be responsible for the mechanical degradation and chemical wear under sliding conditions.

Alloying effects on structural and thermal behavior of Ti{sub 1-x}Zr{sub x}C: A first principles study

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

Chauhan, Mamta, E-mail: mamta-physics@yahoo.co.in; Gupta, Dinesh C., E-mail: sosfizix@gmail.com

2016-05-06

The formation energy, equilibrium lattice parameter, bulk modulus, Debye temperature and heat capacity at constant volume have been calculated for TiC, ZrC, and their intermediate alloys (Ti{sub 1-x}Zr{sub x}C, x = 0,0.25.0.5,0.75,1) using first principles approach. The calculated values of lattice parameter and bulk modulus agree well with the available experimental and earlier theoretical reports. The variation of lattice parameter and bulk modulus with the change in concentration of Zr atom in Ti{sub 1-x}Zr{sub x}C has also been reported. The heat capacities of TiC, ZrC, and their intermediate alloys have been calculated by considering both vibrational and electronic contributions.

Wear Resistance Enhancement of Ti-6Al-4 V Alloy by Applying Zr-Modified Silicide Coatings

NASA Astrophysics Data System (ADS)

Li, Xuan; Hu, Guangzhong; Tian, Jin; Tian, Wei; Xie, Wenling; Li, Xiulan

2018-03-01

Zr-modified silicide coatings were prepared on Ti-6Al-4 V alloy by pack cementation process to enhance its wear resistance. The microstructure and wear properties of the substrate and the coatings were comparatively investigated using GCr15 and Al2O3 as the counterparts under different sliding loads. The obtained Zr-modified silicide coating had a multilayer structure, consisting of a thick (Ti, X)Si2 (X represents Al, Zr and V elements) outer layer, a TiSi middle layer and a Ti5Si4 + Ti5Si3 inner layer. The micro-hardness of the coating was much higher than the substrate and displayed a decrease tendency from the coating surface to the interior. Sliding against either GCr15 or Al2O3 balls, the coatings showed superior anti-friction property to the Ti-6Al-4 V alloy, as confirmed by its much lower wear rate under each employed sliding condition.

Features of Crystallization of Rapidly Quenched Ni45Ti32Hf18Cu5 and Ni25Ti32Hf18Cu25 Alloys from Melt with High-Temperature Shape Memory Effect

NASA Astrophysics Data System (ADS)

Pushin, A. V.; Pushin, V. G.; Kuntsevich, T. E.; Kuranova, N. N.; Makarov, V. V.; Uksusnikov, A. N.; Kourov, N. I.

2017-12-01

A comparative study of the structure and the chemical and phase composition of Ni45Ti32Hf18Cu5 and Ni25Ti32Hf18Cu25 amorphous alloys obtained by fast-quenching of melt stream by spinning has been carried out by transmission and scanning electron microscopy and X-ray diffraction. The critical temperatures of their devitrification were determined by the data of temperatures measurements of electrical resistance. The features of the formation of ultrafine structure and the phase transformation at the vitrification depending on the regimes of heat treatment and chemical composition of alloy have been established.

HfSe2 and ZrSe2: Two-dimensional semiconductors with native high-κ oxides

PubMed Central

Mleczko, Michal J.; Zhang, Chaofan; Lee, Hye Ryoung; Kuo, Hsueh-Hui; Magyari-Köpe, Blanka; Moore, Robert G.; Shen, Zhi-Xun; Fisher, Ian R.; Nishi, Yoshio; Pop, Eric

2017-01-01

The success of silicon as a dominant semiconductor technology has been enabled by its moderate band gap (1.1 eV), permitting low-voltage operation at reduced leakage current, and the existence of SiO2 as a high-quality “native” insulator. In contrast, other mainstream semiconductors lack stable oxides and must rely on deposited insulators, presenting numerous compatibility challenges. We demonstrate that layered two-dimensional (2D) semiconductors HfSe2 and ZrSe2 have band gaps of 0.9 to 1.2 eV (bulk to monolayer) and technologically desirable “high-κ” native dielectrics HfO2 and ZrO2, respectively. We use spectroscopic and computational studies to elucidate their electronic band structure and then fabricate air-stable transistors down to three-layer thickness with careful processing and dielectric encapsulation. Electronic measurements reveal promising performance (on/off ratio > 106; on current, ~30 μA/μm), with native oxides reducing the effects of interfacial traps. These are the first 2D materials to demonstrate technologically relevant properties of silicon, in addition to unique compatibility with high-κ dielectrics, and scaling benefits from their atomically thin nature. PMID:28819644

Efficient UV-emitting X-ray phosphors: octahedral Zr(PO 4) 6 luminescence centers in potassium hafnium-zirconium phosphates K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3

NASA Astrophysics Data System (ADS)

Torardi, C. C.; Miao, C. R.; Li, J.

2003-02-01

Potassium hafnium-zirconium phosphates, K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3, are broad-band UV-emitting phosphors. At room temperature, they have emission peak maxima at approximately 322 and 305 nm, respectively, under 30 kV peak molybdenum X-ray excitation. Both phosphors demonstrate luminescence efficiencies that make them up to ˜60% as bright as commercially available CaWO 4 Hi-Plus. The solid-state and flux synthesis conditions, and X-ray excited UV luminescence of these two phosphors are discussed. Even though the two compounds have different atomic structures, they contain zirconium in the same active luminescence environment as that found in highly efficient UV-emitting BaHf 1- xZr x(PO 4) 2. All the three materials have hafnium and zirconium in octahedral coordination via oxygen-atom corner sharing with six separate PO 4 tetrahedra. This octahedral Zr(PO 4) 6 moiety appears to be an important structural element for efficient X-ray excited luminescence, as are the edge-sharing octahedral TaO 6 chains for tantalate emission.

Effects of Fabrication Parameters on Interface of Zirconia and Ti-6Al-4V Joints Using Zr55Cu30Al10Ni5 Amorphous Filler

NASA Astrophysics Data System (ADS)

Liu, Yuhua; Hu, Jiandong; Shen, Ping; Guo, Zuoxing; Liu, Huijie

2013-09-01

ZrO2 was brazed to Ti-6Al-4V using a Zr55Cu30Al10Ni5 (at.%) amorphous filler in a high vacuum at 1173-1273 K. The influences of brazing temperature, holding time, and cooling rate on the microstructure and shear strength of the joints were investigated. The interfacial microstructures can be characterized as ZrO2/ZrO2- x + TiO/(Zr,Ti)2(Cu,Ni)/(Zr,Ti)2(Cu,Ni,Al)/acicular Widmanstäten structure/Ti-6Al-4V. With the increase in the brazing temperature, both the thickness of the ZrO2- x + TiO layer and the content of the (Zr,Ti)2(Cu,Ni) phase decreased. However, the acicular Widmanstäten structure gradually increased. With the increase in the holding time, the (Zr,Ti)2(Cu,Ni) phase decreased, and the thickness of the (Zr,Ti)2(Cu,Ni) + (Zr,Ti)2(Cu,Ni,Al) layer decreased. In addition, cracks formed adjacent to the ZrO2 side under rapid cooling. The microstructures produced under various fabrication parameters directly influence the shear strength of the joints. When ZrO2 and Ti-6Al-4V couples were brazed at 1173 K for 10 min and then cooled at a rate of 5 K/min, the maximum shear strength of 95 MPa was obtained.

Microstructural Evolution of the Interface Between Pure Titanium and Low Melting Point Zr-Ti-Ni(Cu) Filler Metals

NASA Astrophysics Data System (ADS)

Lee, Dongmyoung; Sun, Juhyun; Kang, Donghan; Shin, Seungyoung; Hong, Juhwa

2014-12-01

Low melting point Zr-based filler metals with melting point depressants (MPDs) such as Cu and Ni elements are used for titanium brazing. However, the phase transition of the filler metals in the titanium joint needs to be explained, since the main element of Zr in the filler metals differs from that of the parent titanium alloys. In addition, since the MPDs easily form brittle intermetallics, that deteriorate joint properties, the phase evolution they cause needs to be studied. Zr-based filler metals having Cu content from 0 to 12 at. pct and Ni content from 12 to 24 at. pct with a melting temperature range of 1062 K to 1082 K (789 °C to 809 °C) were wetting-tested on a titanium plate to investigate the phase transformation and evolution at the interface between the titanium plate and the filler metals. In the interface, the alloys system with Zr, Zr2Ni, and (Ti,Zr)2Ni phases was easily changed to a Ti-based alloy system with Ti, Ti2Ni, and (Ti,Zr)2Ni phases, by the local melting of parent titanium. The dissolution depths of the parent metal were increased with increasing Ni content in the filler metals because Ni has a faster diffusion rate than Cu. Instead, slow diffusion of Cu into titanium substrate leads to the accumulation of Cu at the molten zone of the interface, which could form undesirable Ti x Cu y intermetallics. This study confirmed that Zr-based filler metals are compatible with the parent titanium metal with the minimum content of MPDs.

Pressure-dependent structure of the null-scattering alloy Ti 0.676 Zr 0.324

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

Zeidler, Anita; Guthrie, Malcolm; Salmon, Philip S.

2015-05-13

The room temperature structure of the alloy Ti0.676Zr0.324Ti0.676Zr0.324 was measured by X-ray diffraction under compression at pressures up to ~30GPa. This alloy is used as a construction material in high pressure neutron-scattering research and has a mean coherent neutron scattering length of zero, that is, it is a so-called null-scattering alloy. A broad phase transition was observed from a hexagonal close-packed α-phase to a hexagonal ω-phase, which started at a pressure of ≲12GPa≲12GPa and was completed by ~25GPa. The data for the α-phase were fitted by using a third-order Birch–Murnaghan equation of state, giving an isothermal bulk modulus B0=87(4)GPaB0=87(4)GPa andmore » pressure derivative B'0=6.6(8)B0'=6.6(8). The results will help to ensure that accurate structural information can be gained from in situ high pressure neutron diffraction work on amorphous and liquid materials where the Ti0.676Zr0.324Ti0.676Zr0.324 alloy is used as a gasket material.« less

Influence of Zr doping on structure and morphology of TiO2 nanorods prepared using hydrothermal method

NASA Astrophysics Data System (ADS)

Muslimin, Masliana; Jumali, Mohammad Hafizuddin; Tee, Tan Sin; Beng, Lee Hock; Hui, Tan Chun; Chin, Yap Chi

2018-04-01

The aim of this work is to investigate the effect of Zr doping on TiO2 nanostructure. TiO2 nanorods thin films with different Zr-doping concentrations (6 × 10-3 M, 13 × 10-3 M and 25 × 10-3 M) were successfully prepared using a simple hydrothermal method. The structural and morphological properties of the samples were evaluated using XRD and FESEM respectively. The XRD results revealed that the TiO2 in all samples stabilized as rutile phase. The FESEM micrographs confirmed that TiO2 exist as square like nanorods with blunt tips. Although the crystallographic nature remains unchanged, the introduction of Zr has altered the surface density, structure and morphology of TiO2 which subsequently will have significant effect on its properties.

First-principles quantum molecular dynamics study of Ti x Zr1-x N(111)/SiN y heterostructures and comparison with experimental results.

PubMed

Ivashchenko, Volodymyr; Veprek, Stan; Pogrebnjak, Alexander; Postolnyi, Bogdan

2014-04-01

The heterostructures of five monolayers B1-Ti x Zr 1- x N(111), x = 1.0, 0.6, 0.4 and 0.0 (where B1 is a NaCl-type structure) with one monolayer of a Si 3 N 4 -like Si 2 N 3 interfacial layer were investigated by means of first-principles quantum molecular dynamics and a structure optimization procedure using the Quantum ESPRESSO code. Slabs consisting of stoichiometric TiN and ZrN and random, as well as segregated, B1-Ti x Zr 1- x N(111) solutions were considered. The calculations of the B1-Ti x Zr 1- x N solid solutions, as well as of the heterostructures, showed that the pseudo-binary TiN-ZrN system exhibits a miscibility gap. The segregated heterostructures in which Zr atoms surround the Si y N z interface were found to be the most stable. For the Zr-rich heterostructures, the total energy of the random solid solution was lower compared to that of the segregated one, whereas for the Ti-rich heterostructures the opposite tendency was observed. Hard and super hard Zr-Ti-Si-N coatings with thicknesses from 2.8 to 3.5 μ m were obtained using a vacuum arc source with high frequency stimulation. The samples were annealed in a vacuum and in air at 1200 °C. Experimental investigations of Zr-Ti-N, Zr-Ti-Si-N and Ti-Si-N coatings with different Zr, Ti and Si concentrations were carried out for comparison with results obtained from Ti x Zr 1 - x N(111)/SiN y systems. During annealing, the hardness of the best series samples was increased from (39.6 ± 1.4) to 53.6 GPa, which seemed to indicate that a spinodal segregation along grain interfaces was finished. A maximum hardness of 40.8 GPa before and 55 GPa after annealing in air at 500 °C was observed for coatings with a concentration of elements of Si≽ (7-8) at.%, Ti ≽ 22 at.% and Zr ⩽ 70 at.%.

Coexistence of diode-like volatile and multilevel nonvolatile resistive switching in a ZrO2/TiO2 stack structure.

PubMed

Li, Yingtao; Yuan, Peng; Fu, Liping; Li, Rongrong; Gao, Xiaoping; Tao, Chunlan

2015-10-02

Diode-like volatile resistive switching as well as nonvolatile resistive switching behaviors in a Cu/ZrO₂/TiO₂/Ti stack are investigated. Depending on the current compliance during the electroforming process, either volatile resistive switching or nonvolatile resistive switching is observed. With a lower current compliance (<10 μA), the Cu/ZrO₂/TiO₂/Ti device exhibits diode-like volatile resistive switching with a rectifying ratio over 10(6). The permanent transition from volatile to nonvolatile resistive switching can be obtained by applying a higher current compliance of 100 μA. Furthermore, by using different reset voltages, the Cu/ZrO₂/TiO₂/Ti device exhibits multilevel memory characteristics with high uniformity. The coexistence of nonvolatile multilevel memory and diode-like volatile resistive switching behaviors in the same Cu/ZrO₂/TiO₂/Ti device opens areas of applications in high-density storage, logic circuits, neural networks, and passive crossbar memory selectors.

Surface phenomena of hydroxyapatite film on the nanopore formed Ti-29Nb-xZr alloy by anodization for bioimplants.

PubMed

Kim, Eun-Ju; Jeong, Yong-Hoon; Choe, Han-Cheol

2013-03-01

In this study, surface phenomena of hydroxyapatite (HA) film on the nanopore formed Ti-29Nb-xZr alloy by anodization for bioimplants have been investigated by electron beam physical vapor deposition (EB-PVD), field emission scanning electron microscope (FE-SEM), X-ray diffractometer (XRD), potentiostat and contact angle. The microstructure of Ti-29Nb-xZr alloys exhibited equiaxed structure and alpha" phase decreased, whereas beta phase increased as Zr content increased. The increment of Zr contents in HA coated nanotubular Ti-29Nb-xZr alloys showed good corrosion potential in 0.9% NaCI solution. The wettability of HA coated nanotubular surface was higher than that of non-coated samples.

Improved conversion efficiency of dye sensitized solar cell using Zn doped TiO{sub 2}-ZrO{sub 2} nanocomposite

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

Tomar, Laxmi J., E-mail: laxmi-tomar86@yahoo.com; Bhatt, Piyush J.; Desai, Rahul K.

TiO{sub 2}-ZrO{sub 2} and Zn doped TiO{sub 2}-ZrO{sub 2} nanocomposites were prepared by hydrothermal method for dye sensitized solar cell (DSSC) application. The structural and optical properties were investigated by X –ray diffraction (XRD) and UV-Visible spectroscopy respectively. XRD results revealed the formation of material in nano size. The average crystallite size is 22.32 nm, 17.41 nm and 6.31 nm for TiO{sub 2}, TiO{sub 2}-ZrO{sub 2} and Zn doped TiO{sub 2}-ZrO{sub 2} nanocomposites respectively. The optical bandgap varies from 2.04 eV to 3.75 eV. Dye sensitized solar cells were fabricated using the prepared material. Pomegranate juice was used as a sensitizer and graphitemore » coated conducting glass plate was used as counter electrode. The I – V characteristics were recorded to measure photo response of DSSC. Photovoltaic parameter like open circuit voltage, power conversion efficiency, and fill factor were evaluated for fabricated solar cell. The power conversion efficiency of DSSC fabricated with TiO{sub 2}, TiO{sub 2}-ZrO{sub 2} and Zn doped TiO{sub 2}-ZrO{sub 2} nanocomposites were found 0.71%, 1.97% and 4.58% respectively.« less

Superelasticity, corrosion resistance and biocompatibility of the Ti-19Zr-10Nb-1Fe alloy.

PubMed

Xue, Pengfei; Li, Yan; Li, Kangming; Zhang, Deyuan; Zhou, Chungen

2015-05-01

Microstructure, mechanical properties, superelasticity and biocompatibility of a Ti-19Zr-10Nb-1Fe alloy are investigated. X-ray diffraction spectroscopy and transmission electron microscopy observations show that the as-cast Ti-19Zr-10Nb-1Fe alloy is composed of α' and β phases, but only the β phase exists in the as-rolled and as-quenched alloys. The tensile stress-strain tests indicate that the as-quenched alloy exhibits a good combination of mechanical properties with a large elongation of 25%, a low Young's modulus of 59 GPa and a high ultimate tensile stress of 723 MPa. Superelastic recovery behavior is found in the as-quenched alloy during tensile tests, and the corresponding maximum of superelastic strain is 4.7% at the pre-strain of 6%. A superelastic recovery of 4% with high stability is achieved after 10 cyclic loading-unloading training processes. Potentiodynamic polarization and ion release measurements indicate that the as-quenched alloy shows a lower corrosion rate in Hank's solution and a much less ion release rate in 0.9% NaCl solution than those of the NiTi alloys. Cell culture results indicate that the osteoblasts' adhesion and proliferation are similar on both the Ti-19Zr-10Nb-1Fe and NiTi alloys. A better hemocompatibility is confirmed for the as-quenched Ti-19Zr-10Nb-1Fe alloy, attributed to more stable platelet adhesion and small activation degree, and a much lower hemolysis rate compared with the NiTi alloy. Copyright © 2015 Elsevier B.V. All rights reserved.

Geochemical characteristics of aluminum depleted and undepleted komatiites and HREE-enriched low-Ti tholeiites, western Abitibi greenstone belt: A heterogeneous mantle plume-convergent margin environment

NASA Astrophysics Data System (ADS)

Fan, J.; Kerrich, R.

1997-11-01

A compositionally diverse suite of komatiites, komatiitic basalts, and basalts coexist in the Tisdale volcanic assemblage of the late-Archean (˜2.7 Ga) Abitibi greenstone belt. The komatiites are characterized by a spectrum of REE patterns, from low total REE contents (9 ppm) and pronounced convex-up patterns to greater total REE (18 ppm) and approximately flat-distributions. Thorium and niobium are codepleted with LREE. Komatiites with the most convex-up patterns have low Al 2O 3 (4.7 wt%) contents and Al 2O 3/TiO 2(12) ratios; they are interpreted to be the Al-depleted variety of komatiite derived from a depleted mantle source. Those komatiites and komatiitic basalts with flatter REE patterns are characterized by greater Al 2O 3 (7.0 wt%) and near chondritic Al 2O 3/TiO 2 (20) ratios; they are interpreted to be Al-undepleted komatiites generated from trace element undepleted mantle. For the komatiites and komatiitic basalts collectively, Gd/Ybn ratios are negatively correlated with La/Smn, but positively with MgO and Ni. The spectrum of patterns is interpreted as mixing between Al, HREE, Y-depleted, and Sc-depleted komatiites and Al-undepleted komatiites in a heterogeneous mantle plume. Auminum-depleted komatiites are characterized by negative Zr and Hf anomalies, consistent with majorite garnet-liquid D's for HFSE and REEs, signifying melt segregation at depths of >400 km. Tisdale Al-undepleted komatiites and komatiitic basalts have small negative to zero Zr(Hf)/MREE fractionation, signifying melt segregation in or above the garnet stability field. Collectively, the komatiites have correlations of Zr/Zr∗ and Hf/Hf ∗ with Gd/Ybn, and hence the Zr(Hf)/MREE fractionations are unlikely to have stemmed from alteration or crustal contamination. Two types of basalts are present. Type I basalts are Mg-tholeiites with near flat REE and primitive mantle normalized patterns, compositionally similar to abundant Mg-tholeiites associated with both Al-undepleted and Al

Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1993-01-01

El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

Preparation and Characterization of Ferroelectric BaTi0.91(Hf0.5, Zr0.5)0.09O3 Thin Films by Sol-Gel Process Using Titanium and Zirconium Alkoxides

NASA Astrophysics Data System (ADS)

Thongrueng, Jirawat; Nishio, Keishi; Nagata, Kunihiro; Tsuchiya, Toshio

2000-09-01

Sol-gel-derived BaTi0.91(Hf0.5, Zr0.5)0.09O3 (BTHZ-9) thin films have been successfully prepared on Pt and Pt(111)/Ti/SiO2/Si(100) substrates by spin-coating and sintering from 550 to 900°C for 2 h in oxygen ambient. X-ray diffraction measurement indicated that the single perovskite phase of the BTHZ-9 thin films was obtained at heat treatment above 650°C. The formation temperature of the double-alkoxy-derived BTHZ-9 thin films was lower by at least 80°C than that of the films prepared from only titanium alkoxide. The microstructure of the films was observed by atomic force microscopy and scanning electron microscopy. The grain size of the films increased from 70 to 200 nm with increasing sintering temperature ranging from 650 to 850°C. The maximum peak for the dielectric constant, corresponding to the Curie point (87°C), was broad and lower in magnitude compared with that of the BTHZ-9 bulk ceramics. Tensile stresses resulting from the differences between thermal expansion coefficients of the substrate and the film caused poor electrical properties. BTHZ-9 thin films exhibited a well-saturated polarization-electric field hysteresis loop. The polarization and coercive field for the 850-nm-thick BTHZ-9 thin film prepared on Pt/Ti/SiO2/Si substrate at 750°C were determined to be 8 μC/cm2 and 15 kV/cm, respectively. Those of the BTHZ-9 thin film prepared on Pt substrate at 850°C were found to be 9 μC/cm2 and 18 kV/cm, respectively.

Temperature-dependent local structural properties of redox Pt nanoparticles on TiO 2 and ZrO 2 supports

DOE PAGES

Jeong, Eun -Suk; Park, Chang -In; Jin, Zhenlan; ...

2015-01-21

This paper examined the local structural properties of Pt nanoparticles on SiO 2, TiO 2–SiO 2, and ZrO 2–SiO 2 supports to better understand the impact of oxide-support type on the performance of Pt-based catalysts. In situ X-ray absorption fine structure (XAFS) measurements were taken for the Pt L3-edge in a temperature range from 300 to 700 K in He, H 2, and O 2 gas environments. The XAFS measurements demonstrated that Pt atoms were highly dispersed on TiO 2–SiO 2 and ZrO 2–SiO 2 forming pancake-shaped nanoparticles, whereas Pt atoms formed larger particles of hemispherical shapes on SiO 2more » supports. Contrary to the SiO 2 case, the coordination numbers for Pt, Ti, and Zr around Pt atoms on the TiO 2–SiO 2 and ZrO 2–SiO 2 supports were nearly constant from 300 to 700 K under the different gas environments. These results are consistent with the improvements in thermal stability of Pt nanoparticles achieved by incorporating TiO 2 or ZrO 2 on the surface of SiO 2 supports. XAFS analysis further indicated that the enhanced dispersion and stability of Pt were a consequence of the strong metal support interaction via Pt–Ti and Pt–Zr bonds.« less

Highly efficient Zr doped-TiO2/glass fiber photocatalyst and its performance in formaldehyde removal under visible light.

PubMed

Huang, Chao; Ding, Yaping; Chen, Yingwen; Li, Peiwen; Zhu, Shemin; Shen, Shubao

2017-10-01

Zr-doped-TiO 2 loaded glass fiber (ZT/GF) composite photocatalysts with different Zr/Ti ratios were prepared with a sol-gel process. Zr 4+ can replace Ti 4+ in the TiO 2 lattice, which is conducive to forming the anatase phase and reducing the calcination temperature. The glass fiber carrier was responsible for better dispersion and loading of Zr-doped-TiO 2 particles, improving the applicability of the Zr-doped-TiO 2 . The ZT/GF photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis) and Barrett-Joyner-Halenda (BJH). The performance of photocatalysts with different loading was evaluated in formaldehyde degradation under visible light at room temperature. ZT/GF0.2 exhibited the highest activity, with a formaldehyde removal rate as high as 95.14% being observed, which is better than that of the photocatalyst particles alone. The stability of the catalyst was also tested, and ZT/GF exhibited excellent catalytic performance with 94.38% removal efficiency, even after seven uses. Copyright © 2017. Published by Elsevier B.V.

Electrical Properties of Ultrathin Hf-Ti-O Higher k Gate Dielectric Films and Their Application in ETSOI MOSFET.

PubMed

Xiong, Yuhua; Chen, Xiaoqiang; Wei, Feng; Du, Jun; Zhao, Hongbin; Tang, Zhaoyun; Tang, Bo; Wang, Wenwu; Yan, Jiang

2016-12-01

Ultrathin Hf-Ti-O higher k gate dielectric films (~2.55 nm) have been prepared by atomic layer deposition. Their electrical properties and application in ETSOI (fully depleted extremely thin SOI) PMOSFETs were studied. It is found that at the Ti concentration of Ti/(Ti + Hf) ~9.4%, low equivalent gate oxide thickness (EOT) of ~0.69 nm and acceptable gate leakage current density of 0.61 A/cm 2 @ (V fb  - 1)V could be obtained. The conduction mechanism through the gate dielectric is dominated by the F-N tunneling in the gate voltage range of -0.5 to -2 V. Under the same physical thickness and process flow, lower EOT and higher I on /I off ratio could be obtained while using Hf-Ti-O as gate dielectric compared with HfO 2 . With Hf-Ti-O as gate dielectric, two ETSOI PMOSFETs with gate width/gate length (W/L) of 0.5 μm/25 nm and 3 μm/40 nm show good performances such as high I on , I on /I off ratio in the magnitude of 10 5 , and peak transconductance, as well as suitable threshold voltage (-0.3~-0.2 V). Particularly, ETSOI PMOSFETs show superior short-channel control capacity with DIBL <82 mV/V and subthreshold swing <70 mV/decade.

The adhesion performance of epoxy coating on AA6063 treated in Ti/Zr/V based solution

NASA Astrophysics Data System (ADS)

Zhu, Wen; Li, Wenfang; Mu, Songlin; Yang, Yunyu; Zuo, Xi

2016-10-01

An environment-friendly titanium/zirconium/vanadium-based (Ti/Zr/V) conversion coating was prepared on aluminum alloy 6063 (AA6063). The epoxy powder coatings were applied on the AA6063 samples with/without Ti/Zr/V conversion coatings via electrostatic spraying. The morphology and composition of the conversion coating were studied by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The surface free energy components of AA6063 samples were measured by a static contact angle measuring device with Owens method. The adhesion properties of the epoxy coating on AA6063 treated with different conversion times were evaluated using a pull-off tester. The Ti/Zr/V conversion coating was mainly composed of metal oxide (TiO2, ZrO2, V2O5, Al2O3, etc.), metal fluoride (ZrF4, AlF3, etc.) and metal organic complex. The formation time of this conversion coating was reduced to 50 s. After such surface treatment, the samples' surface roughness was increased and the contact angle with water was decreased. Both the surface free energy and the work of adhesion were increased. The adhesion strength between the epoxy coating and AA6063 was enhanced significantly.

Tunneling current in HfO2 and Hf0.5Zr0.5O2-based ferroelectric tunnel junction

NASA Astrophysics Data System (ADS)

Dong, Zhipeng; Cao, Xi; Wu, Tong; Guo, Jing

2018-03-01

Ferroelectric tunnel junctions (FTJs) have been intensively explored for future low power data storage and information processing applications. Among various ferroelectric (FE) materials studied, HfO2 and H0.5Zr0.5O2 (HZO) have the advantage of CMOS process compatibility. The validity of the simple effective mass approximation, for describing the tunneling process in these materials, is examined by computing the complex band structure from ab initio simulations. The results show that the simple effective mass approximation is insufficient to describe the tunneling current in HfO2 and HZO materials, and quantitative accurate descriptions of the complex band structures are indispensable for calculation of the tunneling current. A compact k . p Hamiltonian is parameterized to and validated by ab initio complex band structures, which provides a method for efficiently and accurately computing the tunneling current in HfO2 and HZO. The device characteristics of a metal/FE/metal structure and a metal/FE/semiconductor (M-F-S) structure are investigated by using the non-equilibrium Green's function formalism with the parameterized effective Hamiltonian. The result shows that the M-F-S structure offers a larger resistance window due to an extra barrier in the semiconductor region at off-state. A FTJ utilizing M-F-S structure is beneficial for memory design.

C60 and U ion irradiation of Gd 2Ti xZr 2-xO 7 pyrochlore

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

Zhang, Jiaming; Toulemonde, Marcel; Lang, Maik

2015-08-01

Gd 2Ti xZr 2-xO 7 (x = 0 to 2) pyrochlore was irradiated by 30 MeV C 60 clusters, which provide an extremely high ionizing energy density. Here, high-resolution transmission electron microscopy revealed a complex ion-track structure in Gd 2Ti 2O 7 and Gd 2TiZrO 7, consisting of an amorphous core and a shell of a disordered, defect-fluorite structure.

Energy band alignment of antiferroelectric (Pb,La)(Zr,Sn,Ti)O3

NASA Astrophysics Data System (ADS)

Klein, Andreas; Lohaus, Christian; Reiser, Patrick; Dimesso, Lucangelo; Wang, Xiucai; Yang, Tongqing

2017-06-01

The energy band alignment of antiferroelectric (Pb,La)(Zr,Sn,Ti)O3 is studied with photoelectron spectroscopy using interfaces with high work function RuO2 and low work function Sn-doped In2O3 (ITO). It is demonstrated how spectral deconvolution can be used to determine absolute Schottky barrier heights for insulating materials with a high accuracy. Using this approach it is found that the valence band maximum energy of (Pb,La)(Zr,Sn,Ti)O3 is found to be comparable to that of Pb- and Bi-containing ferroelectric materials, which is ∼1 eV higher than that of BaTiO3. The results provide additional evidence for the occupation of the 6s orbitals as origin of the higher valence band maximum, which is directly related to the electrical properties of such compounds. The results also verify that the energy band alignment determined by photoelectron spectroscopy of as-deposited electrodes is not influenced by polarisation. The electronic structure of (Pb,La)(Zr,Sn,Ti)O3 should enable doping of the material without strongly modifying its insulating properties, which is crucial for high energy density capacitors. Moreover, the position of the energy bands should result in a great freedom of selecting electrode materials in terms of avoiding charge injection.

Zr-doped TiO2 supported on delaminated clay materials for solar photocatalytic treatment of emerging pollutants.

PubMed

Belver, C; Bedia, J; Rodriguez, J J

2017-01-15

Solar light-active Zr-doped TiO 2 nanoparticles were successfully immobilized on delaminated clay materials by a one-step sol-gel route. Fixing the amount of TiO 2 at 65wt.%, this work studies the influence of Zr loading (up to 2%) on the photocatalytic activity of the resulting Zr-doped TiO 2 /clay materials. The structural characterization demonstrates that all samples were formed by a delaminated clay with nanostructured anatase assembled on its surface. The Zr dopant was successfully incorporated into the anatase lattice, resulting in a slight deformation of the anatase crystal and the reduction of the band gap. These materials exhibit high surface area with a disordered mesoporous structure formed by TiO 2 particles (15-20nm) supported on a delaminated clay. They were tested in the solar photodegradation of antipyrine, usually used as an analgesic drug and selected as an example of emerging pollutant. High degradation rates have been obtained at low antipyrine concentrations and high solar irradiation intensities with the Zr-doped TiO 2 /clay catalyst, more effective than the undoped one. This work demonstrates the potential application of the synthesis method for preparing novel and efficient solar-light photocatalysts based on metal-doped anatase and a delaminated clay. Copyright © 2016 Elsevier B.V. All rights reserved.

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide

NASA Astrophysics Data System (ADS)

Mao, Dongsen; Lu, Guanzhong

2007-02-01

The effect of B 2O 3 addition on the crystallization of amorphous TiO 2-ZrO 2 mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO 2-ZrO 2 mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO 2-ZrO 2 into a crystalline ZrTiO 4 compound, while a larger amount of boria (⩾8 wt%) promotes the crystallization process. FT-IR spectroscopy and 11B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO 4 units delay, while a build-up of trigonal BO 3 promote, the crystallization of amorphous TiO 2-ZrO 2 to form ZrTiO 4 crystals.

The intrinsic disorder related alloy scattering in ZrNiSn half-Heusler thermoelectric materials

PubMed Central

Xie, Hanhui; Wang, Heng; Fu, Chenguang; Liu, Yintu; Snyder, G. Jeffrey; Zhao, Xinbing; Zhu, Tiejun

2014-01-01

The intrinsic structural disorder dramatically affects the thermal and electronic transport in semiconductors. Although normally considered an ordered compound, the half-Heusler ZrNiSn displays many transport characteristics of a disordered alloy. Similar to the (Zr,Hf)NiSn based solid solutions, the unsubstituted ZrNiSn compound also exhibits charge transport dominated by alloy scattering, as demonstrated in this work. The unexpected charge transport, even in ZrNiSn which is normally considered fully ordered, can be explained by the Ni partially filling interstitial sites in this half-Heusler system. The influence of the disordering and defects in crystal structure on the electron transport process has also been quantitatively analyzed in ZrNiSn1-xSbx with carrier concentration nH ranging from 5.0×1019 to 2.3×1021 cm−3 by changing Sb dopant content. The optimized carrier concentration nH ≈ 3–4×1020 cm−2 results in ZT ≈ 0.8 at 875K. This work suggests that MNiSn (M = Hf, Zr, Ti) and perhaps most other half-Heusler thermoelectric materials should be considered highly disordered especially when trying to understand the electronic and phonon structure and transport features. PMID:25363573

Electronic structure of a laterally graded ZrO2-TiO2 film on Si(100) prepared by metal-organic chemical vapor deposition in ultrahigh vacuum

NASA Astrophysics Data System (ADS)

Richter, J. H.; Karlsson, P. G.; Sandell, A.

2008-05-01

A TiO2-ZrO2 film with laterally graded stoichiometry has been prepared by metal-organic chemical vapor deposition in ultrahigh vacuum. The film was characterized in situ using synchrotron radiation photoelectron spectroscopy (PES) and x-ray absorption spectroscopy. PES depth profiling clearly shows that Ti ions segregate toward the surface region when mixed with ZrO2. The binding energy of the ZrO2 electronic levels is constant with respect to the local vacuum level. The binding energy of the TiO2 electronic levels is aligned to the Fermi level down to a Ti /Zr ratio of about 0.5. At a Ti /Zr ratio between 0.1 and 0.5, the TiO2 related electronic levels become aligned to the local vacuum level. The addition of small amounts of TiO2 to ZrO2 results in a ZrO2 band alignment relative to the Fermi level that is less asymmetric than for pure ZrO2. The band edge positions shift by -0.6eV for a Ti /Zr ratio of 0.03. This is explained in terms of an increase in the work function when adding TiO2, an effect that becomes emphasized by Ti surface segregation.

Preparation of ZrO II/nano-TiO II composite powder by sol-gel method

NASA Astrophysics Data System (ADS)

Baharvandi, H. R.; Mohammadi, E.; Abdizadeh, H.; Hadian, A. M.; Ehsani, N.

2007-07-01

The effects of concentration of TTIP, amount of distilled water, and calcination temperature on morphology and particle size distribution of ZrO II/nano-TiO II catalysts were investigated. Mixed ZrO II/nano-TiO II powders were prepared by a modified sol-gel method by varying the mole fraction of TTIP from 0.002 to 0.01, H IIO/TTIP fraction from 2 to 8, and various stirring time (2, 4, and 10 h). The prepared ZrO II/nano-TiO II powders have been characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and TG/DTA. Each oxide was calcined at the temperature between 110 and 1000°C. The results showed that the calcinations temperature has a pronounced effect on the phase formation and particle size of the calcined zirconium titanate (ZT) powders.

Effect of film thickness on the ferroelectric and dielectric properties of low-temperature (400 °C) Hf0.5Zr0.5O2 films

NASA Astrophysics Data System (ADS)

Kim, Si Joon; Mohan, Jaidah; Lee, Jaebeom; Lee, Joy S.; Lucero, Antonio T.; Young, Chadwin D.; Colombo, Luigi; Summerfelt, Scott R.; San, Tamer; Kim, Jiyoung

2018-04-01

We report on the effect of the Hf0.5Zr0.5O2 (HZO) film thickness on the ferroelectric and dielectric properties using pulse write/read measurements. HZO films of thicknesses ranging from 5 to 20 nm were annealed at 400 °C for 1 min in a nitrogen ambient to be compatible with the back-end of the line thermal budget. As the HZO film thickness decreases, low-voltage operation (1.0 V or less) can be achieved without the dead layer effect, although switching polarization (Psw) tends to decrease due to the smaller grain size. Meanwhile, for 20-nm-thick HZO films prepared under the identical stress (similar TiN top electrode thickness and thermal budget), the Psw and dielectric constant are reduced because of additional monoclinic phase formation.

Synaptic Plasticity and Learning Behaviors Mimicked in Single Inorganic Synapses of Pt/HfOx/ZnOx/TiN Memristive System

NASA Astrophysics Data System (ADS)

Wang, Lai-Guo; Zhang, Wei; Chen, Yan; Cao, Yan-Qiang; Li, Ai-Dong; Wu, Di

2017-01-01

In this work, a kind of new memristor with the simple structure of Pt/HfOx/ZnOx/TiN was fabricated completely via combination of thermal-atomic layer deposition (TALD) and plasma-enhanced ALD (PEALD). The synaptic plasticity and learning behaviors of Pt/HfOx/ZnOx/TiN memristive system have been investigated deeply. Multilevel resistance states are obtained by varying the programming voltage amplitudes during the pulse cycling. The device conductance can be continuously increased or decreased from cycle to cycle with better endurance characteristics up to about 3 × 103 cycles. Several essential synaptic functions are simultaneously achieved in such a single double-layer of HfOx/ZnOx device, including nonlinear transmission properties, such as long-term plasticity (LTP), short-term plasticity (STP), and spike-timing-dependent plasticity. The transformation from STP to LTP induced by repetitive pulse stimulation is confirmed in Pt/HfOx/ZnOx/TiN memristive device. Above all, simple structure of Pt/HfOx/ZnOx/TiN by ALD technique is a kind of promising memristor device for applications in artificial neural network.

Single layer of MX3(M = Ti, Zr; X = S, Se, Te): a new platform for nano-electronics and optics

NASA Astrophysics Data System (ADS)

Jin, Yingdi; Li, Xingxing; Yang, Jinlong

A serial of two dimensional titanium and zirconium trichalcogenides nanosheets MX3 (M=Ti, Zr; X=S, Se, Te) are investigated based on first-principles calculations. The evaluated low cleavage energy indicates that stable two dimensional monolayers can be exfoliated from their bulk crystals in experiment. Electronic studies reveal very rich electronic properties in these monolayers, including metallic TiTe3 and ZrTe3, direct band gap semiconductor TiS3 and indirect band gap semiconductors TiSe3, ZrS3 and ZrSe3. The band gaps of all the semiconductors are between 0.57~1.90 eV, which implies their potential applications in nano-electronics. And the calculated effective masses demonstrate highly anisotropic conduction properties for all the semiconductors. Optically, TiS3 and TiSe3 monolayers exhibit good light absorption in the visible and near-infrared region respectively, indicating their potential applications in optical devices. In particular, the highly anisotropic optical absorption of TiS3 monolayer suggests it could be used in designing nano optical waveguide polarizers.

Oriented and ordered mesoporous ZrO{sub 2}/TiO{sub 2} fibers with well-organized linear and spring structure

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

Zhu, Luyi, E-mail: zhuly@sdu.edu.cn; Liu, Benxue; Qin, Weiwei, E-mail: jiuyuan.1001@163.com

Graphical abstract: The ultra-stable order mesoporous ZrO{sub 2}/TiO{sub 2} fibers with well-organized linear and spring structure and large surface area under higher temperatures were prepared by a simple EISA process. - Highlights: • The ZrO{sub 2}/TiO{sub 2} fibers were prepared by EISA process combined with steam heat-treatment. • The mesoporous ZrO{sub 2}/TiO{sub 2} fibers have well-organized linear and spring structure. • The fibers were composed of oval rod nanocrystals of ZrTiO{sub 4}. - Abstract: The ultra-stable order mesoporous ZrO{sub 2}/TiO{sub 2} fibers with well-organized linear and spring structure and large surface areas under higher temperatures were prepared by a (simplemore » evaporation-induced assembly) EISA process. The preparation, microstructures and formation processes were characterized by Fourier transformation infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N{sub 2} adsorption–absorption measurements. The fibers take on pinstripe configuration which is very orderly along or perpendicular to the axial direction of the fibers. The diameters of the pinstripe are in the region of 200–400 nm and arranges regularly, which are composed of oval rod nanocrystals of ZrTiO{sub 4}.« less

Fatigue in artificially layered Pb(Zr,Ti)O3 ferroelectric films

NASA Astrophysics Data System (ADS)

Jiang, A. Q.; Scott, J. F.; Dawber, M.; Wang, C.

2002-12-01

We have performed fatigue tests on lead zirconate titanate (PZT) multilayers having stacks of Pb(Zr0.8Ti0.2)O3/Pb(Zr0.2Ti0.8)O3 with repeated distances of 12 formula groups. The results are compared with single-layer n-type (0.5 at. % Ta-doped) PZT films. We conclude that fatigue is dominated by space-charge layers in each case, but that in the multilayer such space charge accumulates at the layer interfaces, rather than at the electrode-dielectric interface. The model, which includes both drift and diffusion, is quantitative and yields a rate-limiting mobility of 6.9±0.9×10-12 cm2/V s, in excellent agreement with the oxygen vacancy mobility for perovskite oxides obtained from Zafar et al.

Preliminary Tests for Ti-Mo-Zr-Ta Alloys as Potential Biomaterials

NASA Astrophysics Data System (ADS)

Bălţatu, M. S.; Vizureanu, P.; Bălan, T.; Lohan, M.; Ţugui, C. A.

2018-06-01

Nowadays, there is a continuing concern for the research and development of alloys for medical and biomedical applications. In order to check the biocompatible character of a new Ti-Mo-Zr-Ta alloys, it is necessary to carry out preliminary laboratory tests to follow how a biomaterial surface would interact with the host. The paper presents tests for Ti-Mo-Zr-Ta alloys like contact angle and DSC test to identify biocompatible character. Contact angle measurement is an experimental technique used to assess the hydrophilic or hydrophobic character of surfaces by reference to the 90º contact angle value and to characterize the thermal behavior, for temperature range between 36.5-37.2ºC, interval which a biomaterial works inside the healthy human body, was used DSC test.

Phase stability, magnetic, electronic, half-metallic and mechanical properties of a new equiatomic quaternary Heusler compound ZrRhTiIn: A first-principles investigation

NASA Astrophysics Data System (ADS)

Wang, Jia-Xing; Chen, Z. B.; Gao, Y. C.

2018-05-01

In this manuscript, we have studied the electronic, magnetic, half-metallic and mechanical properties of a new Zr-based equiatomic quaternary Heusler (EQH) compound, ZrRhTiIn using first-principles calculations. The generalized gradient approximation (GGA) calculation results imply that at its equilibrium lattice constant of 6.70 Å, ZrRhTiIn is a half-metallic material (HMM) with a considerable band gap (Ebg) of 0.530 eV and a spin-filter/half-metallic band-gap (EHM) of 0.080 eV in the minority-spin channel. For ZrRhTiIn, the formation energy of -2.738 eV and the cohesive energy of 21.38 eV indicate that it is a thermodynamically stable material according to theory. The minority-spin EHM arises from the hybridization among Zr-4d, Ti-3d and Rh-4d electrons. The calculated total magnetic moment of ZrRhTiIn is 2 μB, meeting the well-known Slater-Pauling rule Mt = Zt -18. Furthermore, uniform strain and tetragonal strain were applied in this work to examine the magneto-electronic and half-metallic behaviors of the ZrRhTiIn system. Finally, we show that ZrRhTiIn is mechanically stable, ductile and anisotropic.

Zr-doped TiO2 as a thermostabilizer in plasmon-enhanced dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Pasche, Anastasia; Grohe, Bernd; Mittler, Silvia; Charpentier, Paul A.

2017-07-01

Harvesting solar energy is a promising solution toward meeting the world's ever-growing energy demand. Dye-sensitized solar cells (DSSCs) are hybrid organic-inorganic solar cells with tremendous potential for commercial application, but they are plagued by inefficiency due to their poor sunlight absorption. Plasmonic silver nanoparticles (AgNPs) have been shown to enhance the absorptive properties of DSSCs, but their plasmonic resonance can cause thermal damage resulting in cell deterioration. Hence, the influence of Zr-doped TiO2 on the efficiency of plasmon-enhanced DSSCs was studied, showing that 5 mol.% Zr-doping of the photoactive TiO2 material can improve the photovoltaic performance of DSSCs by 44%. By examining three different DSSC designs, it became clear that the efficiency enhancing effect of Zr strongly depends on the proximity of the Zr-doped material to the plasmonic AgNPs.

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

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

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE PAGES

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.; ...

2017-03-20

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Structural and Kinetic Hydrogen Sorption Properties of Zr0.8Ti0.2Co Alloy Prepared by Ball Milling

PubMed Central

He, Hui; Tang, Tao; Huang, Zhiyong; Sang, Ge; Zhang, Guanghui; Ba, Jingwen; Liu, Meng

2018-01-01

The effects of ball milling on the hydrogen sorption kinetics and microstructure of Zr0.8Ti0.2Co have been systematically studied. Kinetic measurements show that the hydrogenation rate and amount of Zr0.8Ti0.2Co decrease with increasing the ball milling time. However, the dehydrogenation rate accelerates as the ball milling time increases. Meanwhile, the disproportionation of Zr0.8Ti0.2Co speeds up after ball milling and the disproportionation kinetics is clearly inclined to be linear with time at 500°C. It is found from X-ray powder diffraction (XRD) results that the lattice parameter of Zr0.8Ti0.2Co gradually decreases from 3.164 Å to 3.153 Å when the ball milling time extends from 0 h to 8 h, which is mainly responsible for the hydrogen absorption/desorption behaviors. In addition, scanning electron microscope (SEM) images demonstrate that the morphology of Zr0.8Ti0.2Co has obviously changed after ball milling, which is closely related to the hydrogen absorption kinetics. Besides, high-resolution transmission electron microscopy (HRTEM) images show that a large number of disordered microstructures including amorphous regions and defects exist after ball milling, which also play an important role in hydrogen sorption performances. This work will provide some insights into the principles of how to further improve the hydrogen sorption kinetics and disproportionation property of Zr0.8Ti0.2Co. PMID:29721128

Fe-Al interface intermixing and the role of Ti, V, and Zr as a stabilizing interlayer at the interface

NASA Astrophysics Data System (ADS)

Priyantha, W.; Smith, R. J.; Chen, H.; Kopczyk, M.; Lerch, M.; Key, C.; Nachimuthu, P.; Jiang, W.

2009-03-01

Fe-Al bilayer interfaces with and without interface stabilizing layers (Ti, V, Zr) were fabricated using dc magnetron sputtering. Intermixing layer thickness and the effectiveness of the stabilizing layer (Ti, V, Zr) at the interface were studied using Rutherford backscattering spectrometry (RBS) and x-ray reflectometry (XRR). The result for the intermixing thickness of the AlFe layer is always higher when Fe is deposited on Al as compared to when Al is deposited on Fe. By comparing measurements with computer simulations, the thicknesses of the AlFe layers were determined to be 20.6 Å and 41.1 Å for Al/Fe and Fe/Al bilayer systems, respectively. The introduction of Ti and V stabilizing layers at the Fe-Al interface reduced the amount of intermixing between Al and Fe, consistent with the predictions of model calculations. The Zr interlayer, however, was ineffective in stabilizing the Fe-Al interface in spite of the chemical similarities between Ti and Zr. In addition, analysis suggests that the Ti interlayer is not effective in stabilizing the Fe-Al interface when the Ti interlayer is extremely thin (˜3 Å) for these sputtered metallic films.

One-pot synthesis and optical properties of Eu3+-doped nanocrystalline TiO2 and ZrO2

NASA Astrophysics Data System (ADS)

Julián, Beatriz; Corberán, Rosa; Cordoncillo, Eloisa; Escribano, Purificación; Viana, Bruno; Sanchez, Clément

2005-11-01

A simple and versatile one-pot sol-gel synthesis of Eu3+-doped nanocrystalline TiO2 and ZrO2 nanomaterials is reported in this paper. It consists of the controlled crystallization of Eu3+-doped TiO2 or ZrO2 nanoparticles from an initial solution containing the metal alkoxide, the lanthanide precursor, a complexing agent and a non-complexing acid. The main interest is that it could be extended to different lanthanide ions and inorganic metal oxides to prepare other multifunctional nanomaterials. The characterization by XRD, HRTEM and SAED techniques showed that the TiO2 and ZrO2 crystallization takes place at very low temperatures (60 °C) and that the crystallite size can be tailored by modifying the synthetic conditions. The optical properties of the resulting materials were studied by emission spectra and decay measurements. Both Eu3+:TiO2 and Eu3+:ZrO2 samples exhibited long lifetime values after removing organic components (τ = 0.7 and 1.3 ms, respectively), but the Eu3+:ZrO2 system is specially promising for photonic applications since its τ value is longer than some reported for other inorganic or hybrid matrices in which Eu3+ ions are complexed. This behaviour has been explained through an effective dispersion of the lanthanide ions within the ZrO2 nanocrystals.

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors

NASA Astrophysics Data System (ADS)

Zhang, Min; Yu, Xinluan; Lu, Dandan; Yang, Jianjun

2013-12-01

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail.

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors

PubMed Central

2013-01-01

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail. PMID:24369051

Facile synthesis and enhanced visible light photocatalytic activity of N and Zr co-doped TiO2 nanostructures from nanotubular titanic acid precursors.

PubMed

Zhang, Min; Yu, Xinluan; Lu, Dandan; Yang, Jianjun

2013-12-26

Zr/N co-doped TiO2 nanostructures were successfully synthesized using nanotubular titanic acid (NTA) as precursors by a facile wet chemical route and subsequent calcination. These Zr/N-doped TiO2 nanostructures made by NTA precursors show significantly enhanced visible light absorption and much higher photocatalytic performance than the Zr/N-doped P25 TiO2 nanoparticles. Impacts of Zr/N co-doping on the morphologies, optical properties, and photocatalytic activities of the NTA precursor-based TiO2 were thoroughly investigated. The origin of the enhanced visible light photocatalytic activity is discussed in detail.

Reactive spark plasma synthesis of CaZrTi2O7 zirconolite ceramics for plutonium disposition

NASA Astrophysics Data System (ADS)

Sun, Shi-Kuan; Stennett, Martin C.; Corkhill, Claire L.; Hyatt, Neil C.

2018-03-01

Near single phase zirconolite ceramics, prototypically CaZrTi2O7, were fabricated by reactive spark plasma sintering (RSPS), from commercially available CaTiO3, ZrO2 and TiO2 reagents, after processing at 1200 °C for only 1 h. Ceramics were of theoretical density and formed with a controlled mean grain size of 1.9 ± 0.6 μm. The reducing conditions of RSPS afforded the presence of paramagnetic Ti3+, as demonstrated by EPR spectroscopy. Overall, this study demonstrates the potential for RSPS to be a disruptive technology for disposition of surplus separated plutonium stockpiles in ceramic wasteforms, given its inherent advantage of near net shape products and rapid throughput.

Improving fatigue resistance of Pb(Zr,Ti)O3 thin films by using PbZrO3 buffer layers

NASA Astrophysics Data System (ADS)

Mensur Alkoy, Ebru; Uchiyama, Kiyoshi; Shiosaki, Tadashi; Alkoy, Sedat

2006-05-01

Ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) thin films with PbZrO3 (PZ) buffer layers were prepared on Pt(111)/Ti/SiO2/Si(100) substrates using a hybrid rf magnetron sputtering and sol-gel process. Texture of PZT films was found to depend on Pb content of PZ buffer layers. Buffered PZT films displayed comparable ferroelectric properties (2Pr=38-53 μC/cm2,2Ec=136-170 kV/cm) with unbuffered PZT. Asymmetric leakage current and fatigue behavior with superior fatigue resistance was observed in PZ buffered PZT compared to unbuffered films. PZ buffer layers were found to affect crystallization and texture of PZT, and act as a capacitive interface layer possibly blocking charge injection from electrodes.

A comparison of the fatigue behavior of cast Ti-7.5Mo with c.p. titanium, Ti-6Al-4V and Ti-13Nb-13Zr alloys.

PubMed

Lin, Chia-Wei; Ju, Chien-Ping; Chern Lin, Jiin-Huey

2005-06-01

The purpose of the present study is to compare the high-cycle fatigue behavior of newly developed Ti-7.5Mo alloy with that of c.p. Ti, Ti-13Nb-13Zr and Ti-6Al-4V alloys in their as-cast state. Experimental results indicate that Ti-6Al-4V and c.p. Ti have higher stress-controlled fatigue resistance but lower strain-controlled fatigue resistance than Ti-7.5Mo and Ti-13Nb-13Zr. Among four materials Ti-7.5Mo demonstrates the best strain-controlled fatigue performance. The fracture surfaces of the present materials are comprised of three morphologically distinct zones: crack initiation zone, crack propagation zone, and the final-stage overload zone. The fatigue cracks almost always initiate from casting-induced surface/subsurface pores. A river pattern is observed in the propagation zone. In the overload zone dimples are typically observed. Three factors most significantly affecting the fatigue performance of the present materials are the presence of the casting-induced surface/subsurface pores; the location of the pores; and the inherent mechanical properties of the materials.

Phase composition, microstructure, and mechanical properties of porous Ti-Nb-Zr alloys prepared by a two-step foaming powder metallurgy method.

PubMed

Rao, X; Chu, C L; Zheng, Y Y

2014-06-01

Porous Ti-Nb-Zr alloys with different porosities from 6.06 to 62.8% are prepared by a two-step foaming powder metallurgy method using TiH2, Nb, and Zr powders together with 0 to 50wt% of NH4HCO3. The effects of the amounts of Nb and Zr as well as the sintering temperature (1473 to 1673K) on their phase composition, porosity, morphology, and mechanical characteristics are investigated. By controlling the porosity, Nb and Zr concentrations as well as the sintering temperature, porous Ti-Nb-Zr alloys with different mechanical properties can be obtained, for example, the hardness between 290 and 63HV, the compressive strength between 1530.5 and 73.4MPa, and the elastic modulus between 10.8 and 1.2GPa. The mechanical properties of the sintered porous Ti-Nb-Zr alloys can be tailored to match different requirements for the human bones and are thus potentially useful in the hard tissue implants. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thickness dependent thermoelectric properties of SrTiO3/SrLaTiO3 and SrZrO3/SrLaTiO3 heterostructures

NASA Astrophysics Data System (ADS)

Ishii, Masatoshi; Baniecki, John; Schafranek, Robert; Kerman, Kian; Kurihara, Kazuaki

2013-03-01

Thermoelectric power generators will be required for future sensor network systems. SrTiO3 (STO) is one candidate thermoelectric material due to its non-toxicity and comparable power factor to Bismuth telluride. The energy conversion efficiency of SrTiO3-based thermoelectric energy conversion elements has been reported to be enhanced by quantum size effects, such as the two dimensional (2D) electron gas in SrTiO3/SrTi0.8Nb0.2O3/SrTiO3. Nevertheless, a complete understanding of the mechanisms for the reported increase in efficiency are missing owing to a lack of understanding of the thickness dependence of the transport properties. In the talk, we will present a study of the thickness dependence of the transport properties of SrTiO3/SrLaTiO3 and SrZrO3/SrLaTiO3 heterostructures. The SrZrO3/SrLaTiO3 interface has a large conduction band off-set of 1.9 eV which can be utilized to confine electrons in a 2D quantum well. Characterization of the thermopower, conductivity, and Hall effect will be presented as a function of the SrLaTiO3 thickness down to a few unit cells and the implications of the thickness dependence of the transport properties on carrier confinement and increasing the efficiency STO-based 2DEG quantum well structures will be discussed.

Role of point defects and HfO2/TiN interface stoichiometry on effective work function modulation in ultra-scaled complementary metal-oxide-semiconductor devices

NASA Astrophysics Data System (ADS)

Pandey, R. K.; Sathiyanarayanan, Rajesh; Kwon, Unoh; Narayanan, Vijay; Murali, K. V. R. M.

2013-07-01

We investigate the physical properties of a portion of the gate stack of an ultra-scaled complementary metal-oxide-semiconductor (CMOS) device. The effects of point defects, such as oxygen vacancy, oxygen, and aluminum interstitials at the HfO2/TiN interface, on the effective work function of TiN are explored using density functional theory. We compute the diffusion barriers of such point defects in the bulk TiN and across the HfO2/TiN interface. Diffusion of these point defects across the HfO2/TiN interface occurs during the device integration process. This results in variation of the effective work function and hence in the threshold voltage variation in the devices. Further, we simulate the effects of varying the HfO2/TiN interface stoichiometry on the effective work function modulation in these extremely-scaled CMOS devices. Our results show that the interface rich in nitrogen gives higher effective work function, whereas the interface rich in titanium gives lower effective work function, compared to a stoichiometric HfO2/TiN interface. This theoretical prediction is confirmed by the experiment, demonstrating over 700 meV modulation in the effective work function.

Thermal Evaporation Loss Measurements on Quasicrystal (Ti-Zr-Ni) and Glass Forming (Vit 106 and Vit 106a) Liquids

NASA Astrophysics Data System (ADS)

Blodgett, M. E.; Gangopadhyay, A. K.; Kelton, K. F.

2015-04-01

Thermal evaporation loss measurements made using the electrostatic levitation (ESL) technique for one binary Ti-Zr, two ternary Ti-Zr-Ni, and two glass-forming (Vit 106 and Vit 106a) alloy liquids are reported. The containerless environment enables measurements not only for the equilibrium liquids but also for the metastable supercooled liquids. The data follow the Langmuir equation when the activity coefficient of the solute atoms, a measure for the deviation from the ideal solution behavior, is taken into account. An estimate for the activity coefficient of Ni in the Ti-Zr liquid is made from these data, demonstrating the effectiveness of ESL for such measurements.

Design and development of NiTi-based precipitation-strengthened high-temperature shape memory alloys for actuator applications

NASA Astrophysics Data System (ADS)

Hsu, Derek Hsen Dai

As a vital constituent in the field of smart materials and structures, shape memory alloys (SMAs) are becoming ever-more important due to their wide range of commercial and industrial applications such as aircraft couplings, orthodontic wires, and eyeglasses frames. However, two major obstacles preventing SMAs from fulfilling their potential as excellent actuator materials are: 1) the lack of commercially-viable SMAs that operate at elevated temperatures, and 2) the degradation of mechanical properties and shape memory behavior due to thermal cyclic fatigue. This research utilized a thermodynamically-driven systems design approach to optimize the desired properties by controlling the microstructure and processing of high-temperature SMAs (HTSMAs). To tackle the two aforementioned problems with HTSMAs, the introduction of Ni2TiAl coherent nanoprecipitates in a Ni-Ti-Zr/Hf HTSMA matrix is hypothesized to strengthen the martensite phase while simultaneously increasing the transformation temperature. Differential scanning calorimetry (DSC) was used to determine the transformation temperatures and thermal cyclic stability of each alloy. Also, microstructural characterization was performed using X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atom probe tomography (APT). Lastly, compression testing was used to assess the mechanical behavior of the alloys. From the investigation of the first set of Ni48.5Ti31.5-X Zr20AlX (X = 0, 1, 2, 3) prototype alloys, Al addition was found to decrease the transformation temperatures, decrease the thermal cyclic stability, but also increase the strength due to the nucleation and growth of embrittling NiTi2 and NiTiZr Laves phases. However, the anticipated Heusler phase precipitation did not occur. The next study focused on Ni50Ti30-XHf20Al X (X = 0, 1, 2, 3, 4, 5) prototype alloys which replaced Zr with Hf to avoid the formation of brittle Laves phases

Screening on binary Ti alloy with excellent mechanical property and castability for dental prosthesis application

PubMed Central

Li, H. F.; Qiu, K. J.; Yuan, W.; Zhou, F. Y.; Wang, B. L.; Li, L.; Zheng, Y. F.; Liu, Y. H.

2016-01-01

In the present study, the microstructure, mechanical property, castability, corrosion behavior and in vitro cytocompatibility of binary Ti–2X alloys with various alloying elements, including Ag, Bi, Ga, Ge, Hf, In, Mo, Nb, Sn and Zr, were systematically investigated, in order to assess their potential applications in dental field. The experimental results showed that all binary Ti‒2X alloys consisted entirely α–Ti phase. The tensile strength and microhardness of Ti were improved by adding alloying elements. The castability of Ti was significantly improved by separately adding 2 wt.% Bi, Ga, Hf, Mo, Nb, Sn and Zr. The corrosion resistance of Ti in both normal artificial saliva solution (AS) and extreme artificial saliva solution (ASFL, AS with 0.2 wt.% NaF and 0.3 wt.% lactic acid) has been improved by separately adding alloying elements. In addition, the extracts of studied Ti‒2X alloys produced no significant deleterious effect to both fibroblasts L929 cells and osteoblast-like MG63 cells, indicating a good in vitro cytocompatibility, at the same level as pure Ti. The combination of enhanced mechanical properties, castability, corrosion behavior, and in vitro cytocompatibility make the developed Ti‒2X alloys have great potential for future stomatological applications. PMID:27874034

Enhancement of wear and corrosion resistance of low modulus β-type Zr-20Nb-xTi (x=0, 3) dental alloys through thermal oxidation treatment.

PubMed

Zhang, Jianfeng; Gan, Xiaxia; Tang, Hongqun; Zhan, Yongzhong

2017-07-01

In order to obtain material with low elastic modulus, good abrasion resistance and high corrosion stability as screw for dental implant, the biomedical Zr-20Nb and Zr-20Nb-3Ti alloy with low elastic modulus were thermal oxidized respectively at 700°C for 1h and 600°C for 1.25h to obtain the compact oxidized layer to improve its wear resistance and corrosion resistance. The results show that smooth compact oxidized layer (composed of monoclinic ZrO 2 , tetragonal ZrO 2 and 6ZrO 2 -Nb 2 O 5 ) with 22.6μm-43.5μm thickness and 1252-1306HV hardness can be in-situ formed on the surface of the Zr-20Nb-xTi (x=0, 3). The adhesion of oxidized layers to the substrates is determined to be 58.35-66.25N. The oxidized Zr-20Nb-xTi alloys reveal great improvement of the pitting corrosion resistance in comparison with the un-oxidized alloys. In addition, the oxidized Zr-20Nb-3Ti exhibits sharply reduction of the corrosion rates and the oxidized Zr-20Nb shows higher corrosion rates than un-oxidized alloys, which is relevant with the content of the t-ZrO 2 . Wear test in artificial saliva demonstrates that the wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) are superior to pure Ti. All of the un-oxidized Zr-20Nb-xTi (x=0, 3) alloys suffer from serious adhesive wear due to its high plasticity. Because of the protection from compact oxide layer with high adhesion and high hardness, the coefficients of friction and wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) alloys decrease 50% and 95%, respectively. The defects on the oxidized Zr-20Nb have a negative effect on the friction and wear properties. In addition, after the thermal oxidation, compression test show that elastic modulus and strength of Zr-20Nb-xTi (x=0, 3) increase slightly with plastic deformation after 40% of transformation. Furthermore, stripping of the oxidized layer from the alloy matrix did not occur during the whole experiments. As the surface oxidized Zr-20Nb-3Ti alloy has a combination of excellent performance

Bone bonding bioactivity of Ti metal and Ti-Zr-Nb-Ta alloys with Ca ions incorporated on their surfaces by simple chemical and heat treatments.

PubMed

Fukuda, A; Takemoto, M; Saito, T; Fujibayashi, S; Neo, M; Yamaguchi, S; Kizuki, T; Matsushita, T; Niinomi, M; Kokubo, T; Nakamura, T

2011-03-01

Ti15Zr4Nb4Ta and Ti29Nb13Ta4.6Zr, which do not contain the potentially cytotoxic elements V and Al, represent a new generation of alloys with improved corrosion resistance, mechanical properties, and cytocompatibility. Recently it has become possible for the apatite forming ability of these alloys to be ascertained by treatment with alkali, CaCl2, heat, and water (ACaHW). In order to confirm the actual in vivo bioactivity of commercially pure titanium (cp-Ti) and these alloys after subjecting them to ACaHW treatment at different temperatures, the bone bonding strength of implants made from these materials was evaluated. The failure load between implant and bone was measured for treated and untreated plates at 4, 8, 16, and 26 weeks after implantation in rabbit tibia. The untreated implants showed almost no bonding, whereas all treated implants showed successful bonding by 4 weeks, and the failure load subsequently increased with time. This suggests that a simple and economical ACaHW treatment could successfully be used to impart bone bonding bioactivity to Ti metal and Ti-Zr-Nb-Ta alloys in vivo. In particular, implants heat treated at 700 °C exhibited significantly greater bone bonding strength, as well as augmented in vitro apatite formation, in comparison with those treated at 600 °C. Thus, with this improved bioactive treatment process these advantageous Ti-Zr-Nb-Ta alloys can serve as useful candidates for orthopedic devices. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Simultaneous multi-wavelength ultraviolet excited single-phase white light emitting phosphor Ba1-x(Zr,Ti)Si3O9:xEu

NASA Astrophysics Data System (ADS)

Zhou, Zhenzhen; Liu, Guanghui; Ni, Jia; Liu, Wanlu; Liu, Qian

2018-05-01

A kind of novel compound Ba1-x(Zr,Ti)Si3O9:xEu simultaneously activated by different-valence Eu2+ and Eu3+ ions has been successfully synthesized. The existence of Ti4+-O2- charge transfer (CT) transitions in Ba1-xZrSi3O9:xEu is proved by the photoluminescence spectra and first principle calculations, and the Ti4+ ions come from the impurities in commercial ZrO2 raw materials. Under the excitation of multi-wavelength ultraviolet radiation (λEX = 392, 260, 180 nm), Ba1-xZrSi3O9:xEu (x = 0.15) can directly emit nearly white light. The coexistence of multiple luminescent centers and the energy transfer among Zr4+-O2- CT state, Ti4+-O2- CT state, Eu2+ and Eu3+ ions play important roles in the white light emission. Ba1-xZrSi3O9:xEu (x = 0.15) has good thermal stability, in particular, the intensity of emission spectrum (λEX = 392 nm) at 150 °C is ∼96% of that at room temperature. In general, the multi-wavelength ultraviolet-excited single-phase white light emitting phosphor Ba1-x(Zr,Ti)Si3O9:xEu possesses a promise for applications in white light emitting diodes (WLEDs), agriculture, medicine and other photonic fields.

Microstructure characterization and phase transformation kinetic study of ball-milled m-ZrO 2-30 mol% a-TiO 2 mixture by Rietveld method

NASA Astrophysics Data System (ADS)

Pradhan, S. K.; Dutta, H.

2005-05-01

High-energy ball milling of monoclinic ZrO 2-30 mol% anatase TiO 2 mixture at different durations results in the formation of m-ZrO 2-a-TiO 2 solid solution from which the nucleation of nanocrystalline cubic (c) ZrO 2 polymorphic phase sets in. Post-annealing of 12 h ball-milled sample at different elevated temperatures for 1 h results in almost complete formation of c-ZrO 2 phase. Microstructure of the unmilled, all the ball milled and annealed samples has been characterized by Rietveld's X-ray powder structure refinement method. Particle size, rms lattice strain, change in lattice parameters and phase content of individual phases have been estimated from Rietveld analysis, and are utilized to interpret the results. In course of milling, (1 1 1) of cubic lattice became parallel to ( 1bar 1 1) plane of monoclinic lattice due to the orientation effect and cubic phase may have been formed on the (0 0 1) of the m-ZrO 2-a-TiO 2 solid solution lattice. A comparative study of microstructure and phase transformation kinetics of ZrO 2-10, 20 and 30 mol% a-TiO 2 ball-milled and post-annealed samples reveals that rate of phase transformation m→c-ZrO 2 increases with increasing a-TiO 2 concentration and ∼30 mol% of nanocrystalline c-ZrO 2 phase can be obtained within 4 h of milling time in the presence of 30 mol% of a-TiO 2. The post-annealing treatment at 773, 873 and 973 K for 1 h duration each reveals that rate of c-ZrO 2 formation with increasing temperature is retarded with increasing a-TiO 2 concentration but the amount of c-ZrO 2 becomes almost equal (∼95 mol%) at 973 K. It suggests that almost fully stabilized nanocrystalline c-ZrO 2 can be formed by adding a tetravalent solute to m-ZrO 2.

Microstructural and Mechanical Characterization of Ti-12Mo-6Zr Biomaterials Fabricated by Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Daoush, Walid Mohamed Rashad Mohamed; Park, Hee Sup; Inam, Fawad; Lim, Byung Kyu; Hong, Soon Hyung

2015-03-01

Ti-12Mo-6Zr/Al2O3 (titanium biomaterial) was prepared by a powder metallurgy route using Spark Plasma Sintering (SPS). Ti, Mo, and Zr powders were mixed by wet milling with different content of alumina nanoparticles (up to 5 wt pct) as an oxide dispersion strengthening phase. Composite powder mixtures were SPSed at 1273 K (1000 °C) followed by heat treatment and quenching. Composite powders, sintered materials, and heat-treated materials were examined using optical and high-resolution electronic microscopy (scanning and transmission) and X-ray diffraction to characterize particle size, surface morphology, and phase identifications for each composition. All sintered materials were evaluated by measuring density, Vickers hardness, and tensile properties. Fully dense sintered materials were produced by SPS and mechanical properties were found to be improved by subsequent heat treatment. The tensile properties as well as the hardness were increased by increasing the content of Al2O3 nanoparticles in the Ti-12Mo-6Zr matrix.

Lattice Thermal Conductivity of Ultra High Temperature Ceramics ZrB2 and HfB2 from Atomistic Simulations

NASA Technical Reports Server (NTRS)

Lawson, John W.; Murray, Daw S.; Bauschlicher, Charles W., Jr.

2011-01-01

Atomistic Green-Kubo simulations are performed to evaluate the lattice thermal conductivity for single crystals of the ultra high temperature ceramics ZrB2 and HfB2 for a range of temperatures. Recently developed interatomic potentials are used for these simulations. Heat current correlation functions show rapid oscillations which can be identified with mixed metal-Boron optical phonon modes. Agreement with available experimental data is good.

Comparisons of immersion and electrochemical properties of highly biocompatible Ti-15Zr-4Nb-4Ta alloy and other implantable metals for orthopedic implants

NASA Astrophysics Data System (ADS)

Okazaki, Yoshimitsu; Nagata, Hiroyuki

2012-12-01

Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti-15Zr-4Nb-4Ta alloy. The thickness and electrical resistance (Rp) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti-15Zr-4Nb-4Ta than the Ti-6Al-4V alloy. The potential (E10) indicating a current density of 10 μA cm-2 estimated from the anodic polarization curve was significantly higher for the Ti-15Zr-4Nb-4Ta than the Ti-6Al-4V alloy and other metals. Moreover, the oxide film (4-7 nm thickness) formed on the Ti-15Zr-4Nb-4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO2 with small amounts of ZrO2, Nb2O5 and Ta2O5 that made the film electrochemically stable. The Rp of Ti-15Zr-4Nb-4Ta was higher than that of Ti-6Al-4V, i.e. 0.9 Ω cm2 in 0.9% NaCl and 1.3 Ω cm2 in Eagle's medium. This Rp was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti-15Zr-4Nb-4Ta is a potential implant material for long-term clinical use. Moreover, E10 and Rp were found to be useful parameters for assessing biological safety.

Effect of Cr, Ti, V, and Zr Micro-additions on Microstructure and Mechanical Properties of the Al-Si-Cu-Mg Cast Alloy

NASA Astrophysics Data System (ADS)

Shaha, S. K.; Czerwinski, F.; Kasprzak, W.; Friedman, J.; Chen, D. L.

2016-05-01

Uniaxial static and cyclic tests were used to assess the role of Cr, Ti, V, and Zr additions on properties of the Al-7Si-1Cu-0.5Mg (wt pct) alloy in as-cast and T6 heat-treated conditions. The microstructure of the as-cast alloy consisted of α-Al, eutectic Si, and Cu-, Mg-, and Fe-rich phases Al2.1Cu, Al8.5Si2.4Cu, Al5.2CuMg4Si5.1, and Al14Si7.1FeMg3.3. In addition, the micro-sized Cr/Zr/Ti/V-rich phases Al10.7SiTi3.6, Al6.7Si1.2TiZr1.8, Al21.4Si3.4Ti4.7VZr1.8, Al18.5Si7.3Cr2.6V, Al7.9Si8.5Cr6.8V4.1Ti, Al6.3Si23.2FeCr9.2V1.6Ti1.3, Al92.2Si16.7Fe7.6Cr8.3V1.8, and Al8.2Si30.1Fe1.6Cr18.8V3.3Ti2.9Zr were present. During solution treatment, Cu-rich phases were completely dissolved, while the eutectic silicon, Fe-, and Cr/Zr/Ti/V-rich intermetallics experienced only partial dissolution. Micro-additions of Cr, Zr, Ti, and V positively affected the alloy strength. The modified alloy in the T6 temper during uniaxial tensile tests exhibited yield strength of 289 MPa and ultimate tensile strength of 342 MPa, being significantly higher than that for the Al-Si-Cu-Mg base. Besides, the cyclic yield stress of the modified alloy in the T6 state increased by 23 pct over that of the base alloy. The fatigue life of the modified alloy was substantially longer than that of the base alloy tested using the same parameters. The role of Cr, Ti, V, and Zr containing phases in controlling the alloy fracture during static and cyclic loading is discussed.

Low-cost Fe--Ni--Cr alloys for high temperature valve applications

DOEpatents

Muralidharan, Govindarajan

2017-03-28

An Fe--Ni--Cr alloy is composed essentially of, in terms of weight percent: 1 to 3.5 Al, up to 2 Co, 15 to 19.5 Cr, up to 2 Cu, 23 to 40 Fe, up to 0.3 Hf, up to 4 Mn, 0.15 to 2 Mo, up to 0.15 Si, up to 1.05 Ta, 2.8 to 4.3 Ti, up to 0.5 W, up to 0.06 Zr, 0.02 to 0.15 C, 0.0001 to 0.007 N, balance Ni, wherein, in terms of atomic percent: 6.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.10, 0.33.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.065, 4.ltoreq.(Fe+Cr)/(Al+Ti+Zr+Hf+Ta).ltoreq.10, the alloy being essentially free of Nb and V.

Obtaining and Mechanical Properties of Ti-Mo-Zr-Ta Alloys

NASA Astrophysics Data System (ADS)

Bălţatu, M. S.; Vizureanu, P.; Geantă, V.; Nejneru, C.; Țugui, C. A.; Focşăneanu, S. C.

2017-06-01

Ti-based alloys are successfully used in the area of orthopedic biomaterials for their enhanced biocompatibility, good corrosion and mechanical properties. The most suitable metals as an alloying element for orthopedic biomaterials are zirconium, molybdenum and tantalum because are non toxic and have good properties. The paper purpose development of two alloys of Ti-Mo-Zr-Ta (TMZT) prepared by arc-melting with several mechanical properties determined by microindentation. The mechanical properties analyzed was Vickers hardness and dynamic elasticity modulus. The investigated alloys presents a low Young’s modulus, an important condition of biomaterials for preventing stress shielding phenomenon.

Ti-rich komatiites from northern Norway

NASA Astrophysics Data System (ADS)

Barnes, Sarah-Jane; Often, Morten

1990-06-01

Komatiites of the Karasjok Greenstone Belt, northern Norway, show two unusual features: they have certain compositional differences compared with other komatiites, and they are largely volcaniclastic in origin. Their geological setting suggests that the komatiites were crupted into shallow water, thus permitting phreatomagmatic eruption, in a small ocean basin that opened in the Baltic Shield. The major oxides (except for TiO2), the trace elements Y, Sc, V, heavy rare earth elements (HREE), Cr, Co, Ni and the platinum group elements (PGE) cover similar ranges to those observed in other komatiites, but TiO2, Sm, Zr and Hf (Ti-associated elements, TAE) are enriched compared with abundances commonly reported for komatiites. Thus, the Karasjok komatiites have interelement ratios 2 to 3 times greater than chondritic between the TAE and the HREE, PGE, Sc, V, Y, Al (HRE-associated elements, HAE). The light rare earth elements (LREE), Ta and Th are enriched in some samples relative to Ti, Sm, Zr, and Hf, but are depleted in others. One group of rocks that is similar to the Karasjok komatiites both in terms of geological setting and geochemistry is the Baffin Bay picrites. The reason for the high concentrations of TAE in the Karasjok komatiites could be that they formed at lower degrees of partial melting than most komatiites. The greater-than-chondritic TAE/HAE ratios indicate that garnet was a residual phase during their formation, requiring that the melt formed at a pressure greater than 40 kb. A model involving decompression melting of a mantle plume rising in a rifting environment, can explain the main features of the Karasjok komatiites.

Thermal Conductivity and Stability of HfO2-Y2O3 and La2Zr2O7 Evaluated for 1650 Deg C Thermal/Environmental Barrier Coating Applications

NASA Technical Reports Server (NTRS)

Zhu, Dong-Ming; Bansal, Narottam P.; Miller, Robert A.

2003-01-01

HfO2-Y2O3 and La2Zr2O7 are candidate thermal and environmental barrier coating (T/EBC) materials for gas turbine ceramic matrix composite (CMC) combustor applications because of their relatively low thermal conductivity and high temperature capability. In this paper, thermal conductivity and high temperature stability of hot-pressed and plasma sprayed specimens with representative partially-stabilized and fully-cubic HfO2-Y2O3 compositions and La2Zr2O7 were evaluated at temperatures up to 1700 C using a steady-state laser heat-flux technique. Sintering behavior of the plasmasprayed coatings was determined by monitoring the thermal conductivity increases during a 20-hour test period at various temperatures. Durability and failure mechanisms of the HfO2-Y2O3 and La2Zr2O7 coatings on mullite/SiC hexoloy or SiC/SiC CMC substrates were investigated at 1650 C under thermal gradient cyclic conditions. Coating design and testing issues for the 1650 C thermal/environmental barrier coating applications are also discussed.

Effect of structural evolution on mechanical properties of ZrO2 coated Ti-6Al-7Nb-biomedical application

NASA Astrophysics Data System (ADS)

Zalnezhad, E.

2016-05-01

Zirconia (ZrO2) nanotube arrays were fabricated by anodizing pure zirconium (Zr) coated Ti-6Al-7Nb in fluoride/glycerol electrolyte at a constant potential of 60 V for different times. Zr was deposited atop Ti-6Al-7Nb via a physical vapor deposition magnetron sputtering (PVDMS) technique. Structural investigations of coating were performed utilizing X-ray diffraction (XRD) analysis. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to characterize the morphology and microstructure of coatings. Unannealed ZrO2 nanotube arrays were amorphous. Monoclinic and tetragonal ZrO2 appeared when the coated substrates were heat treated at 450 °C and 650 °C, while monoclinic ZrO2 was found at 850 °C and 900 °C. Mechanical properties, including nanohardness and modulus of elasticity, were evaluated at different annealing temperatures using a nanoindentation test. The nanoindentation results show that the nanohardness and modulus of elasticity for Ti-6AL-7Nb increased by annealing ZrO2 coated substrate at 450 °C. The nanohardness and modulus of elasticity for coated substrate decreased with annealing temperatures of 650, 850, and 900 °C. At an annealing temperature of 900 °C, cracks in the ZrO2 thin film coating occurred. The highest nanohardness and elastic modulus values of 6.34 and 218 GPa were achieved at an annealing temperature of 450 °C.

Improving High-Temperature Tensile and Low-Cycle Fatigue Behavior of Al-Si-Cu-Mg Alloys Through Micro-additions of Ti, V, and Zr

NASA Astrophysics Data System (ADS)

Shaha, S. K.; Czerwinski, F.; Kasprzak, W.; Friedman, J.; Chen, D. L.

2015-07-01

High-temperature tensile and low-cycle fatigue tests were performed to assess the influence of micro-additions of Ti, V, and Zr on the improvement of the Al-7Si-1Cu-0.5Mg (wt pct) alloy in the as-cast condition. Addition of transition metals led to modification of microstructure where in addition to conventional phases present in the Al-7Si-1Cu-0.5Mg base, new thermally stable micro-sized Zr-Ti-V-rich phases Al21.4Si4.1Ti3.5VZr3.9, Al6.7Si1.2TiZr1.8, Al2.8Si3.8V1.6Zr, and Al5.1Si35.4Ti1.6Zr5.7Fe were formed. The tensile tests showed that with increasing test temperature from 298 K to 673 K (25 °C to 400 °C), the yield stress and tensile strength of the present studied alloy decreased from 161 to 84 MPa and from 261 to 102 MPa, respectively. Also, the studied alloy exhibited 18, 12, and 5 pct higher tensile strength than the alloy A356, 354 and existing Al-Si-Cu-Mg alloy modified with additions of Zr, Ti, and Ni, respectively. The fatigue life of the studied alloy was substantially longer than those of the reference alloys A356 and the same Al-7Si-1Cu-0.5Mg base with minor additions of V, Zr, and Ti in the T6 condition. Fractographic analysis after tensile tests revealed that at the lower temperature up to 473 K (200 °C), the cleavage-type brittle fracture for the precipitates and ductile fracture for the matrix were dominant while at higher temperature fully ductile-type fracture with debonding and pull-out of cracked particles was identified. It is believed that the intermetallic precipitates containing Zr, Ti, and V improve the alloy performance at increased temperatures.

Universal Correlation between Flatband Voltage and Electron Mobility in TiN/HfSiON Devices with MgO or La2O3 Incorporation and Stack Variation

NASA Astrophysics Data System (ADS)

Mise, Nobuyuki; Kadoshima, Masaru; Morooka, Tetsu; Eimori, Takahisa; Nara, Yasuo; Ohji, Yuzuru

2008-10-01

We investigated the controversial effective workfunction and electron mobility of TiN/HfSiON devices by intentionally adding MgO or La2O3 into HfSiON and by changing the material on TiN or the TiN thickness. As a result, we found a close relationship between the electron mobility at low effective field and the flatband voltage. This relationship is explained on the basis of the fixed charge in HfSiON and its neutralization. The intrinsic workfunction of TiN/HfSiON without charge is determined to be 4.3 eV from the flatband voltage when the electron mobility at low effective field is the highest.

Examination of Multiphase (Zr,Ti)(V,Cr,Mn,Ni)2 Ni-MH Electrode Alloys: Part II. Solid-State Transformation of the Interdendritic B2 Phase

NASA Astrophysics Data System (ADS)

Bendersky, L. A.; Wang, K.; Boettinger, W. J.; Newbury, D. E.; Young, K.; Chao, B.

2010-08-01

Solidification microstructure of multicomponent (Zr,Ti)-Ni-(V,Cr,Mn,Co) alloys intended for use as negative electrodes in Ni-metal hydride (Ni-MH) batteries was studied in Part I of this series of articles. Part II of the series examines the complex internal structure of the interdendritic grains formed by solid-state transformation and believed to play an important role in the electrochemical charge/discharge characteristics of the overall alloy composition. By studying one alloy, Zr21Ti12.5V10Cr5.5Mn5.1Co5.0Ni40.2Al0.5Sn0.3, it is shown that the interdendritic grains solidify as a B2 (Ti,Zr)44(Ni,TM)56 phase, and then undergo transformation to Zr7Ni10-type, Zr9Ni11-type, and martensitic phases. The transformations obey orientation relationships between the high-temperature B2 phase and the low-temperature Zr-Ni-type intermetallics, and consequently lead to a multivariant structure. The major orientation relationship for the orthorhombic Zr7Ni10 type is [011]Zr7Ni10//[001]B2; (100)Zr7Ni10//(100)B2. The orientation relationship for the tetragonal Zr9Ni11 type is [001]Zr9Ni11//[001]B2; (130)Zr9Ni11//(100)B2. Binary Ni-Zr and ternary Ti-Ni-Zr phase diagrams were used to rationalize the formation of the observed domain structure.

AlGaN/GaN High Electron Mobility Transistor Grown and Fabricated on ZrTi Metallic Alloy Buffer Layers

DOE PAGES

Ren, Fan; Pearton, Stephen J.; Ahn, Shihyun; ...

2017-09-26

AlGaN/GaN high electron mobility transistors (HEMTs) were demonstrated for structures grown on ZrTi metallic alloy buffer layers, which provided lattice matching of the in-plane lattice parameter (“a-parameter”) to hexagonal GaN. The quality of the GaN buffer layer and HEMT structure were confirmed with X-ray 2θ and rocking scans as well as cross-section transmission electron microscopy (TEM) images. The X-ray 2θ scans showed full widths at half maximum (FWHM) of 0.06°, 0.05° and 0.08° for ZrTi alloy, GaN buffer layer, and the entire HEMT structure, respectively. TEM of the lower section of the HEMT structure containing the GaN buffer layer andmore » the AlN/ZrTi/AlN stack on the Si substrate showed that it was important to grow AlN on the top of ZrTi prior to growing the GaN buffer layer. Finally, the estimated threading dislocation (TD) density in the GaN channel layer of the HEMT structure was in the 10 8 cm -2 range.« less

Oxidation Resistance, Electrical and Thermal Conductivity, and Spectral Emittance of Fully Dense HfB2 and ZrB2 with SiC, TaSi2, and LaB6 Additives

DTIC Science & Technology

2012-01-26

Resistance , Electrical and Thermal Conductivity, and Spectral Emittance of Fully Dense HfB2 and ZrB2 "With SiC, TaSi2, and LaB6 Additives Sb. GRANT NUMBER... RESISTANCE , ELECTRICAL AND THERMAL CONDUCTIVITY, AND SPECTRAL EMITTANCE OF FULLY DENSE HfB2 AND ZrB2 WITH SiC, TaSi2, AND LaB6 ADDITIVES Air Force Office...thickened regions with dry 220 grit SiC sandpaper so that a low- resistance electrical connection could be achieved. A handheld multimeter was used to measure

Design of refractory high-entropy alloys

DOE PAGES

Gao, M. C.; Carney, C. S.; Dogan, O. N.; ...

2015-09-15

Here, this report presents a design methodology for refractory high-entropy alloys with a body-centered cubic (bcc) structure using select empirical parameters (i.e., enthalpy of mixing, atomic size difference, Ω-parameter, and electronegativity difference) and CALPHAD approach. Sixteen alloys in equimolar compositions ranging from quinary to ennead systems were designed with experimental verification studies performed on two alloys using x-ray diffraction, energy-dispersive spectroscopy, and scanning electron microscopy. Two bcc phases were identified in the as-cast HfMoNbTaTiVZr, whereas multiple phases formed in the as-cast HfMoNbTaTiVWZr. Observed elemental segregation in the alloys qualitatively agrees with CALPHAD prediction. Comparisons of the thermodynamic mixing properties formore » liquid and bcc phases using the Miedema model and CALPHAD are presented. This study demonstrates that CALPHAD is more effective in predicting HEA formation than empirical parameters, and new single bcc HEAs are suggested: HfMoNbTiZr, HfMoTaTiZr, NbTaTiVZr, HfMoNbTaTiZr, HfMoTaTiVZr, and MoNbTaTiVZr.« less

Effect of Ce/Zr molar ratio on the performance of Cu–Ce{sub x}–Zr{sub 1−x}/TiO{sub 2} catalyst for selective catalytic reduction of NO{sub x} with NH{sub 3} in diesel exhaust

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

Sun, Xiaoliang; Gong, Cairong, E-mail: gcr@tju.edu.cn; Lv, Gang

2014-12-15

Graphical abstract: The Cu–Ce{sub 0.25}–Zr{sub 0.75}/TiO{sub 2} catalyst exhibited excellent SCR activity at 165–450 °C within the range of exhaust temperatures of diesel engines. - Highlights: • Cu–Ce{sub x}–Zr{sub 1−x}/TiO{sub 2} catalysts were prepared by a wet impregnation method. • The property for NH{sub 3}-selective catalytic reduction of NO{sub x} were investigated. • The Ce/Zr molar ratio had effects on the performance of Cu–Ce–Zr/TiO{sub 2} catalysts. • The Cu–Ce{sub 0.25}–Zr{sub 0.75}/TiO{sub 2} sample exhibited 100% NO{sub x} conversion between 165 °C and 450 °C. • The factors that govern the activity enhancement were extensively investigated. - Abstract: Copper–cerium–zirconium catalysts loadedmore » on TiO{sub 2} prepared by a wet impregnation method were investigated for NH{sub 3}-selective catalytic reduction of NO{sub x}, aiming to study the effects of the Ce/Zr molar ratio on the performance of Cu–Ce–Zr/TiO{sub 2} catalysts. The Cu–Ce{sub 0.25}–Zr{sub 0.75}/TiO{sub 2} sample exhibited nearly 100% NO{sub x} conversion over a wide temperature range (165–450 °C), which is strikingly superior to that of Cu/TiO{sub 2} (210–389 °C) within the range of exhaust temperatures of diesel engines. The factors that govern the activity enhancement were extensively investigated by using a series of characterization techniques, namely X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction by hydrogen (H{sub 2}-TPR). The results showed that the addition of zirconium and/or cerium refined the copper dispersion, prevented copper crystallization and partially incorporated the copper ions into the zirconia (ceira) lattice, which led to enhance the redox abilities of Cu–Ce–Zr/TiO{sub 2} catalysts.« less

Second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass.

PubMed

Cao, Q P; Li, J F; Zhang, P N; Horsewell, A; Jiang, J Z; Zhou, Y H

2007-06-20

The second amorphous-to-crystalline phase transformation in Cu(60)Ti(20)Zr(20) bulk metallic glass was investigated by differential scanning calorimetry and x-ray diffractometry. The difference of the Gibbs free energies between the amorphous phase and the crystalline products during the transformation is estimated to be about 2.46 kJ mol(-1) at 753 K, much smaller than the 61 kJ mol(-1) obtained assuming that it is a polymorphic transformation. It was revealed that the phase transformation occurs through a eutectic crystallization of Cu(51)Zr(14) and Cu(2)TiZr, having an effective activation energy of the order of 400 kJ mol(-1). The average Avrami exponent n is about 2.0, indicating that the crystallization is diffusion controlled.

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.

Porous TiO2-ZrO2 thin film formed by electrochemical technique to improve the biocompatibility of titanium alloy in physiological environment

NASA Astrophysics Data System (ADS)

Benea, L.; Dănăilă, E.; Ponthiaux, P.

2017-02-01

Porous Ti and Ti alloys have received increasing research interest for bone tissue engineering, especially for dental and orthopaedic implants because they provide cell ingrowths and vascularization, improving of adhesion and osseointegration. The tribocorrosion process is encountered in orthopaedic and dentistry applications, since it is known that the implants are often exposed to simultaneous chemical/electrochemical and mechanical stresses. The purpose of this study was to carry out a systematic investigation of the tribo-electrochemical performance of porous TiO2-ZrO2 thin film formed by anodization of Ti-10Zr alloy surface in an artificial saliva solution and to compare the resulted performance with that of the untreated Ti-10Zr alloy surface in order to be applied for biomedical use. The in situ electrochemical technique used for investigation of tribo-electrochemical degradation was the open circuit potential (OCP) measurement performed before, during and after sliding tests. The results presented herein show that controlled anodic oxidation method can significantly improve the tribocorrosion and friction performances of Ti-10Zr alloy surface intended for biomedical applications.

Compressive Strength Evaluation in Brazed ZrO2/Ti6Al4V Joints Using Finite Element Analysis

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Kee, Se Ho; Jung, Flora; Heo, Yongku; Jung, Jae Pil

2016-05-01

This study aims to synthesize and evaluate the compressive strength of the ZrO2/Ti-6Al-4V joint brazed using an active metal filler Ag-Cu-Sn-Ti, and its application to dental implants assuring its reliability to resist the compressive failure in the actual oral environment. The brazing was performed at a temperature of 750 °C for 30 min in a vacuum furnace under 5 × 10-6 Torr atmosphere. The microstructure of the brazed joint showed the presence of an Ag-rich matrix and a Cu-rich phase, and Cu-Ti intermetallic compounds were observed along the Ti-6Al-4V bonded interface. The compressive strength of the brazed ZrO2/Ti-6Al-4V joint was measured by EN ISO 14801 standard test method. The measured compressive strength of the joint was ~1477 MPa—a value almost five times that of existing dental cements. Finite element analysis also confirmed the high von Mises stress values. The compressive strains in the samples were found concentrated near the Ti-6Al-4V position, matching with the position of the real fractured sample. These results suggest extremely significant compressive strength in ZrO2/Ti-6Al-4V joints using the Ag-Cu-Sn-Ti filler. It is believed that a highly reliable dental implant can be processed and designed using the results of this study.

Fatigue behaviour of boron free and boron containing heat treated Ti-13Zr-13Nb alloy for biomedical applications

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

Majumdar, P., E-mail: m.pallab@gmail.com; Singh, S.B.; Chakraborty, M.

2010-12-15

Fatigue behaviour of heat treated Ti-13Zr-13Nb (TZN) and Ti-13Zr-13Nb-0.5B (TZNB) alloys for biomedical implants has been investigated by rotating bending test. It was found that fatigue strength of TZN and TZNB alloys is comparable with that of conventionally used biomedical titanium alloys. Addition of boron to TZN alloy deteriorates fatigue strength. - Research Highlights: {yields}The microstructure of the aged TZN consists of {alpha} phase in {beta} matrix. {yields}Addition of boron to TZN leads to the formation of dispersed acicular TiB. {yields}Presence of TiB deteriorates the fatigue strength of TZN alloy. {yields}Fatigue strength of aged TZN/TZNB alloys is comparable with biomedicalmore » Ti-alloys.« less

The Mechanical Properties and In Vitro Biocompatibility of PM-Fabricated Ti-28Nb-35.4Zr Alloy for Orthopedic Implant Applications

PubMed Central

Xu, Wei; Li, Ming; Wen, Cuie; Lv, Shaomin; Liu, Chengcheng; Lu, Xin

2018-01-01

A biocompatible Ti-28Nb-35.4Zr alloy used as bone implant was fabricated through the powder metallurgy process. The effects of mechanical milling and sintering temperatures on the microstructure and mechanical properties were investigated systematically, before in vitro biocompatibility of full dense Ti-28Nb-35.4Zr alloy was evaluated by cytotoxicity tests. The results show that the mechanical milling and sintering temperatures have significantly effects on the density and mechanical properties of the alloys. The relative density of the alloy fabricated by the atomized powders at 1500 °C is only 83 ± 1.8%, while the relative density of the alloy fabricated by the ball-milled powders can rapidly reach at 96.4 ± 1.3% at 1500 °C. When the temperature was increased to 1550 °C, the alloy fabricated by ball-milled powders achieve full density (relative density is 98.1 ± 1.2%). The PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C can achieve a wide range of mechanical properties, with a compressive yield strength of 1058 ± 35.1 MPa, elastic modulus of 50.8 ± 3.9 GPa, and hardness of 65.8 ± 1.5 HRA. The in vitro cytotoxicity test suggests that the PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C has no adverse effects on MC3T3-E1 cells with cytotoxicity ranking of 0 grade, which is nearly close to ELI Ti-6Al-4V or CP Ti. These properties and the net-shape manufacturability makes PM-fabricated Ti-28Nb-35.4Zr alloy a low-cost, highly-biocompatible, Ti-based biomedical alloy. PMID:29601517

The Mechanical Properties and In Vitro Biocompatibility of PM-Fabricated Ti-28Nb-35.4Zr Alloy for Orthopedic Implant Applications.

PubMed

Xu, Wei; Li, Ming; Wen, Cuie; Lv, Shaomin; Liu, Chengcheng; Lu, Xin; Qu, Xuanhui

2018-03-30

A biocompatible Ti-28Nb-35.4Zr alloy used as bone implant was fabricated through the powder metallurgy process. The effects of mechanical milling and sintering temperatures on the microstructure and mechanical properties were investigated systematically, before in vitro biocompatibility of full dense Ti-28Nb-35.4Zr alloy was evaluated by cytotoxicity tests. The results show that the mechanical milling and sintering temperatures have significantly effects on the density and mechanical properties of the alloys. The relative density of the alloy fabricated by the atomized powders at 1500 °C is only 83 ± 1.8%, while the relative density of the alloy fabricated by the ball-milled powders can rapidly reach at 96.4 ± 1.3% at 1500 °C. When the temperature was increased to 1550 °C, the alloy fabricated by ball-milled powders achieve full density (relative density is 98.1 ± 1.2%). The PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C can achieve a wide range of mechanical properties, with a compressive yield strength of 1058 ± 35.1 MPa, elastic modulus of 50.8 ± 3.9 GPa, and hardness of 65.8 ± 1.5 HRA. The in vitro cytotoxicity test suggests that the PM-fabricated Ti-28Nb-35.4Zr alloy by ball-milled powders at 1550 °C has no adverse effects on MC3T3-E1 cells with cytotoxicity ranking of 0 grade, which is nearly close to ELI Ti-6Al-4V or CP Ti. These properties and the net-shape manufacturability makes PM-fabricated Ti-28Nb-35.4Zr alloy a low-cost, highly-biocompatible, Ti-based biomedical alloy.

Elevated-Temperature Deformation Properties of a HfC Modified Ti-48Al-2Mn-2Nb Matrix Particulate Composite

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.; Farmer, S. C.; Bors, D. A.; Ray, R.; Lee, D. S.

1994-01-01

Rapid solidification techniques in combination with HIPing have been used to produce Ti-48Al-2Mn-2Nb and a Ti-48Al-2Mn-2Nb+15 wt% HfC composite. While the composite does contain several second phases within the gamma + alpha(sub 2) matrix, none was identified to be HfC. The elevated-temperature properties were determined by constant velocity compression and constant load tensile testing in air between 1000 and 1173 K. Such testing indicated that the elevated temperature strengths of the HfC-modified aluminide was superior to those of the unreinforced matrix with the best 1100 K temperature slow strain rate properties for both materials being achieved after high-temperature annealing prior to testing. Examination of the microstructures after deformation in combination with the measured stress exponents and activation energies suggest that creep resistance of the HfC-modified form is due to solid-solution strengthening from carbon and hafnium rather than the presence of second phases.

Impact of nano and bulk ZrO2, TiO2 particles on soil nutrient contents and PGPR.

PubMed

Karunakaran, Gopalu; Suriyaprabha, Rangaraj; Manivasakan, Palanisamy; Yuvakkumar, Rathinam; Rajendran, Venkatachalam; Kannan, Narayanasamy

2013-01-01

Currently, nanometal oxides are used extensively in different industries such as medicine, cosmetics and food. The increased consumption of nanoparticles (NPs) leads the necessity to understand the fate of the nanoparticles in the environment. The present study focused on the ecotoxicological behaviour of bulk and nano ZrO2 (Zirconia) and TiO2 (Titania) particles on PGPR (plant growth promoting rhizobacteria), soil and its nutrient contents. The microbial susceptibility study showed that nano TiO2 had 13 +/- 0.9 mm (B. megaterium), 15 +/- 0.2 mm (P. fluorescens), 16 +/- 0.2 mm (A. vinelandii) and 12 +/- 0.3 mm (B. brevis) zones of inhibition. However, nano and bulk ZrO2 particles were non-toxic to PGPR. In addition, it was found that toxicity varied depends on the medium of reaction. The soil study showed that nano TiO2 was found to be highly toxic, whereas bulk TiO2 was less toxic towards soil bacterial populations at 1000 mg L(-1). In contrast, nano and bulk ZrO2 were found to be inert at 1000 mg L(-1). The observed zeta potential and hydrophobicity of TiO2 particles causes more toxic than ZrO2 in parallel with particle size. However, nano TiO2 decreases the microbial population as well as nutrient level of the soil but not zirconia. Our finding shows that the mechanism of toxicity depends on size, hydrophobic potential and zeta potential of the metal oxide particles. Thus, it is necessary to take safety measures during the disposal and use of such toxic nanoparticles in the soil to prevent their hazardous effects.

Histomorphometric and histologic evaluation of titanium-zirconium (aTiZr) implants with anodized surfaces.

PubMed

Sharma, Ajay; McQuillan, A James; Shibata, Yo; Sharma, Lavanya A; Waddell, John Neil; Duncan, Warwick John

2016-05-01

The choice of implant surface has a significant influence on osseointegration. Modification of TiZr surface by anodization is reported to have the potential to modulate the osteoblast cell behaviour favouring more rapid bone formation. The aim of this study is to investigate the effect of anodizing the surface of TiZr discs with respect to osseointegration after four weeks implantation in sheep femurs. Titanium (Ti) and TiZr discs were anodized in an electrolyte containing DL-α-glycerophosphate and calcium acetate at 300 V. The surface characteristics were analyzed by scanning electron microscopy, electron dispersive spectroscopy, atomic force microscopy and goniometry. Forty implant discs with thickness of 1.5 and 10 mm diameter (10 of each-titanium, titanium-zirconium, anodized titanium and anodized titanium-zirconium) were placed in the femoral condyles of 10 sheep. Histomorphometric and histologic analysis were performed 4 weeks after implantation. The anodized implants displayed hydrophilic, porous, nano-to-micrometer scale roughened surfaces. Energy dispersive spectroscopy analysis revealed calcium and phosphorous incorporation into the surface of both titanium and titanium-zirconium after anodization. Histologically there was new bone apposition on all implanted discs, slightly more pronounced on anodised discs. The percentage bone-to-implant contact measurements of anodized implants were higher than machined/unmodified implants but there was no significant difference between the two groups with anodized surfaces (P > 0.05, n = 10). The present histomorphometric and histological findings confirm that surface modification of titanium-zirconium by anodization is similar to anodised titanium enhances early osseointegration compared to machined implant surfaces.

Lu-Hf constraints on the evolution of lunar basalts

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

Fujimaki, H.; Tatsumoto, M.

1984-02-15

Very low Ti basalts andd green glass samples from the moon show high Lu/Hf ratios and low Hf concentrations. Low-Ti lunar basalts show high and variable Lu/Hf ratios and higher Hf concentrations, whereas high-Ti lunar basalts show low Lu/Hf ratios and high Hf concentrations. KREEP basalts have constant Lu/Hf ratios and high but variable Hf concentrations. Using the Lu-Hf behavior as a constraint, we propose a model for the mare basalts evolution. This constraint requires extensive crystallization of the primary lunar magma ocean prior to formation of the lunar mare basalt sources and the KREEP basalts. Mare basalts are producedmore » by the melting of the cumulate rocks, and KREEP basalts represent the residual liquid of the magma ocean.« less

Promising Ta-Ti-Zr-Si metallic glass coating without cytotoxic elements for bio-implant applications

NASA Astrophysics Data System (ADS)

Lai, J. J.; Lin, Y. S.; Chang, C. H.; Wei, T. Y.; Huang, J. C.; Liao, Z. X.; Lin, C. H.; Chen, C. H.

2018-01-01

Tantalum (Ta) is considered as one of the most promising metal due to its high corrosion resistance, excellent biocompatibility and cell adhesion/in-growth capabilities. Although there are some researches exploring the biomedical aspects of Ta and Ta based alloys, systematic characterizations of newly developed Ta-based metallic glasses in bio-implant applications is still lacking. This study employs sputtering approach to produced thin-film Ti-based metallic glasses due to the high melting temperature of Ta (3020 °C). Two fully amorphous Ta-based metallic glasses composed of Ta57Ti17Zr15Si11 and Ta75Ti10Zr8Si7 are produced and experimentally characterized in terms of their mechanical properties, bio-corrosion properties, surface hydrophilic characteristics, and in-vitro cell viability and cells attachment tests. Compare to conventional pure Ti and Ta metals, the developed Ta-based metallic glasses exhibit higher hardness and lower modulus which are better match to the mechanical properties of bone. MTS assay results show that Ta-based metallic glasses show comparable cell viability and cell attachment rate compared to that of pure Ti and Ta surface in a 72 h in-vitro test.

Electric Properties of Pb(Sb1/2Nb1/2)O3 PbTiO3 PbZrO3 Ceramics

NASA Astrophysics Data System (ADS)

Kawamura, Yasushi; Ohuchi, Hiromu

1994-09-01

Solid-solution ceramics of ternary system xPb(Sb1/2Nb1/2)O3 yPbTiO3 zPbZrO3 were prepared by the solid-state reaction of powder materials. Ceramic, electric, dielectric and piezoelectric properties and crystal structures of the system were studied. Sintering of the system xPb(Sb1/2Nb1/2)O3 yPbTiO3 zPbZrO3 is much easier than that of each end composition, and well-sintered high-density ceramics were obtained for the compositions near the morphotropic transformation. Piezoelectric ceramics with high relative dielectric constants, high radial coupling coefficient and low resonant resistance were obtained for the composition near the morphotropic transformation. The composition Pb(Sb1/2Nb1/2)0.075Ti0.45Zr0.475O3 showed the highest dielectric constant (ɛr=1690), and the composition Pb(Sb1/2Nb1/2)0.05Ti0.45Zr0.5O3 showed the highest radial coupling coefficient (kp=64%).

In-operando hard X-ray photoelectron spectroscopy study on the impact of current compliance and switching cycles on oxygen and carbon defects in resistive switching Ti/HfO{sub 2}/TiN cells

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

Sowinska, Malgorzata, E-mail: sowinska@ihp-microelectronics.com; Bertaud, Thomas; Walczyk, Damian

2014-05-28

In this study, direct experimental materials science evidence of the important theoretical prediction for resistive random access memory (RRAM) technologies that a critical amount of oxygen vacancies is needed to establish stable resistive switching in metal-oxide-metal samples is presented. In detail, a novel in-operando hard X-ray photoelectron spectroscopy technique is applied to non-destructively investigates the influence of the current compliance and direct current voltage sweep cycles on the Ti/HfO{sub 2} interface chemistry and physics of resistive switching Ti/HfO{sub 2}/TiN cells. These studies indeed confirm that current compliance is a critical parameter to control the amount of oxygen vacancies in themore » conducting filaments in the oxide layer during the RRAM cell operation to achieve stable switching. Furthermore, clear carbon segregation towards the Ti/HfO{sub 2} interface under electrical stress is visible. Since carbon impurities impact the oxygen vacancy defect population under resistive switching, this dynamic carbon segregation to the Ti/HfO{sub 2} interface is suspected to negatively influence RRAM device endurance. Therefore, these results indicate that the RRAM materials engineering needs to include all impurities in the dielectric layer in order to achieve reliable device performance.« less

Effects of shot-peening and atmospheric-pressure plasma on aesthetic improvement of Ti-Nb-Ta-Zr alloy for dental applications

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Suzuki, Yuu; Ito, Michiko; Yamada, Motoko; Matsutake, Sinpei; Takashima, Seigo; Sato, Hisashi; Watanabe, Yoshimi

2018-01-01

Ti and Ti alloys are widely used for biomedical applications such as artificial joints and dental devices because of their good mechanical properties and biochemical compatibility. However, dental devices made of Ti and Ti alloys do not have the same color as teeth, so they are inferior to ceramics and polymers in terms of aesthetic properties. In a previous study, Ti-29Nb-13Ta-4.6Zr was coated with a white Ti oxide layer by heat treatment to improve its aesthetic properties. Shot-peening is a severe plastic deformation process and can introduce a large shear strain on the peened surface. In this study, the effects of shot-peening and atmospheric-pressure plasma on Ti-29Nb-13Ta-4.6Zr were investigated to form a white layer on the surface for dental applications.

Structural, Optical and Impedance Spectroscopic Characterizations of Nanocrystalline A2Ti2Zr5O16 (A = Mg, Ca, Ba and Sr)

NASA Astrophysics Data System (ADS)

Sandeep, K.; Thomas, Jijimon K.; Solomon, Sam

2018-04-01

A nanocrystalline A2Ti2Zr5O16 (A = Mg, Ca, Ba and Sr) system has been synthesized by a modified combustion technique. The cation-deficient calzirtite (Ca2Ti2Zr5O16) is found to be a tetragonal structure with the space group I4(1)/acd. The average size of the particle from the transmission electron microscopy image is estimated to be 23.30 nm and 20.16 nm for Ca2Ti2Zr5O16 and Ba2Ti2Zr5O16, respectively. The optical bandgap calculated using a Tauc plot is between 3.01 eV and 3.46 eV. Raman and Fourier transform infrared spectroscopy (FTIR) studies were carried out to confirm the phase purity of the sample. The scanning electron microscopy (SEM) image of a Ca2Ti2Zr5O16 sample sintered at 1360°C for 3 h shows minimum porosity with 96% of the theoretical density. The frequency-dependent dielectric study shows that the dielectric constant is maximized at low frequencies and decreases as the frequency increases. The Cole-Cole plot reveals that the material exhibits conduction due to the contributions of grain, grain boundary and electrode effects. The photoluminescence spectra of the samples were recorded and the transitions causing emission have been identified.

Studies on corrosion resistance and bio-activity of plasma spray deposited hydroxylapatite (HA) based TiO2 and ZrO2 dispersed composite coatings on titanium alloy (Ti-6Al-4V) and the same after post spray heat treatment

NASA Astrophysics Data System (ADS)

Kumari, Renu; Majumdar, Jyotsna Dutta

2017-10-01

In the present study, the effect of plasma spray deposited hydroxylapatite (HA) based TiO2 dispersed (HA + 50 wt.% TiO2), coating and post spray heat treatment to be referred as HA-TiO2 (heat treated at 650 °C for 2 h) and ZrO2 dispersed (HA + 10 wt.% ZrO2), to be referred as HA-ZrO2 coating (heat treated at 750 °C for 2 h) on corrosion resistance and bioactivity of Ti-6Al-4V substrate has been undertaken. There is partial decomposition of HA to tri-calcium-phosphate (Ca3(PO4)2) and formation of CaTiO3 phase in HA-TiO2 coating and CaZrO3 phase in the HA-ZrO2 coating. Corrosion study in Hank's solution shows that there is shifting of corrosion potential (Ecorr) towards active potential (-1.1 V(SCE) for as-sprayed and post spray heat treated HA-TiO2 coating, -1.1 V(SCE) for as-sprayed HA-ZrO2 coating and -1 V(SCE) for HA-ZO2 coating after post spray heat treatment), and deterioration in pitting corrosion (Epit) resistance in as-sprayed coatings and the same after heat treatment (-0.7 V(SCE) for both HA-TiO2 and HA-ZrO2 coating as compared to as received substrate (-0.3 V(SCE)). The corrosion rate was increased for both the coatings with a maximum increase in HA-ZrO2 coating. Bioactivity test shows a higher degree of apatite deposition in as-sprayed coating and the same after heat treatment as compared to as received Ti-6Al-4V though the as-sprayed one showed a superior behavior.

Processing Ti-25Ta-5Zr Bioalloy via Anodic Oxidation Procedure at High Voltage

NASA Astrophysics Data System (ADS)

Ionita, Daniela; Grecu, Mihaela; Dilea, Mirela; Cojocaru, Vasile Danut; Demetrescu, Ioana

2011-12-01

The current paper reports the processing of Ti-25Ta-5Zr bioalloy via anodic oxidation in NH4BF4 solution under constant potentiostatic conditions at high voltage to obtain more suitable properties for biomedical application. The maximum efficiency of the procedure is reached at highest applied voltage, when the corrosion rate in Hank's solution is decreased approxomately six times. The topography of the anodic layer has been studied using atomic force microscopy (AFM), and the results indicated that the anodic oxidation process increases the surface roughness. The AFM images indicated a different porosity for the anodized surfaces as well. After anodizing, the hydrophilic character of Ti-25Ta-5Zr samples has increased. A good correlation between corrosion rate obtained from potentiodynamic curves and corrosion rate from ions release analysis was obtained.

Improvement of bio-corrosion resistance for Ti42Zr40Si15Ta3 metallic glasses in simulated body fluid by annealing within supercooled liquid region.

PubMed

Huang, C H; Lai, J J; Wei, T Y; Chen, Y H; Wang, X; Kuan, S Y; Huang, J C

2015-01-01

The effects of the nanocrystalline phases on the bio-corrosion behavior of highly bio-friendly Ti42Zr40Si15Ta3 metallic glasses in simulated body fluid were investigated, and the findings are compared with our previous observations from the Zr53Cu30Ni9Al8 metallic glasses. The Ti42Zr40Si15Ta3 metallic glasses were annealed at temperatures above the glass transition temperature, Tg, with different time periods to result in different degrees of α-Ti nano-phases in the amorphous matrix. The nanocrystallized Ti42Zr40Si15Ta3 metallic glasses containing corrosion resistant α-Ti phases exhibited more promising bio-corrosion resistance, due to the superior pitting resistance. This is distinctly different from the previous case of the Zr53Cu30Ni9Al8 metallic glasses with the reactive Zr2Cu phases inducing serious galvanic corrosion and lower bio-corrosion resistance. Thus, whether the fully amorphous or partially crystallized metallic glass would exhibit better bio-corrosion resistance, the answer would depend on the crystallized phase nature. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of calcium pyrophosphate on microstructural evolution and in vitro biocompatibility of Ti-35Nb-7Zr composite by spark plasma sintering.

PubMed

Zhang, L; Tan, J; He, Z Y; Jiang, Y H

2018-09-01

β-type Ti-35Nb-7Zr alloy has attracted considerable attentions as a bone implant material. The alloy, however, has poor bioactivity, which difficult to form a strong osseointegration between the bone tissues. Combining Ti alloy with a bioactive and biodegradable ceramic has been of interest to researchers. But the large difference in physicochemical property of high-melting metal and ceramic elements would bring the manufacturing restriction. In this work, Ti-35Nb-7Zr-CPP composites were fabricated with mechanical alloy of Ti, Nb, Zr and Nano calcium pyrophosphate (CPP) powders mixture followed by spark plasma sintering (SPS) routes. The effect of CPP ceramic on microstructural evolution and in vitro biocompatibility were investigated. As the addition of CPP (10-30 wt%), ceramic elements spreading towards the matrix, the generated metal-ceramic bioactive phases CaTiO 3 are observed well consolidated with β-Ti matrix. With the CPP increasing, Ca and P atoms rapidly migrated to the β-Ti matrix to form granulated Ti 5 P 3 , which leads to the increasing porosity (10%-18%) in the composites. The results demonstrated that the favorable cell viability (the cell proliferation rates were higher than 100%) and growth inside the pores of the composites arise from the rough micro-porous surface and the release of bioactive metal-ceramic phase ions into the biological environment. The enhanced bioactivity and microstructural evolution behaviors of the Ti-35Nb-7Zr-CPP composites may provide a strategy for designing and fabricating multifunctional implants. Copyright © 2018 Elsevier B.V. All rights reserved.

In-plane orientation and composition dependences of crystal structure and electrical properties of {100}-oriented Pb(Zr,Ti)O3 films grown on (100) Si substrates by metal organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Okamoto, Shoji; Sankara Rama Krishnan, P. S.; Okamoto, Satoshi; Yokoyama, Shintaro; Akiyama, Kensuke; Funakubo, Hiroshi

2017-10-01

In-plane orientation-controlled Pb(Zr x ,Ti1- x )O3 (PZT) films with a thickness of approximately 2 µm and a Zr/(Zr + Ti) ratio of 0.39-0.65 were grown on (100) Si substrates by pulsed metal-organic chemical vapor deposition (MOCVD). In-plane-oriented epitaxial PZT films and in-plane random fiber-textured PZT films with {100} out-of-plane orientation were grown on (100)c SrRuO3//(100)c LaNiO3//(100) CeO2//(100) YSZ//(100) Si and (100)c SrRuO3/(100)c LaNiO3/(111) Pt/TiO2/SiO2/(100) Si substrates, respectively. The effects of Zr/(Zr + Ti) ratio and in-plane orientation on the crystal structure, dielectric, ferroelectric, and piezoelectric properties of the films were systematically investigated. The X-ray diffraction measurement showed that the epitaxial PZT films had a higher volume fraction of (100) orientation than the fiber-textured PZT films in the tetragonal Zr/(Zr + Ti) ratio region. A large difference was not detected between the epitaxial films and the fiber-textured films for Zr/(Zr + Ti) ratio dependence of the dielectric constant, and remanent polarization. However, in the rhombohedral phase region [Zr/(Zr + Ti) = 0.65], coercive field was found to be 1.5-fold different between the epitaxial and fiber-textured PZT films. The maximum field-induced strains measured at 0-100 kV/cm by scanning atomic force microscopy were obtained at approximately Zr/(Zr + Ti) = 0.50 and were about 0.5 and 0.3% for the epitaxial and fiber-textured PZT films, respectively.

A thermal study on the structural changes of bimetallic ZrO2-modified TiO2 nanotubes synthesized using supercritical CO2.

PubMed

Lucky, R A; Charpentier, P A

2009-05-13

In this study the thermal behavior of bimetallic ZrO(2)-TiO(2) (10/90 mol/mol) nanotubes are discussed which were synthesized via a sol-gel process in supercritical carbon dioxide (scCO(2)). The effects of calcination temperature on the morphology, phase structure, mean crystallite size, specific surface area and pore volume of the nanotubes were investigated by using a variety of physiochemical techniques. We report that SEM and TEM images showed that the nanotubular structure was preserved at up to 800 degrees C calcination temperature. When exposed to higher temperatures (900-1000 degrees C) the ZrO(2)-TiO(2) tubes deformed and the crystallites fused together, forming larger crystallites, and a bimetallic ZrTiO(4) species was detected. These results were further examined using TGA, FTIR, XRD and HRTEM analysis. The BET textural properties demonstrated that the presence of a small amount of Zr in the TiO(2) matrix inhibited the grain growth, stabilized the anatase phase and increased the thermal stability.

Effect of Zr Doping on Structural and Ferroelectric Properties of Lead-Free Bi0.5(Na0.80K0.20)0.5TiO3 Films

NASA Astrophysics Data System (ADS)

Quan, Ngo Duc; Hung, Vu Ngoc; Dung, Dang Duc

2017-10-01

Environmentally friendly lead-free Bi0.5(Na0.80K0.20)0.5(Ti1- x Zr x )O3 (BNKT- xZr) ferroelectric films with Zr4+ doping concentration x in the range from 0 to 0.05 have been grown on Pt/Ti/SiO2/Si substrates via chemical solution deposition. The effects of Zr4+ substitution on the crystal structure and ferroelectric properties of the films were investigated. X-ray diffraction data revealed that the BNKT- xZr films possessed rhombohedral and tetragonal symmetries at a morphotropic phase boundary when a small amount of Zr4+ doping was added. P- E hysteresis loops typical of ferroelectric materials were observed for all compositions. Zr4+ substituted for Ti4+ in the BNKT- xZr films and remarkably enhanced the ferroelectric properties. The remanent ( P r) and maximum polarization ( P m) reached their highest values of 14.0 μC/cm2 and 35.7 μC/cm2, respectively, at x = 0.02. These values, which are equivalent to the highest P r and P m values in previous reports on lead-free films with different compositions, compare well with those of Pb(Zr,Ti)O3 (PZT) films. Therefore, BNKT- xZr films with optimal Zr4+ concentration could substitute for PZT films in lead-free piezo-microelectromechanical systems (MEMS) devices.

Electrical and dielectric properties of ZnO and CeO{sub 2} doped ZrTi{sub 2}O{sub 6} ceramic

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

George, Aneesh; Thomas, Jijimon K.; John, Annamma

2014-01-28

Zirconium oxide (ZrO{sub 2}) and titanium dioxide (TiO{sub 2}) are the important catalyst supports, since it has acidic and basic properties. The intermediate phase zirconium titanate ZrTi{sub 2}O{sub 6}, which is a solid solution with Zr:Ti ratio 1:2 has outstanding dielectric properties. The effects of doping of ZnO and CeO{sub 2} on the dielectric and electrical properties of ZrTi{sub 2}O{sub 6} ceramic are investigated. On adding 0.5 wt% ZnO, the dielectric constant is increased but, on adding CeO{sub 2}, the dielectric constant is decreased. The bulk density of pure sample sintered at 1530 °C is 91% of theoretical density whilemore » that of the doped samples sintered at 1450 °C is more than 94% of theoretical density. Scanning electron micrographs reveal that the samples are well sintered with minimum porosity. The semicircle behavior in the Cole-Cole plots at room temperature reveals that the samples are good ionic conductor. The induced impedance is reduced for doped samples and this can be used as a material for electrolyte in Solid Oxide Fuel Cell.« less

Grindability of cast Ti-Hf alloys.

PubMed

Kikuchi, Masafumi; Takahashi, Masatoshi; Sato, Hideki; Okuno, Osamu; Nunn, Martha E; Okabe, Toru

2006-04-01

As part of our systematic studies characterizing the properties of titanium alloys, we investigated the grindability of a series of cast Ti-Hf alloys. Alloy buttons with hafnium concentrations up to 40 mass% were made using an argon-arc melting furnace. Each button was cast into a magnesia-based mold using a dental titanium casting machine; three specimens were made for each metal. Prior to testing, the hardened surface layer was removed. The specimens were ground at five different speeds for 1 min at 0.98 N using a carborundum wheel on an electric dental handpiece. Grindability was evaluated as the volume of metal removed per minute (grinding rate) and the volume ratio of metal removed compared to the wheel material lost (grinding ratio). The data were analyzed using ANOVA. A trend of increasing grindability was found with increasing amounts of hafnium, although there was no statistical difference in the grindability with increasing hafnium contents. We also found that hafnium may be used to harden or strengthen titanium without deteriorating the grindability.

[Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks

PubMed Central

2017-01-01

Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12(COO)16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12(COO)16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts. PMID:29392182

Thermomechanical processing of aluminum micro-alloyed with Sc, Zr, Ti, B, and C

NASA Astrophysics Data System (ADS)

McNamara, Cameron T.

Critical exploration of the minimalistic high strength low alloy aluminum (HSLA-Al) paradigm is necessary for the continued development of advanced aluminum alloys. In this study, scandium (Sc) and zirconium (Zr) are examined as the main precipitation strengthening additions, while magnesium (Mg) is added to probe the synergistic effects of solution and precipitation hardening, as well as the grain refinement during solidification afforded by a moderate growth restriction factor. Further, pathways of recrystallization are explored in several potential HSLA-Al syste =ms sans Sc. Aluminum-titanium-boron (Al-Ti-B) and aluminum-titanium-carbon (Al-Ti-C) grain refining master alloys are added to a series of Al-Zr alloys to examine both the reported Zr poisoning effect on grain size reduction and the impact on recrystallization resistance through the use of electron backscattered diffraction (EBSD) imaging. Results include an analysis of active strengthening mechanisms and advisement for both constitution and thermomechanical processing of HSLA-Al alloys for wrought or near-net shape cast components. The mechanisms of recrystallization are discussed for alloys which contain a bimodal distribution of particles, some of which act as nucleation sites for grain formation during annealing and others which restrict the growth of the newly formed grains.

Effects of Zr, Ti, and Al Additions on Nonmetallic Inclusions and Impact Toughness of Cast Low-Alloy Steel

NASA Astrophysics Data System (ADS)

Bizyukov, Pavel V.; Giese, Scott R.

2017-04-01

A microalloying of the low-carbon and low-alloy cast steel was conducted with Zr, Ti, and Al that were added to the steel in four combinations. After heat treatment, the samples were tested for impact toughness at room temperature using the Charpy method. The highest values of impact toughness were obtained in the group treated with Zr, while Zr-Ti and Zr-Ti-Al groups showed moderate toughness values; the lowest values were observed in the Zr-Al group. Difference among the treatment groups was observed in the fracture mechanisms, morphology, and area distribution of the inclusions. High toughness values achieved in the trials treated with zirconium corresponded with smooth ductile fracture. The metal treated with a combination of zirconium and titanium had a relatively small area occupied by inclusions, but its toughness was also moderate. Lowest impact toughness values corresponded with the larger area occupied by the inclusions in the trials treated with aluminum. Also, a connection between the solubility product [Al][N] and impact toughness was established. The study also provides a qualitative description and quantitative analysis of the nonmetallic inclusions formation as a result of microalloying treatment. The precipitation sequence of the inclusions was described based on the thermochemical calculations for the nonmetallic compounds discovered in the experimental steel. A description of the size distribution, morphology, and composition was conducted for the oxides, nitrides, sulfides, and multiphase particles.

Electrochemical Characteristics of Cell Cultured Ti-Nb-Zr Alloys After Nano-Crystallized Si-HA Coating.

PubMed

Jeong, Yong-Hoon; Choe, Han-Cheol

2015-01-01

The aim of this study was to investigate the electrochemical characteristics of nano crystallized Si-HA coating on Ti-Nb-Zr alloy after human osteoblast like (HOB) cell attachment. The Ti-Nb-Zr alloy was manufactured with 35 wt.% of Nb and 10 wt.% of Zr by arc melting furnace to appropriate physical properties as biomaterials. The HA and Si-substituted coatings were prepared by electron-beam physical vapor deposition method with 0.5, 0.8 and 1.2 wt.% of Si contents, and nano aging treatment was performed 500 degrees C for 1 h. The characteristics of coating surface were analyzed by field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, respectively. To evaluate of cell attachment on cell cultured surface, the potentiodynamic test was performed on the surface using HOB cells. The results showed that the Si-HA coating surface showed higher tendency of cell attachment than that of single HA coating, corrosion resistance value was increased by dense of cell attachment.

Electrode characteristics of nanocrystalline (Zr, Ti)(V, Cr, Ni) 2.41 compound

NASA Astrophysics Data System (ADS)

Majchrzycki, W.; Jurczyk, M.

The electrochemical properties of nanocrystalline Zr 0.35Ti 0.65V 0.85Cr 0.26Ni 1.30 alloy, which has the hexagonal C14 type structure, have been investigated. This material has been prepared using mechanical alloying (MA) followed by annealing. The amorphous phase forms directly from the starting mixture of the elements, without other phase formation. Heating the MA samples at 1070 K for 0.5 h resulted in the creation of ordered alloy. This alloy was used as negative electrode for Ni-MH x battery. The electrochemical results show very little difference between the nanocrystalline and polycrystalline powders, as compared with the substantial difference between these and the amorphous powder. In the annealed nanocrystalline Zr 0.35Ti 0.65V 0.85Cr 0.26Ni 1.30 powders discharging capacities up to 150 mA h g -1 (at 160 mA g -1 discharging current) have been measured. The properties of nanocrystalline electrode were attributed to the structural characteristics of the compound caused by mechanical alloying.

Preparation and Characterization of BaTiO3-PbZrTiO3 Coating for Pyroelectric Energy Harvesting

NASA Astrophysics Data System (ADS)

Raghavendra, R. M.; Praneeth, K. P. S. S.; Dutta, Soma

2017-01-01

Harvesting energy from waste heat is a promising field of research as there are significant energy recovery opportunities from various waste thermal energy sources. The present study reports pyroelectric energy harvesting using thick film prepared from a (x)BaTiO3-(1 - x)PbZr0.52Ti0.48O3 (BT-PZT) solid solution. The developed BT-PZT system is engineered to tune the ferro to paraelectric phase transition temperature of it in-between the phase transition temperature of BaTiO3 (393 K) and PbZrTiO3 (573 K) with higher pyroelectric figure-of-merit (FOM). The temperature-dependent dielectric behavior of the material has revealed the ferro- to paraelectric phase transition at 427 K with a maximum dielectric constant of 755. The room-temperature (298 K) pyroelectric coefficient (Pi) of the material was obtained as 738.63 μC/m2K which has yielded a significantly high FOM of 1745.8 J m-3 K-2. The enhancement in pyroelectric property is attributed to the morphotopic phase transition between tetragonal and rhombohedral PZT phases in the BT-PZT system. The developed BT-PZT system is capable of generating a power output of 1.3 mW/m2 near the Curie temperature with a constant rate (0.11 K/s) of heating. A signal conditioning circuit has been developed to rectify the time-varying current and voltage signals obtained from the harvester during heating cycles. The output voltage generated by the pyroelectric harvester has been stored in a capacitor for powering wearable electronics.

Fundamental Thermal and Mechanical Properties of Boride Ceramics

DTIC Science & Technology

2014-02-28

Zr ,Y)B2 ( Zr ,Hf)B2 ( Zr ,Ti)B2 ZrB2 El ec tri ca l R es is tiv ity (µ Ω -c m ) Temperature (°C) Figure 17. Electrical resistivity as a function...family as Zr , namely Ti and Hf, had minimal effect on thermal conductivity, while others such as Nb , Ta, and W had an increasing impact based on their...diffusivity (α), heat capacity (Cp) from the NIST-JANAF tables, and bulk density (ρ) using Equation 6. (5) (6) Electrical resistivity

Investigation of static properties of medical alloys Ti-(20-30)Nb-(10-13)Ta-5Zr

NASA Astrophysics Data System (ADS)

Sergienko, K. V.; Sevost’yanov, M. A.; Konushkin, S. V.; Nasakina, E. O.; Baikin, A. S.; Shatova, L. A.; Kolmakov, A. G.

2018-04-01

In the work, static properties of TiNbTaZr titanium alloy were carried out. The search for a NiTi alloy replacement is necessary for medical products to eliminate the negative effects of nickel on the body. Conclusions are drawn about the adequacy of the mechanical properties of the test alloy for use in stent implants.

On the origin of bulk glass forming ability in Cu-Hf, Zr alloys

NASA Astrophysics Data System (ADS)

Ristić, Ramir; Zadro, Krešo; Pajić, Damir; Figueroa, Ignacio A.; Babić, Emil

2016-04-01

Understanding the formation of bulk metallic glasses (BMG) in metallic systems and finding a reliable criterion for selection of BMG compositions are among the most important issues in condensed-matter physics and material science. Using the results of magnetic susceptibility measurements performed on both amorphous and crystallized Cu-Hf alloys (30-70 at% Cu) we find a correlation between the difference in magnetic susceptibilities of corresponding glassy and crystalline alloys and the variation in the glass forming ability (GFA) in these alloys. Since the same correlation can be inferred from data for the properties associated with the electronic structure of Cu-Zr alloys, it seems quite general and may apply to other glassy alloys based on early and late transition metals. This correlation is plausible from the free-energy considerations and provides a simple way to select the compositions with high GFA.

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

DOE PAGES

Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

2017-07-19

Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

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

Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

Effect of Spark Plasma Sintering on the Structure and Properties of Ti1−xZrxNiSn Half-Heusler Alloys

PubMed Central

Downie, Ruth A.; Popuri, Srinivas R.; Ning, Huanpo; Reece, Mike J.; Bos, Jan-Willem G.

2014-01-01

XNiSn (X = Ti, Zr and Hf) half-Heusler alloys have promising thermoelectric properties and are attracting enormous interest for use in waste heat recovery. In particular, multiphase behaviour has been linked to reduced lattice thermal conductivities, which enables improved energy conversion efficiencies. This manuscript describes the impact of spark plasma sintering (SPS) on the phase distributions and thermoelectric properties of Ti0.5Zr0.5NiSn based half-Heuslers. Rietveld analysis reveals small changes in composition, while measurement of the Seebeck coefficient and electrical resistivities reveals that all SPS treated samples are electron doped compared to the as-prepared samples. The lattice thermal conductivities fall between 4 W·m−1·K−1 at 350 K and 3 W·m−1·K−1 at 740 K. A maximum ZT = 0.7 at 740 K is observed in a sample with nominal Ti0.5Zr0.5NiSn composition. PMID:28788234

Kinetic and mechanistic aspects of propene oligomerization with ionic organozirconium and -hafnium compounds: Crystal structures of [Cp* {sub 2}MMe(THT)]{sup +}[BPh{sub 4}]{sup {minus}} (M=Zr, Hf)

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

Eshuis, J.J.W.; Tan, Y.Y.; Meetsma, A.

1992-01-01

In N,N-dimethylaniline the ionic complexes [Cp{sup *}{sub 2}MMe(THT)]{sup +}[BPh{sub 4}]{sup {minus}}(M=Zr,Hf) oligomerize propene to low molecular weight oligomers. At room temperature for M = Zr a rather broad molecular weight distribution is obtained (C{sub 6} to C{sub 24}), whereas for M = Hf only one dimer (4-methyl-1-pentene) and one trimer (4,6-dimethyl-1-heptene) are formed. With an increase in temperature the product composition shifts to lower molecular weights, but the specific formation of head-to-tail oligomers is retained. The oligomers are formed by {beta}-Me transfer from the growing oligopropene alkyl chain to the metal center. The molecular weight distributions of the oligomers producedmore » at temperature between 5 and 45 {degrees}C are satisfactorily described by the Flory-Schulz theory. This allows the calculation of ratios of rate coefficients for propagation (k{sub p}) and termination (k{sub t}). Inactivation of the catalysts is caused by two different mechanisms. At room temperature allylic C-H activation of monomer and isobutene (formed by a minor {beta}-H transfer termination) gives inactive (meth) allyl compounds, [Cp{sup *} {sub 2}M({eta}{sup 3}-C{sub 3}H{sub 5})]{sup +} and [Cp{sup *}{sub 2}M({eta}{sup 3}-C{sub 4}H{sub 7})]{sup +} (M = Zr, Hf). At elevated temperatures (>45 {degrees}C) catalytically inactive zwitterionic complexes Cp{sup *}{sub M}{sup +}-m-C{sub 6}H{sub 4}-BPh{sub 3}{sup {minus}}(M = Zr, Hf) are formed through aromatic C-H activation. Reactivation of the inactive (meth)allyl complexes can be achieved by addition of hydrogen to the oligomerization mixtures. 38 refs., 4 figs., 7 tabs.« less

Investigation of microstructure, micro-mechanical and optical properties of HfTiO{sub 4} thin films prepared by magnetron co-sputtering

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

Mazur, Michal, E-mail: michal.mazur@pwr.edu.pl; Wojcieszak, Damian; Domaradzki, Jaroslaw

2015-12-15

Highlights: • HfTiO{sub 4} thin films were deposited by magnetron co-sputtering. • As-prepared and annealed at 800 °C thin films were nanocrystalline. • Optical properties and hardness were investigated in relation to thin films structure. • Hardness was 3-times higher in the case of as-deposited thin films. • HfTiO{sub 4} thin films are suitable for use as optical coatings with protective properties. - Abstract: Titania (TiO{sub 2}) and hafnium oxide (HfO{sub 2}) thin films are in the focus of interest to the microelectronics community from a dozen years. Because of their outstanding properties like, among the others, high stability, highmore » refractive index, high electric permittivity, they found applications in many optical and electronics domains. In this work discussion on the hardness, microstructure and optical properties of as-deposited and annealed HfTiO{sub 4} thin films has been presented. Deposited films were prepared using magnetron co-sputtering method. Performed investigations revealed that as-deposited coatings were nanocrystalline with HfTiO{sub 4} structure. Deposited films were built from crystallites of ca. 4–12 nm in size and after additional annealing an increase in crystallites size up to 16 nm was observed. Micro-mechanical properties, i.e., hardness and elastic modulus were determined using conventional load-controlled nanoindentation testing. the annealed films had 3-times lower hardness as-compared to as-deposited ones (∼9 GPa). Based on optical investigations real and imaginary components of refractive index were calculated, both for as-deposited and annealed thin films. The real refractive index component increased after annealing from 2.03 to 2.16, while extinction coefficient increased by an order from 10{sup −4} to 10{sup −3}. Structure modification was analyzed together with optical energy band-gap, Urbach energy and using Wemple–DiDomenico model.« less

Evaluation of AlGaN/GaN high electron mobility transistors grown on ZrTi buffer layers with sapphire substrates

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

Ren, Fan; Pearton, Stephen J.; Ahn, Shihyun

Here, AlGaN/GaN high electron mobility transistors (HEMTs) have been grown on sapphire substrates, using ZrTi buffer layers to provide in-plane lattice-matching to hexagonal GaN. X-ray diffraction (XRD) as well as cross-section transmission electron microscopy (TEM) were used to assess the quality of the HEMT structure. The XRD 2θ scans showed full-width-at-half-maximum values of 0.16°, 0.07°, and 0.08° for ZrTi alloy, GaN buffer layer, and the entire HEMT structure, respectively. TEM studies of the GaN buffer layer and the AlN/ZrTi/AlN stack showed the importance of growing thin AlN buffer layers on the ZrTi layer prior to growth of the GaN buffermore » layer. The density of threading dislocations in the GaN channel layer of the HEMT structure was estimated to be in the 10 8 cm –2 range. The HEMT device exhibited a saturation drain current density of 820 mA/mm, and the channel of the fabricated HEMTs could be well modulated. A cutoff frequency (f T) of 8.9 GHz and a maximum frequency of oscillation (f max) of 17.3 GHz were achieved for HEMTs with gate dimensions of 1 × 200 μm.« less

Evaluation of AlGaN/GaN high electron mobility transistors grown on ZrTi buffer layers with sapphire substrates

DOE PAGES

Ren, Fan; Pearton, Stephen J.; Ahn, Shihyun; ...

2016-09-21

Here, AlGaN/GaN high electron mobility transistors (HEMTs) have been grown on sapphire substrates, using ZrTi buffer layers to provide in-plane lattice-matching to hexagonal GaN. X-ray diffraction (XRD) as well as cross-section transmission electron microscopy (TEM) were used to assess the quality of the HEMT structure. The XRD 2θ scans showed full-width-at-half-maximum values of 0.16°, 0.07°, and 0.08° for ZrTi alloy, GaN buffer layer, and the entire HEMT structure, respectively. TEM studies of the GaN buffer layer and the AlN/ZrTi/AlN stack showed the importance of growing thin AlN buffer layers on the ZrTi layer prior to growth of the GaN buffermore » layer. The density of threading dislocations in the GaN channel layer of the HEMT structure was estimated to be in the 10 8 cm –2 range. The HEMT device exhibited a saturation drain current density of 820 mA/mm, and the channel of the fabricated HEMTs could be well modulated. A cutoff frequency (f T) of 8.9 GHz and a maximum frequency of oscillation (f max) of 17.3 GHz were achieved for HEMTs with gate dimensions of 1 × 200 μm.« less

Synthesis, characterization and biological study on Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide and bis(3-hydroxyimino)butan-2-ylidene)-oxalohydrazide.

PubMed

El-Asmy, A A; El-Gammal, O A; Radwan, H A

2010-09-01

Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide (H(2)L(1)) and oxalyl bis(diacetylmonoxime hydrazone) [its IUPAC name is oxalyl bis(3-hydroxyimino)butan-2-ylidene)oxalohydrazide] (H(4)L(2)) have been synthesized and characterized by partial elemental analysis, spectral (IR; electronic), thermal and magnetic measurements. [Cr(L(1))(H(2)O)(3)(Cl)].H(2)O, [ZrO(HL(1))(2)].C(2)H(5)OH, [UO(2)(L(1))(H(2)O)(2)] [ZrO(H(3)L(2))(Cl)](2).2H(2)O, [HfO(H(3)L(2))(Cl)](2).2H(2)O and [UO(2)(H(2)L(2))].2H(2)O have been suggested. H(2)L(1) behaves as a monobasic or dibasic bidentate ligand while H(4)L(2) acts as a tetrabasic octadentate with the two metal centers. The molecular modeling of the two ligands have been drawn and their molecular parameters were calculated. Examination of the DNA degradation of H(2)L(1) and H(4)L(2) as well as their complexes revealed that direct contact of [ZrO(H(3)L(2))(Cl)](2).2H(2)O or [HfO(H(3)L(2))(Cl)](2).2H(2)O degrading the DNA of Eukaryotic subject. The ligands and their metal complexes were tested against Gram's positive Bacillus thuringiensis (BT) and Gram's negative (Escherichia coli) bacteria. All compounds have small inhibitory effects. Copyright 2010 Elsevier B.V. All rights reserved.

Incorporating Small Fatigue Crack Growth in Probabilistic Life Prediction: Effect of Stress Ratio in Ti-6Al-2Sn-4Zr-6-Mo (Preprint)

DTIC Science & Technology

2012-08-01

growth rates as well as the variability in the same, in the + titanium alloy, Ti-6Al-2Sn-4Zr-6Mo (Ti- 6 -2- 4 - 6 ) was studied at 260°C. A probabilistic...were obtained in a separate study on the effect of R on the small-crack growth regime in another + titanium alloy, Ti- 6 - 4 [32]. Given that crack...microstructure of Ti-6Al-2Sn-4Zr-6Mo (Ti- 6 -2- 4 - 6 ) at 260°C with particular emphasis on incorporating small-crack data into probabilistic life prediction

Effects of Plasma ZrN Metallurgy and Shot Peening Duplex Treatment on Fretting Wear and Fretting Fatigue Behavior of Ti6Al4V Alloy.

PubMed

Tang, Jingang; Liu, Daoxin; Zhang, Xiaohua; Du, Dongxing; Yu, Shouming

2016-03-23

A metallurgical zirconium nitride (ZrN) layer was fabricated using glow metallurgy using nitriding with zirconiuming prior treatment of the Ti6Al4V alloy. The microstructure, composition and microhardness of the corresponding layer were studied. The influence of this treatment on fretting wear (FW) and fretting fatigue (FF) behavior of the Ti6Al4V alloy was studied. The composite layer consisted of an 8-μm-thick ZrN compound layer and a 50-μm-thick nitrogen-rich Zr-Ti solid solution layer. The surface microhardness of the composite layer is 1775 HK 0.1 . A gradient in cross-sectional microhardness distribution exists in the layer. The plasma ZrN metallurgical layer improves the FW resistance of the Ti6Al4V alloy, but reduces the base FF resistance. This occurs because the improvement in surface hardness results in lowering of the toughness and increasing in the notch sensitivity. Compared with shot peening treatment, plasma ZrN metallurgy and shot peening composite treatment improves the FW resistance and enhances the FF resistance of the Ti6Al4V alloy. This is attributed to the introduction of a compressive stress field. The combination of toughness, strength, FW resistance and fatigue resistance enhance the FF resistance for titanium alloy.

Densities of Active species in N2/H2 RF and HF afterglows: application to surface nitriding of TiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Ricard, André; Sarrette, Jean-Philippe; Wang, Yunfei; Kim, Yu-Kwon

2017-10-01

N2/0-5% H2 flowing afterglows from Radio Frequency (RF) and High Frequency (HF) sources have been analyzed by optical emission spectroscopy. In similar conditions (pressure 5-6 Torr, flow rate 0.5 slm and power 100 W), it is found in pure N2 a nearly constant N-atom density from the pink to the late afterglow, which is higher in HF than in RF: (1-2) and 0.4 × 1015 cm-3, respectively. With a N2/2% H2 gas mixture, the early afterglows is changed to a late afterglow with about the same N-atom density for both RF and HF cases: (8-9) × 1014 cm-3. Anatase TiO2 nanocrystals and Atomic Layer Deposition-grown films were exposed to the RF afterglows at room temperature. XPS analysis of the samples has shown that the highest N/Ti ratio of 0.24 can be achieved with the pure N2 late afterglow. In the HF pure N2 late afterglow, however, the N/Ti coverage was limited to 0.04 in spite of higher N-atom density. Such differences in the N content between the two RF and HF cases are attributed to the presence of a high O-atom impurity of 2 × 1013 cm-3 in HF as compared to that (8 × 1011 cm-3) in RF. Contribution to the topical issue "Plasma Sources and Plasma Processes (PSPP)", edited by Luis Lemos Alves, Thierry Belmonte and Tiberiu Minea

Luna 16 - Some Li, K, Rb, Sr, Ba, rare-earth, Zr, and Hf concentrations.

NASA Technical Reports Server (NTRS)

Philpotts, J. A.; Schnetzler, C. C.; Schuhmann, S.; Thomas , H. H.; Bottino, M. L.

1972-01-01

Concentrations of Li, K, Rb, Sr, Na, rare-earths, Zr and Hf have been determined for some Luna 16 core materials by mass-spectrometric isotope-dilution. Two regolith fines samples from different depths in the core, and four rock-chips, including both igneous rocks and breccias, have similar trace-element concentrations. The Luna 16 materials have general lunar trace-element characteristics but differ from other returned lunar samples in a manner that suggests the presence of excess feldspar. Unless the Luna 16 igneous rocks are fused soils, they appear to represent either partial plagioclase cumulates or the least differentiated igneous material yet returned from the moon. The similarity in trace-element concentrations of the igneous rocks and the fines would then suggest largely local derivation of the Luna 16 regolith.

Microstructure and Properties of a Refractory NbCrMo0.5Ta0.5ZrTi Alloy (Preprint)

DTIC Science & Technology

2011-10-01

slightly enriched with Nb , Mo and Ta and depleted with Zr and Cr, and its lattice parameter after HIP was a = 324.76 ± 0.16 pm. The BCC2 phase was...FCC phase was highly enriched with Cr and it was identified as a Laves C15 phase, ( Zr ,Ta)(Cr,Mo, Nb )2, with the lattice parameter a = 733.38 ± 0.18 pm...with Nb , Mo and Ta and depleted with Zr and Cr, and its lattice parameter after HIP was a = 324.76 ± 0.16 pm. The BCC2 phase was enriched with Zr and Ti

Investigation of the stability of glass-ceramic composites containing CeTi 2 O 6 and CaZrTi 2 O 7 after ion implantation

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

Paknahad, Elham; Grosvenor, Andrew P.

Glass-ceramic composite materials have been investigated for nuclear waste sequestration applications due to their ability to incorporate large amounts of radioactive waste elements. A key property that needs to be understood when developing nuclear waste sequestration materials is how the structure of the material responds to radioactive decay of nuclear waste elements, which can be simulated by high energy ion implantation. Borosilicate glass-ceramic composites containing brannerite-type (CeTi2O6) or zirconolite-type (CaZrTi2O7) oxides were synthesized at different annealing temperatures and investigated after being implanted with high-energy Au ions to mimic radiation induced structural damage. Backscattered electron (BSE) images were collected to investigatemore » the interaction of the brannerite crystallites with the glass matrix before and after implantation and showed that the morphology of the crystallites in the composite materials were not affected by radiation damage. Surface sensitive Ti K-edge glancing angle XANES spectra collected from the implanted composite materials showed that the structures of the CeTi2O6 and CaZrTi2O7 ceramics were damaged as a result of implantation; however, analysis of Si L2,3-edge XANES spectra indicated that the glass matrix was not affected by ion implantation.« less

Investigation of the stability of glass-ceramic composites containing CeTi2O6 and CaZrTi2O7 after ion implantation

NASA Astrophysics Data System (ADS)

Paknahad, Elham; Grosvenor, Andrew P.

2017-12-01

Glass-ceramic composite materials have been investigated for nuclear waste sequestration applications due to their ability to incorporate large amounts of radioactive waste elements. A key property that needs to be understood when developing nuclear waste sequestration materials is how the structure of the material responds to radioactive decay of nuclear waste elements, which can be simulated by high energy ion implantation. Borosilicate glass-ceramic composites containing brannerite-type (CeTi2O6) or zirconolite-type (CaZrTi2O7) oxides were synthesized at different annealing temperatures and investigated after being implanted with high-energy Au ions to mimic radiation induced structural damage. Backscattered electron (BSE) images were collected to investigate the interaction of the brannerite crystallites with the glass matrix before and after implantation and showed that the morphology of the crystallites in the composite materials were not affected by radiation damage. Surface sensitive Ti K-edge glancing angle XANES spectra collected from the implanted composite materials showed that the structures of the CeTi2O6 and CaZrTi2O7 ceramics were damaged as a result of implantation; however, analysis of Si L2,3-edge XANES spectra indicated that the glass matrix was not affected by ion implantation.

Synthesis and Characterization of Zr-BASED Amorphous and Crystalline Composite Coating on Ti Substrate by Laser Cladding

NASA Astrophysics Data System (ADS)

Tang, D. M.; Zhang, D. C.; Peng, W.; Luo, Z. C.; Wu, X. Q.; Wang, Y. M.; Lin, J. G.

2014-02-01

A thin strip of a Zr-based alloy with a composition of Zr60Cu25Fe5Al10 (in atom percent) was used as a raw material, and the composite coatings containing Zr-based amorphous phase and crystallites on Ti substrate were fabricated by a one-step laser cladding method without protection. The microstructure, phase constitution, microhardness and wear properties of the coatings were investigated. The results indicate that the microstructure of the coatings is strongly dependent on the laser scanning speed under the conditions of the laser power of 1300 W and laser beam diameter of 6 mm, and the composite coating mainly containing amorphous phase with a small amount of the crystallites can be obtained at the laser scanning speed of 10 mm/s. The composite coating exhibits much higher microhardness than the pure Ti substrate, and thus it behaves superior wear resistance in comparison with the substrate.

Impedance of (CoFeZr)0,559(PbZrTiO3)0,441 nanocomposite annealed in a tubular furnace

NASA Astrophysics Data System (ADS)

Boiko, Oleksandr

2016-12-01

The objective of the present research has been to determine the influence of annealing in tubular furnace on capacity of (CoFeZr)0,559(PbZrTiO3)0,441 nanocomposite produced by ion beam sputtering using combined argon and oxygen beam. The phase angle of the nanocomposite directly after preparing demonstrates negative values, which indicates the capacitive type of electrical conductivity of the material. The rapid increase of conductivity when frequency increases indicates hopping conductance in the material. The additional polarization of the nanocomposite occurs with its extinction in the area of high frequencies. The electrons relaxation time has been defined as of ca τ = 1,25×10-4 s. Annealing of nanocomposite sample x = 55.9 at.% at temperature Ta = 548 K causes phase angle obtains positive values in high frequency area, which indicates the change of conduction type from capacitive to inductive. The voltage resonance phenomenon occurs in the material. Annealing in temperature of Ta = 648 K causes changes of the nanomaterials capacity. The additional oxidization of CoFeZr metallic phase nanograins which provides to the potential barrier formation around potential wells (CoFeZr nanoparticles).

Chemical separation of Mo and W from terrestrial and extraterrestrial samples via anion exchange chromatography.

PubMed

Nagai, Yuichiro; Yokoyama, Tetsuya

2014-05-20

A new two-stage chemical separation method was established using an anion exchange resin, Eichrom 1 × 8, to separate Mo and W from four natural rock samples. First, the distribution coefficients of nine elements (Ti, Fe, Zn, Zr, Nb, Mo, Hf, Ta, and W) under various chemical conditions were determined using HCl, HNO3, and HF. On the basis of the obtained distribution coefficients, a new technique for the two-stage chemical separation of Mo and W, along with the group separation of Ti-Zr-Hf, was developed as follows: 0.4 M HCl-0.5 M HF (major elements), 9 M HCl-0.05 M HF (Ti-Zr-Hf), 9 M HCl-1 M HF (W), and 6 M HNO3-3 M HF (Mo). After the chemical procedure, Nb remaining in the W fraction was separated using 9 M HCl-3 M HF. On the other hand, Nb and Zn remaining in the Mo fraction were removed using 2 M HF and 6 M HCl-0.1 M HF. The performance of this technique was evaluated by separating these elements from two terrestrial and two extraterrestrial samples. The recovery yields for Mo, W, Zr, and Hf were nearly 100% for all of the examined samples. The total contents of the Zr, Hf, W, and Mo in the blanks used for the chemical separation procedure were 582, 9, 29, and 396 pg, respectively. Therefore, our new separation technique can be widely used in various fields of geochemistry, cosmochemistry, and environmental sciences and particularly for multi-isotope analysis of these elements from a single sample with significant internal isotope heterogeneities.

Dynamic recrystallization behavior of a biomedical Ti-13Nb-13Zr alloy.

PubMed

Bobbili, Ravindranadh; Madhu, V

2016-06-01

The dynamic recrystallization (DRX) behavior of a biomedical titanium Ti-13Nb-13Zr alloy has been investigated using the high temperature compression tests under wide range of strain rates (0.001-1/s) and temperatures 900-1050°C. A constitutive equation represented as a function of temperature, strain rate and true strain is developed and the hot deformation apparent activation energy is calculated about 534kJ/mol. By considering the exponential relationship between work-hardening rate (θ) and stress, a new mathematical model was proposed for predicting flow stress up to the critical strain during hot deformation. The mathematical model for predicting flow stress up to the critical strain exhibits better consistency and accuracy. The DRX kinetic equation of Ti-13Nb-13Zr alloy is described as XDRX=1-exp[-0.32(Ɛ-ƐcƐ(*))(2.3)] . The DRX kinetic model was validated by microstructure observation. It was also found that the process of DRX was promoted by decreasing strain rate and increasing deformation temperature. Eventually, the continuous dynamic recrystallization (CDRX) was identified to be the DRX mechanism using transmission electron microscope (TEM). Copyright © 2015 Elsevier Ltd. All rights reserved.

Biocompatible low Young's modulus achieved by strong crystallographic elastic anisotropy in Ti-15Mo-5Zr-3Al alloy single crystal.

PubMed

Lee, S-H; Todai, M; Tane, M; Hagihara, K; Nakajima, H; Nakano, T

2012-10-01

The elastic anisotropy of the Ti-15Mo-5Zr-3Al (mass%) β-Ti alloy, an ISO certified biomedical material, was investigated using its single crystal. It was revealed that the Young's modulus exhibited pronounced anisotropy. The Young's modulus was reduced to 44.4GPa along the 〈100〉 direction in the Ti-15Mo-5Zr-3Al single crystal, that is comparable to that of human cortical bones. We determined the strategy that β-Ti alloys with extremely low moduli can be developed by reducing the electron-atom (e/a) ratio in alloys, and by suppressing the formation of the ω-phase at the same time. This new knowledge must lead to the development of "single crystalline β-Ti implant materials" as hard tissue replacements for reducing the stress shielding effect. Copyright © 2012 Elsevier Ltd. All rights reserved.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

PubMed Central

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-01-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I–V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later. PMID:28252106

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

NASA Astrophysics Data System (ADS)

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers.

PubMed

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-02

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO 2 /nanoporous-Si and the TiO 2 /nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO 2 /nanoporous Si are lower than that of the HfO 2 /nanoporous Si, the former is more stable than the later.

Enhanced electrical properties of SrBi4Ti4O15 ceramic with addition of ZrO2

NASA Astrophysics Data System (ADS)

Mamatha, B.; Rani, G. Neeraja; Shankar, J.

2018-04-01

Polycrystalline SrBi4Ti3.95Zr0.05O15 (SBZT) ceramic was prepared by solid-state double sintering method. It was characterized by X-Ray Diffraction (XRD) and Scanning Electron Micrograph (SEM). With the increased addition of ZrO2, the electrical properties as dielectric, ferroelectric and piezoelectric were studied. From XRD, single-phase formation with orthorhombic structure was identified by the increase of ZrO2. The remnant polarization (Pr) and dielectric constant was found to be increased with the increase of ZrO2. With the increase of ZrO2, Curie temperature (Tc) was found to be decreased. The planar electromechanical coupling coefficient (Kp = 0.57) and Piezoelectric coefficient (d33 = 18 pC/N) was found to be increased with the increase of ZrO2.

First-Principles Study of the Jahn-Teller Distortion in the Ti1-XVXH2 and Zr1-XNbxH2 Alloys

NASA Astrophysics Data System (ADS)

Quijano, Ramiro; de Coss, Romeo; Singh, David

2008-03-01

The transition metal dihydrides TiH2 and ZrH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Electronic band structure calculations have shown that TiH2 and ZrH2 in the cubic phase display a very flat band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. In order to understand the role of band filling in controlling the structural instability of the transition metal dihydrides, we have performed a first-principles total energy study of the Ti1-XVxH2 and Zr1-xNbxH2 alloys. The calculations were performed using FP-LAPW method within the (DFT) and we use the GGA for exchange correlation functional energy. The critical concentration for which the Jahn-Teller effect is suppressed, was determined from the evolution of the tetragonal-cubic energy barrier. We discuss the electronic mechanism of the structural-instability, in terms of the band filling. From the obtained results we conclude that the tetragonal distortion in TiH2 and ZrH2 is not produced only by a Jahn-Teller Effect. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 43830-F.

Ab initio study for the IR spectroscopy of PbTiO3 and PbZrO3, primary blocks of PbZr1‑x Ti x O3

NASA Astrophysics Data System (ADS)

Peperstraete, Yoann; Amzallag, Emilie; Tétot, Robert; Roy, Pascale

2018-05-01

PbTiO3 (PT) and PbZrO3 (PZ) are the two primary blocks of the solid solution PbZr1‑x Ti x O3 (PZT). They can be modelled in different ways; but, in order to do comparable DFT calculations on PZT, with different values of x, one must find a unique method that can be used for both PT and PZ. In particular, we want to evaluate their vibrational properties to compare them with experimental data. Density functional theory (DFT) is used to perform structure geometry optimizations and electronic structure calculations, both on low- and high-temperature phase. Then, harmonic vibrational frequencies of their low-temperature phase are determined for transverse and longitudinal optical (TO & LO) phonons. Moreover, a detailed study of the eigenvectors shows that accurate calculations are necessary to correctly interpret and understand the IR spectra. In the end, the comparison of our theoretical results with previous experimental and theoretical data confirm the strong potential of the SOGGA (second-order generalized gradient approximation) functional to correctly describe PT, PZ and, hopefully, PZT; especially their structural and vibrational properties.

Ferroelectric Polarization-Modulated Interfacial Fine Structures Involving Two-Dimensional Electron Gases in Pb(Zr,Ti)O3/LaAlO3/SrTiO3 Heterostructures.

PubMed

Wang, Shuangbao; Bai, Yuhang; Xie, Lin; Li, Chen; Key, Julian D; Wu, Di; Wang, Peng; Pan, Xiaoqing

2018-01-10

Interfacial fine structures of bare LaAlO 3 /SrTiO 3 (LAO/STO) heterostructures are compared with those of LAO/STO heterostructures capped with upward-polarized Pb(Zr 0.1 ,Ti 0.9 )O 3 (PZT up ) or downward-polarized Pb(Zr 0.5 ,Ti 0.5 )O 3 (PZT down ) overlayers by aberration-corrected scanning transmission electron microscopy experiments. By combining the acquired electron energy-loss spectroscopy mapping, we are able to directly observe electron transfer from Ti 4+ to Ti 3+ and ionic displacements at the interface of bare LAO/STO and PZT down /LAO/STO heterostructure unit cell by unit cell. No evidence of Ti 3+ is observed at the interface of the PZT up /LAO/STO samples. Furthermore, the confinement of the two-dimensional electron gas (2DEG) at the interface is determined by atomic-column spatial resolution. Compared with the bare LAO/STO interface, the 2DEG density at the LAO/STO interface is enhanced or depressed by the PZT down or PZT up overlayer, respectively. Our microscopy studies shed light on the mechanism of ferroelectric modulation of interfacial transport at polar/nonpolar oxide heterointerfaces, which may facilitate applications of these materials as nonvolatile memory.

Alloying effect on the room temperature creep characteristics of a Ti-Zr-Be bulk metallic glass

NASA Astrophysics Data System (ADS)

Gong, Pan; Wang, Sibo; Li, Fangwei; Wang, Xinyun

2018-02-01

The effect of alloying elements (e.g. Fe, Al, and Ni) on the room temperature creep behavior of a lightweight Ti41Zr25Be34 bulk metallic glass (BMG) was investigated via nanoindentation tests. The generalized Kelvin model was adopted to describe the creep curves. The strain rate sensitivity m has been derived as a measure of the creep resistance. The compliance spectrum and retardation spectrum were also derived. The results show that the creep resistance of Ti41Zr25Be34 alloy can be obviously improved with the addition of alloying elements, and the most effective element is found to be Al. The mechanism for enhancing the creep resistance was discussed in terms of the scale variation of the shear transformation zone induced by alloying.

Pyroelectric response in crystalline hafnium zirconium oxide (Hf 1- x Zr x O 2 ) thin films

DOE PAGES

Smith, S. W.; Kitahara, A. R.; Rodriguez, M. A.; ...

2017-02-13

Pyroelectric coefficients were measured for 20 nm thick crystalline hafnium zirconium oxide (Hf 1-xZr xO 2) thin films across a composition range of 0 ≤ x ≤ 1. Pyroelectric currents were collected near room temperature under zero applied bias and a sinusoidal oscillating temperature profile to separate the influence of non-pyroelectric currents. The pyroelectric coefficient was observed to correlate with zirconium content, increased orthorhombic/tetragonal phase content, and maximum polarization response. The largest measured absolute value was 48 μCm -2K -1 for a composition with x = 0.64, while no pyroelectric response was measured for compositions which displayed no remanent polarizationmore » (x = 0, 0.91, 1).« less

Memory effects in a Al/Ti:HfO2/CuPc metal-oxide-semiconductor device

NASA Astrophysics Data System (ADS)

Tripathi, Udbhav; Kaur, Ramneek

2016-05-01

Metal oxide semiconductor structured organic memory device has been successfully fabricated. Ti doped hafnium oxide (Ti:HfO2) nanoparticles has been fabricated by precipitation method and further calcinated at 800 °C. Copper phthalocyanine, a hole transporting material has been utilized as an organic semiconductor. The electrical properties of the fabricated device have been studied by measuring the current-voltage and capacitance-voltage characteristics. The amount of charge stored in the nanoparticles has been calculated by using flat band condition. This simple approach for fabricating MOS memory device has opens up opportunities for the development of next generation memory devices.

Microstructure and mechanical properties investigation of in situ TiB2 and ZrB2 reinforced Al-4Cu composites

NASA Astrophysics Data System (ADS)

Lutfi Anis, Ahmad; Ramli, Rosmamuhammadani; Darham, Widyani; Zakaria, Azlan; Talari, Mahesh Kumar

2016-02-01

Conventional Al-Cu alloys exhibit coarse grain structure leading to inferior mechanical properties in as-cast condition. Expensive thermo-mechanical treatments are needed to improve microstructure and corresponding mechanical properties. In situ Al-based composites were developed to improve mechanical properties by dispersion strengthening and grain refinement obtained by the presence of particulates in the melt during solidification. In this work Al-4Cu - 3TiB2 and Al-4Cu-3ZrB2 in situ composites were prepared by liquid casting method. XRD, electron microscopy and mechanical tests were performed on suitably sectioned and metallographically prepared surfaces to investigate the phase distribution, hardness and tensile properties. It was found that the reinforcement particles were segregated along the grain boundaries of Al dendrites. Tensile fracture morphology for both Al-4Cu - 3TiB2 and Al-4Cu-3ZrB2 were analyzed and compared to determine the fracture propagation mechanism in the composites. Al-4Cu-3ZrB2 in situ composites displayed higher strength and hardness compared to Al-4Cu-3TiB2 which could be ascribed to the stronger interfacial bonding between the Al dendrites and ZrB2 particulates as evidenced from fractographs.

Low-Temperature Reactivities of Ultra-High Temperature Ceramics (Hf-X System)

DTIC Science & Technology

2005-12-01

as interacting fillers with the preceramic polymer formulations. In situ formation of the SiC phase was also evaluated as a practical approach in...led to a renewal of activities to fabricate MB2/ SiC composites as the materials of choice, because of their high thermal and oxidation resistance...HfB2/ SiC composite microstructures (and also HfC, ZrB2, and ZrC composites ) under pressureless conditions. These can be employed in reactive and

Electrochemical characterization of pulsed layer deposited hydroxyapatite-zirconia layers on Ti-21Nb-15Ta-6Zr alloy for biomedical application

NASA Astrophysics Data System (ADS)

Izquierdo, Javier; Bolat, Georgiana; Cimpoesu, Nicanor; Trinca, Lucia Carmen; Mareci, Daniel; Souto, Ricardo Manuel

2016-11-01

A new titanium base Ti-21Nb-15Ta-6Zr alloy covered with hydroxyapatite-zirconia (HA-ZrO2) by pulsed laser deposition (PLD) technique was characterized regarding its corrosion resistance in simulated physiological Ringer's solution at 37 °C. For the sake of comparison, Ti-6Al-4V standard implant alloy, with and without hydroxyapatite-zirconia coating, was also characterized. Multiscale electrochemical analysis using both conventional averaging electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization, and spatially-resolved microelectrochemical techniques (scanning electrochemical microscopy, SECM) were used to investigate the electrochemical behaviour of the materials. In addition, scanning electron microscopy evidenced that no relevant surface morphology changes occurred on the materials upon immersion in the simulated physiological solution, despite variations in their electrochemical behaviour. Although uncoated metals appear to show better performances during conventional corrosion tests, the response is still quite similar for the HA-ZrO2 coated materials while providing superior resistance towards electron transfer due to the formation of a more dense film on the surface, thus effectively behaving as a passive material. It is believed corrosion of the HA-ZrO2 coated Ti-21Nb-15Ta-6Zr alloy will have negligible effect upon biochemical and cellular events at the bone-implant interface and could facilitate osseointegration.

New intermetallic MIrP (M=Ti, Zr, Nb, Mo) and MgRuP compounds related with MoM'P (M'=Ni and Ru) superconductor

NASA Astrophysics Data System (ADS)

Kito, Hijiri; Iyo, Akira; Wada, Toshimi

2011-01-01

Using a cubic-anvil high-pressure apparatus, ternary iridium phosphides MIrP (M=Ti, Zr, Nb, Mo) and MgRuP have been prepared by reaction of stoichiometric amounts of each metal and phosphide powders at around 2 Gpa and above 1523 K for the first time. The structure of these compounds prepared at high-pressure has been characterized by X-ray powder diffraction. Diffraction lines of these compounds are assigned by the index of the Co2Si-type structure. The electrical resistivity and the d.c magnetic susceptibility of MIrP (M=Ti, Zr, Nb, Mo) have measured at low temperatures. Unfortunately, no superconducting transition for MIrP (M=Ti, Zr, Nb, Mo) and MgRuP are observed down to 2 K.

Growth and microstructure formation of isothermally-solidified Zircaloy-4 joints brazed by a Zr-Ti-Cu-Ni amorphous alloy ribbon

NASA Astrophysics Data System (ADS)

Kim, K. H.; Lim, C. H.; Lee, J. G.; Lee, M. K.; Rhee, C. K.

2013-10-01

The microstructure and growth characteristics of Zircaloy-4 joints brazed by a Zr48Ti16Cu17Ni19 (at.%) amorphous filler metal have been investigated with regard to the controlled isothermal solidification and intermetallic formation. Two typical joints were produced depending on the isothermal brazing temperature: (1) a dendritic growth structure including bulky segregation in the central zone (at 850 °C), and (2) a homogeneous dendritic structure throughout the joint without segregation (at 890 °C). The primary α-Zr phase was solidified isothermally, nucleating to grow into a joint with a cellular or dendritic structure. Also, the continuous Zr2Ni and particulate Zr2Cu phases were formed in the segregated center zone and at the intercellular region, respectively, owing to the different solubility and atomic mobility of the solute elements (Ti, Cu, and Ni) in the α-Zr matrix. A disappearance of the central Zr2Ni phase was also rate-controlled by the outward diffusion of the Cu and Ni elements. When the detrimental Zr2Ni intermetallic phase was eliminated by a complete isothermal solidification at 890 °C, the strengths of the joints were high enough to cause yielding and fracture in the base metal, exceeding those of the bulk Zircaloy-4, at room temperature as well as at elevated temperatures (up to 400 °C).

Effect of Zirconium Addition on Microstructure and Mechanical Property of TiC/Ti6A14V Composites

NASA Astrophysics Data System (ADS)

Ma, Xuliang; Wang, Xiang; Li, Li; Gai, Pengtao; Zhu, Chengwu

TiC/Ti6A14V composites with different Zr additions were prepared successfully in a consumable vacuum arc furnace equipped with a water-cooled copper crucible and the effect of the Zr content on the microstructure and mechanical property of 15 vol.%TiC/Ti6A14V composites was investigated by XRD, SEM and hardness testing. The results show that when the level of Zr addition is less than 4 wt.%, the morphology of the primary TiC in the composites is dendrite, and the petal-shape, piece-shape or palpus-shape eutectic TiC separates out around the primary TiC. The average size of the primary TiC decreases and the amount of eutectic TiC increases gradually with increasing Zr content. The effects of Zr on morphology of the primary TiC weaken with further addition of Zr. And the hardness (HRC) of composites was obviously increased in the whole range of Zr addition. The refinement mechanism of Zr was attributed to the combined effects of increase in nucleation rate at the constitutionally supercooled zone ahead of the solidification front and reduction in growth rate.

Reactive sputter deposition of metal oxide nanolaminates

NASA Astrophysics Data System (ADS)

Rubin Aita, Carolyn

2008-07-01

We discuss the reactive sputter deposition of metal oxide nanolaminates on unheated substrates using four archetypical examples: ZrO2 Al2O3, HfO2 Al2O3, ZrO2 Y2O3, and ZrO2 TiO2. The pseudobinary bulk phase diagrams corresponding to these nanolaminates represent three types of interfaces. I. Complete immiscibility (ZrO2 Al2O3 and HfO2 Al2O3). II. Complete miscibility (ZrO2 Y2O3). III. Limited miscibility without a common end-member lattice (ZrO2 TiO2). We found that, although reactive sputter deposition is a far-from-equilibrium process, thermodynamic considerations strongly influence both phase formation within layers and at interfaces. We show that pseudobinary phase diagrams can be used to predict interfacial cation mixing in the nanolaminates. However, size effects must be considered to predict specific structures. In the absence of pseudoepitaxy, size effects play a significant role in determining the nanocrystalline phases that form within a layer (e.g. tetragonal ZrO2, tetragonal HfO2, and orthorhombic HfO2) and at interfaces (e.g. monoclinic (Zr,Ti)O2). These phases are not bulk standard temperature and pressure phases. Their formation is understood in terms of self-assembly into the lowest energy structure in individual critical nuclei.

Effect of annealing temperature on microstructure and superelastic properties of a Ti-18Zr-4.5Nb-3Sn-2Mo alloy.

PubMed

Fu, Jie; Kim, Hee Young; Miyazaki, Shuichi

2017-01-01

In this study a new superelastic Ti-18Zr-4.5Nb-3Sn-2Mo alloy was prepared by adding 2at% of Mo as a substitute for Nb to the Ti-18Zr-11Nb-3Sn alloy, and heat treatment at different temperatures was conducted. The temperature dependence of superelasticity and annealing texture was investigated. Texture showed a dependence of annealing temperature: the specimen annealed at 923K for 0.3ks exhibited {113} β <47¯1> β type texture which was similar to the deformation texture, while specimens annealed at 973, 1073K, and 1173K showed {001} β <110> β type recrystallization texture which was preferable for recovery strain. The largest recovery strain of 6.2%, which is the same level as that of the Ti-18Zr-11Nb-3Sn alloy, was obtained in the specimen annealed at 1173K for 0.3ks due to the well-developed {001} β <110> β type recrystallization texture. The Ti-18Zr-3Nb-3Sn-2Mo alloy presented a higher tensile strength compared with the Ti-18Zr-11Nb-3Sn alloy when heat treated at 1173K for 0.3ks, which was due to the solid solution strengthening effect of Mo. Annealing at 923K for 0.3ks was effective in obtaining a good combination of a high strength as 865MPa and a large recovery strain as 5.6%. The high recovery strain was due to the high stress at which the maximum recovery stain was obtained which was attributed to the small grain size formed at low annealing temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Very large phase shift of microwave signals in a 6 nm Hf x Zr1-x O2 ferroelectric at ±3 V

NASA Astrophysics Data System (ADS)

Dragoman, Mircea; Modreanu, Mircea; Povey, Ian M.; Iordanescu, Sergiu; Aldrigo, Martino; Romanitan, Cosmin; Vasilache, Dan; Dinescu, Adrian; Dragoman, Daniela

2017-09-01

In this letter, we report for the first time very large phase shifts of microwaves in the 1-10 GHz range, in a 1 mm long gold coplanar interdigitated structure deposited over a 6 nm Hf x Zr1-x O2 ferroelectric grown directly on a high resistivity silicon substrate. The phase shift is larger than 60° at 1 GHz and 13° at 10 GHz at maximum applied DC voltages of ±3 V, which can be supplied by a simple commercial battery. In this way, we demonstrate experimentally that the new ferroelectrics based on HfO2 could play an important role in the future development of wireless communication systems for very low power applications.

Influence of N2 partial pressure on structural and microhardness properties of TiN/ZrN multilayers deposited by Ar/N2 vacuum arc discharge

NASA Astrophysics Data System (ADS)

Naddaf, M.; Abdallah, B.; Ahmad, M.; A-Kharroub, M.

2016-08-01

The influence of N2 partial pressure on structural, mechanical and wetting properties of multilayered TiN/ZrN thin films deposited on silicon substrates by vacuum arc discharge of (N2 + Ar) gas mixtures is investigated. X-ray diffraction (XRD) results show that the average texturing coefficient of (1 1 1) orientation and the grain size of both TiN and ZrN individual layers increase with increasing the N2 partial pressure. The Rutherford back scattering (RBS) measurements and analysis reveal that incorporation of the nitrogen in the film increases with increasing the N2 partial pressure and both TiN and ZrN individual layers have a nitrogen over-stoichiometry for N2 partial pressure ⩾50%. The change in the film micro-hardness is correlated to the changes in crystallographic texture, grain size, stoichiometry and the residual stress in the film as a function of the N2 partial pressure. In particular, stoichiometry of ZrN and TiN individual is found to play the vital role in determining the multilayer hardness. The multilayer film deposited at N2 partial pressure of 25% has the best stoichiometric ratio of both TiN and ZrN layers and the highest micro-hardness of about 32 GPa. In addition, water contact angle (WCA) measurements and analysis show a decrease in the work of adhesion on increasing the N2 partial pressure.

Energetics of Single Substitutional Impurities in NiTi

NASA Technical Reports Server (NTRS)

Good, Brian S.; Noebe, Ronald

2003-01-01

Shape-memory alloys are of considerable current interest, with applications ranging from stents to Mars rover components. In this work, we present results on the energetics of single substitutional impurities in B2 NiTi. Specifically, energies of Pd, Pt, Zr and Hf impurities at both Ni and Ti sites are computed. All energies are computed using the CASTEP ab initio code, and, for comparison, using the quantum approximate energy method of Bozzolo, Ferrante and Smith. Atomistic relaxation in the vicinity of the impurities is investigated via quantum approximate Monte Carlo simulation, and in cases where the relaxation is found to be important, the resulting relaxations are applied to the ab initio calculations. We compare our results with available experimental work.

A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

NASA Astrophysics Data System (ADS)

Powell, C. J.; Smekal, W.; Werner, W. S. M.

2005-09-01

We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. We report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.

Chromium-free conversion coatings based on inorganic salts (Zr/Ti/Mn/Mo) for aluminum alloys used in aircraft applications

NASA Astrophysics Data System (ADS)

Santa Coloma, P.; Izagirre, U.; Belaustegi, Y.; Jorcin, J. B.; Cano, F. J.; Lapeña, N.

2015-08-01

Novel chromium-free conversion coatings based on Zr/Ti/Mn/Mo compounds were developed at a pilot scale to improve the corrosion resistance of the AA2024-T3 and AA7075-T6 aluminum alloys for aircraft applications. The influence of the presence of Zr and Ti in the Zr/Ti/Mn/Mo conversion bath's formulation on the corrosion resistance of the coated alloys was investigated. The corrosion resistance provided by the conversion coatings was evaluated by salt spray exposure and potentiodynamic sweeps. Optical and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) and atomic force microscopy (AFM) operating in the Kelvin Probe mode (SKPFM) were used to provide microstructural information of the coated samples that achieved the best results in the corrosion tests. The salt spray test evidenced the higher corrosion resistance of the coated samples compared to the bare surfaces for both alloys. The potentiodynamic tests showed that the corrosion current density decreased for coated AA7075-T6 and AA2024-T3 alloys, which indicated an obvious improvement of the corrosion resistance with all the processes for both alloys. Although the corrosion resistance of the coated samples appeared to be higher for the alloy AA7075-T6 than for the alloy AA2024-T3, both alloys achieved the best corrosion protection with the coatings deposited from conversion bath formulations containing no titanium salts. The microscopy analysis on the coated AA7075-T6 samples revealed that a local deposition of Zr compounds and, possibly, an oxidation process occurred in the vicinity of the alloy's intermetallic particles. The amount of the Zr deposits at these locations increased with coating's formulations without Ti, which provided the best corrosion resistance. The Cr-free conversion coatings developed in this study for the AA7075-T6 and AA2024-T3 alloys do not meet yet the strict requirements of the aircraft industry. However, they significantly improved the corrosion

Characterization and Evaluation of Ti-Zr-V Non-evaporable Getter Films Used in Vacuum Systems

NASA Astrophysics Data System (ADS)

Ferreira, M. J.; Seraphim, R. M.; Ramirez, A. J.; Tabacniks, M. H.; Nascente, P. A. P.

Among several methods used to obtain ultra-high vacuum (UHV) for particles accelerators chambers, it stands out the internal coating with metallic films capable of absorbing gases, called NEG (non-evaporable getter). Usually these materials are constituted by elements of great chemical reactivity and solubility (such as Ti, Zr, and V), at room temperature for oxygen and other gases typically found in UHV, such as H2, CO, and CO2. Gold and ternary Ti-Zr-V films were produced by magnetron sputtering, and their composition, structure, morphology, and aging characteristics were characterized by energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field emission gun sc anning electronmicroscopy (FEG-SEM), atomic force microscopy (AFM), high resolution transmission electron microscopy (HRTEM). The comparison between the produced films and commercial samples indicated that the desirable characteristics depend on the nanometric structure of the films and that this structure is sensitive to the heat treatments.

Improved photocatalytic degradation rates of phenol achieved using novel porous ZrO2-doped TiO2 nanoparticulate powders.

PubMed

McManamon, Colm; Holmes, Justin D; Morris, Michael A

2011-10-15

This paper studies the photocatalytic degradation of phenol using zirconia-doped TiO(2) nanoparticles. ZrO(2) was chosen due to its promising results during preliminary studies. Particles smaller than 10nm were synthesised and doped with quantities of ZrO(2) ranging from 0.5 to 4% (molar metal content). Particles were calcined at different temperatures to alter the TiO(2) structure, from anatase to rutile, in order to provide an ideal ratio of the two phases. Powder X-ray diffraction (PXRD) analysis was used to examine the transformation between anatase and rutile. Degradation of phenol was carried out using a 40 W UV bulb at 365 nm and results were measured by UV-vis spectrometry. TEM images were obtained and show the particles exhibit a highly ordered structure. TiO(2) doped with 1% ZrO(2) (molar metal content) calcined at 700 °C proved to be the most efficient catalyst. This is due to an ideal anatase:rutlie ratio of 80:20, a large surface area and the existence of stable electron-hole pairs. ZrO(2) doping above the optimum loading acted as an electron-hole recombination centre for electron-hole pairs and reduced photocatalytic degradation. Synthesised photocatalysts compared favourably to the commercially available photocatalyst P25. The materials also demonstrated the ability to be recycled with similar results to those achieved on fresh material after 5 uses. Copyright © 2011 Elsevier B.V. All rights reserved.

Search for thermoelectrics with high figure of merit in half-Heusler compounds with multinary substitution

NASA Astrophysics Data System (ADS)

Choudhary, Mukesh K.; Ravindran, P.

2018-04-01

In order to improve the thermoelectric performance of TiCoSb we have substituted 50% of Ti equally with Zr and Hf at Ti site and Sb with Sn and Se equally at Sb site. The electronic structure of Ti0.5Zr0.25Hf0.25CoSn0.5Se0.5 is investigated using the full potential linearized augmented plane wave method and the thermoelectric transport properties are calculated on the basis of semi-classical Boltzmann transport theory. Our band structure calculations show that Ti0.5Zr0.25Hf0.25CoSn0.5Se0.5 has semiconducting behavior with indirect band gap value of 0.98 eV which follow the empirical rule of 18 valence-electron content to bring semiconductivity in half Heusler compounds, indicating that one can have semiconducting behavior in multinary phase of half Heusler compounds if they full fill the 18 VEC rule and this open-up the possibility of designing thermoelectrics with high figure of merit in half Heusler compounds. We show that at high temperature of around 700K Ti0.5Zr0.25Hf0.25CoSn0.5Se0.5 has high thermoelectric figure of merit of ZT = 1.05 which is higher than that of TiCoSb (˜ 0.95) suggesting that by going from ternary to multinary phase system one can enhance the thermoelectric figure of merit at higher temperatures.

Electron Microprobe Analysis of Hf in Zircon: Suggestions for Improved Accuracy of a Difficult Measurement

NASA Astrophysics Data System (ADS)

Fournelle, J.; Hanchar, J. M.

2013-12-01

It is not commonly recognized as such, but the accurate measurement of Hf in zircon is not a trivial analytical issue. This is important to assess because Hf is often used as an internal standard for trace element analyses of zircon by LA-ICPMS. The issues pertaining to accuracy revolve around: (1) whether the Hf Ma or the La line is used; (2) what accelerating voltage is applied if Zr La is also measured, and (3) what standard for Hf is used. Weidenbach, et al.'s (2004) study of the 91500 zircon demonstrated the spread (in accuracy) of possible EPMA values for six EPMA labs, 2 of which used Hf Ma, 3 used Hf La, and one used Hf Lb, and standards ranged from HfO2, a ZrO2-HfO2 compound, Hf metal, and hafnon. Weidenbach, et al., used the ID-TIMS values as the correct value (0.695 wt.% Hf.), for which not one of the EPMA labs came close to that value (3 were low and 3 were high). Those data suggest: (1) that there is a systematic underestimation error of the 0.695 wt% Hf (ID-TIMS Hf) value if Hf Ma is used; most likely an issue with the matrix correction, as the analytical lines and absorption edges of Zr La, Si Ka and Hf Ma are rather tightly packed in the electromagnetic spectrum. Mass absorption coefficients are easily in error (e.g., Donovan's determination of the MAC of Hf by Si Ka of 5061 differs from the typically used Henke value of 5449 (Donovan et al, 2002); and (2) For utilization of the Hf La line, however, the second order Zr Ka line interferes with Hf La if the accelerating voltage is greater than 17.99 keV. If this higher keV is used and differential mode PHA is applied, only a portion of the interference is removed (e.g., removal of escape peaks), causing an overestimation of Hf content. Unfortunately, it is virtually impossible to apply an interference correction in this case, as it is impossible to locate Hf-free Zr probe standard. We have examined many of the combinations used by those six EPMA labs and concluded that the optimal EPMA is done with Hf

TiS2 and ZrS2 single- and double-wall nanotubes: first-principles study.

PubMed

Bandura, Andrei V; Evarestov, Robert A

2014-02-15

Hybrid density functional theory has been applied for investigations of the electronic and atomic structure of bulk phases, nanolayers, and nanotubes based on titanium and zirconium disulfides. Calculations have been performed on the basis of the localized atomic functions by means of the CRYSTAL-2009 computer code. The full optimization of all atomic positions in the regarded systems has been made to study the atomic relaxation and to determine the most favorable structures. The different layered and isotropic bulk phases have been considered as the possible precursors of the nanotubes. Calculations on single-walled TiS2 and ZrS2 nanotubes confirmed that the nanotubes obtained by rolling up the hexagonal crystalline layers with octahedral 1T morphology are the most stable. The strain energy of TiS2 and ZrS2 nanotubes is small, does not depend on the tube chirality, and approximately obeys to D(-2) law (D is nanotube diameter) of the classical elasticity theory. It is greater than the strain energy of the similar TiO2 and ZrO2 nanotubes; however, the formation energy of the disulfide nanotubes is considerably less than the formation energy of the dioxide nanotubes. The distance and interaction energy between the single-wall components of the double-wall nanotubes is proved to be close to the distance and interaction energy between layers in the layered crystals. Analysis of the relaxed nanotube shape using radial coordinate of the metal atoms demonstrates a small but noticeable deviation from completely cylindrical cross-section of the external walls in the armchair-like double-wall nanotubes. Copyright © 2013 Wiley Periodicals, Inc.

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

NASA Astrophysics Data System (ADS)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-03-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

α″ Martensite and Amorphous Phase Transformation Mechanism in TiNbTaZr Alloy Incorporated with TiO2 Particles During Friction Stir Processing

NASA Astrophysics Data System (ADS)

Ran, Ruoshi; Liu, Yiwei; Wang, Liqiang; Lu, Eryi; Xie, Lechun; Lu, Weijie; Wang, Kuaishe; Zhang, Lai-Chang

2018-06-01

This work studied the formation of the α″ martensite and amorphous phases of TiNbTaZr alloy incorporated with TiO2 particles during friction stir processing. Formation of the amorphous phase in the top surface mainly results from the dissolution of oxygen, rearrangement of the lattice structure, and dislocations. High-stress stemming caused by dislocations and high-stress concentrations at crystal-amorphous interfaces promote the formation of α″ martensite. Meanwhile, an α″ martensitic transformation is hindered by oxygen diffusion from TiO2 to the matrix, thereby increasing resistance to shear.

Distribution of impurity states and charge transport in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} nanocomposites

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

Liu, Yuanfeng; Makongo, Julien P.A.; Page, Alexander

Energy filtering of charge carriers in a semiconducting matrix using atomically coherent nanostructures can lead to a significant improvement of the thermoelectric figure of merit of the resulting composite. In this work, several half-Heusler/full-Heusler (HH/FH) nanocomposites with general compositions Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} (0≤x≤0.15 and y=0.005, 0.01 and 0.025) were synthesized in order to investigate the behavior of extrinsic carriers at the HH/FH interfaces. Electronic transport data showed that energy filtering of carriers at the HH/FH interfaces in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} samples strongly depends on the doping level (y value) as well as the energymore » levels occupied by impurity states in the samples. For example, it was found that carrier filtering at HH/FH interfaces is negligible in Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 1−y}Sb{sub y} (y=0.01 and 0.025) composites where donor states originating from Sb dopant dominate electronic conduction. However, we observed a drastic decrease in the effective carrier density upon introduction of HH/FH interfaces for the mechanically alloyed Zr{sub 0.25}Hf{sub 0.75}Ni{sub 1+x}Sn{sub 0.995}Sb{sub 0.005} samples where donor states from unintentional Fe impurities contribute the largest fraction of conduction electrons. This work demonstrates the ability to synergistically integrate the concepts of doping and energy filtering through nanostructuring for the optimization of electronic transport in semiconductors. - Graphical abstract: Electronic transport in semiconducting half-Heusler (HH) matrices containing full-Heusler (FH) nanoinclusions strongly depends on the energy distribution of impurity states within the HH matrix with respect to the magnitude of the potential energy barrier at the HH/FH interfaces. - Highlights: • Coherent nanostructures enhanced thermoelectric behavior of half-Heusler alloys. • Nanostructures act as energy

Improved interfacial and electrical properties of GaAs metal-oxide-semiconductor capacitors with HfTiON as gate dielectric and TaON as passivation interlayer

NASA Astrophysics Data System (ADS)

Wang, L. S.; Xu, J. P.; Zhu, S. Y.; Huang, Y.; Lai, P. T.

2013-08-01

The interfacial and electrical properties of sputtered HfTiON on sulfur-passivated GaAs with or without TaON as interfacial passivation layer (IPL) are investigated. Experimental results show that the GaAs metal-oxide-semiconductor capacitor with HfTiON/TaON stacked gate dielectric annealed at 600 °C exhibits low interface-state density (1.0 × 1012 cm-2 eV-1), small gate leakage current (7.3 × 10-5 A cm-2 at Vg = Vfb + 1 V), small capacitance equivalent thickness (1.65 nm), and large equivalent dielectric constant (26.2). The involved mechanisms lie in the fact that the TaON IPL can effectively block the diffusions of Hf, Ti, and O towards GaAs surface and suppress the formation of interfacial As-As bonds, Ga-/As-oxides, thus unpinning the Femi level at the TaON/GaAs interface and improving the interface quality and electrical properties of the device.

Stability of Ceramics in Hydrogen between 4000 and 4500 F

NASA Technical Reports Server (NTRS)

May, Charles E.; Koneval, Donald; Fryburg, George C.

1959-01-01

The various reactions that are possible between hydrogen and certain ceramic materials are discussed as well as the means of measuring the extent of such reactions. Powdered carbides, nitrides, borides, and oxides were tested. These materials were heated inductively in a tungsten cup between 4000 and 4500 F for two 1-hour periods under a static hydrogen atmosphere. Weight, pressure, and diffraction pattern changes were observed, and these served to indicate the extent of reaction. Most of the ceramics, HfC, ZrC, TiC, TaC, NbC, WC, MO2C, HfN, ZrN, NbN, ZrB2, NbB2, and WB, showed less reaction than the minimum detectable value. However, the ceramics, TiN, TaN, HfB2, TiB2, ZrO2, and Cr2O3, apparently reacted to a measurable extent with hydrogen. Reactions of SiC, VC, and TaB2 with hydrogen were not determinable because of their incompatibility with the tungsten container.

Metastable phase transformation and hcp-ω transformation pathways in Ti and Zr under high hydrostatic pressures

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

Gao, Lei; Ding, Xiangdong, E-mail: dingxd@mail.xjtu.edu.cn, E-mail: ekhard@esc.cam.ac.uk; Sun, Jun

2016-07-18

The energy landscape of Zr at high hydrostatic pressure suggests that its transformation behavior is strongly pressure dependent. This is in contrast to the known transition mechanism in Ti, which is essentially independent of hydrostatic pressure. Generalized solid-state nudged elastic band calculations at constant pressure shows that α-Zr transforms like Ti only at the lowest pressure inside the stability field of ω-phase. Different pathways apply at higher pressures where the energy landscape contains several high barriers so that metastable states are expected, including the appearance of a transient bcc phase at ca. 23 GPa. The global driving force for the hcp-ωmore » transition increases strongly with increasing pressure and reaches 23.7 meV/atom at 23 GPa. Much of this energy relates to the excess volume of the hcp phase compared with its ω phase.« less

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

2017-01-28

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionicmore » radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

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.

Purification of nuclear grade Zr scrap as the high purity dense Zr deposits from Zirlo scrap by electrorefining in LiF-KF-ZrF4 molten fluorides

NASA Astrophysics Data System (ADS)

Park, Kyoung Tae; Lee, Tae Hyuk; Jo, Nam Chan; Nersisyan, Hayk H.; Chun, Byong Sun; Lee, Hyuk Hee; Lee, Jong Hyeon

2013-05-01

Zirconium (Zr) has commonly been used as a cladding material of nuclear fuel. Moreover, it is regarded as the only material that can be used for nuclear fuel cladding because it has the lowest neutron capture cross section of any metal element and because it has high corrosion resistance and size stability. In this study, Hf-free Zr tubes (Zr-1Nb-1Sn-0.1Fe) were used as anode materials and electrorefining was performed in a LiF-KF eutectic 6 wt.% ZrF4 molten fluoride salt system. As a result of electrolysis, Zr scrap metal was recycled into pure Zr with low levels of impurities, and the size and density of the Zr deposit was controlled using applied current density.

Acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces: A comprehensive periodic DFT study

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2016-12-06

A comprehensive study of acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces was carried out by means of calculations based on periodic density functional theory, using the Perdew–Burke–Ernzerhof exchange–correlation functional. It was found that the bonding of acetylene was significantly affected by the electronic and structural properties of the carbide surfaces. The adsorbate interacted with metal and/or carbon sites of the carbide. The interaction of acetylene with the TiC(001) and ZrC(001) surfaces was strong (binding energies higher than $-$3.5 eV), while moderate acetylene adsorption energies were observed on δ-MoC(001) ($-$1.78 eV to –0.66 eV). Adsorption energies, charge density difference plotsmore » and Mulliken charges suggested that the binding of the hydrocarbon to the surface had both ionic and covalent contributions. According to the C–C bond lengths obtained, the adsorbed molecule was modified from acetylene-like into ethylene-like on the δ-MoC(001) surface (desired behavior for hydrogenation reactions) but into ethane-like on TiC(001) and ZrC(001). The obtained results suggest that the δ-MoC(001) surface is expected to have the best performance in selective hydrogenation reactions to convert alkynes into alkenes. Another advantage of δ-MoC(001) is that, after C 2H 2 adsorption, surface carbon sites remain available, which are necessary for H 2 dissociation. Furthermore, these sites were occupied when C 2H 2 was adsorbed on TiC(001) and ZrC(001), limiting their application in the hydrogenation of alkynes.« less

Large Energy Density, Excellent Thermal Stability, and High Cycling Endurance of Lead-Free BaZr0.2Ti0.8O3 Film Capacitors.

PubMed

Sun, Zixiong; Ma, Chunrui; Wang, Xi; Liu, Ming; Lu, Lu; Wu, Ming; Lou, Xiaojie; Wang, Hong; Jia, Chun-Lin

2017-05-24

A large energy storage density (ESD) of 30.4 J/cm 3 and high energy efficiency of 81.7% under an electrical field of 3 MV/cm was achieved at room temperature by the fabrication of environmentally friendly lead-free BaZr 0.2 Ti 0.8 O 3 epitaxial thin films on Nb-doped SrTiO 3 (001) substrates by using a radio-frequency magnetron sputtering system. Moreover, the BZT film capacitors exhibit great thermal stability of the ESD from 16.8 J/cm 3 to 14.0 J/cm 3 with efficiency of beyond 67.4% and high fatigue endurance (up to 10 6 cycles) in a wide temperature range from room temperature to 125 °C. Compared to other BaTiO 3 -based energy storage capacitor materials and even Pb-based systems, BaZr 0.2 Ti 0.8 O 3 thin film capacitors show either high ESD or great energy efficiency. All of these excellent results revealed that the BaZr 0.2 Ti 0.8 O 3 film capacitors have huge potential in the application of modern electronics, such as locomotive and pulse power, in harsh working environments.

Solid state amorphization of metastable Al 0.5TiZrPdCuNi high entropy alloy investigated by high voltage electron microscopy

DOE PAGES

Nagase, Takeshi; Takeuchi, Akira; Amiya, Kenji; ...

2017-07-18

Here, the phase stability of high entropy alloy (HEA), Al 0.5TiZrPdCuNi, under fast electron irradiation was studied by in-situ high voltage electron microscopy (HVEM). The initial phase of this alloy quenched from the melt was dependent on cooling rate. At high cooling rates an amorphous phase was obtained, whereas a body-centered cubic ( b.c.c.) phase were obtained at low cooling rates. By thermal crystallization of the amorphous phase b.c.c. phase nano-crystals were formed. Upon fast electron irradiation solid state amorphization (SSA) was observed in b.c.c. phase regardless of the initial microstructure (i.e., “coarse crystalline structure” or “nano-crystalline structure with grainmore » boundaries as a sink for point defects”). SSA behavior in the Al 0.5TiZrPdCuNi HEAs was investigated by in-situ transmission electron microscopy observations. Because the amorphization is very rarely achieved in a solid solution phase under fast electron irradiation in common metallic materials, this result suggests that the Al 0.5TiZrPdCuNi HEA from other common alloys and the other HEAs. The differences in phase stability against the irradiation between the Al 0.5TiZrPdCuNi HEA and the other HEAs were discussed. This is the first experimental evidence of SSA in HEAs stimulated by fast electron irradiation.« less

Effects of Plasma ZrN Metallurgy and Shot Peening Duplex Treatment on Fretting Wear and Fretting Fatigue Behavior of Ti6Al4V Alloy

PubMed Central

Tang, Jingang; Liu, Daoxin; Zhang, Xiaohua; Du, Dongxing; Yu, Shouming

2016-01-01

A metallurgical zirconium nitride (ZrN) layer was fabricated using glow metallurgy using nitriding with zirconiuming prior treatment of the Ti6Al4V alloy. The microstructure, composition and microhardness of the corresponding layer were studied. The influence of this treatment on fretting wear (FW) and fretting fatigue (FF) behavior of the Ti6Al4V alloy was studied. The composite layer consisted of an 8-μm-thick ZrN compound layer and a 50-μm-thick nitrogen-rich Zr–Ti solid solution layer. The surface microhardness of the composite layer is 1775 HK0.1. A gradient in cross-sectional microhardness distribution exists in the layer. The plasma ZrN metallurgical layer improves the FW resistance of the Ti6Al4V alloy, but reduces the base FF resistance. This occurs because the improvement in surface hardness results in lowering of the toughness and increasing in the notch sensitivity. Compared with shot peening treatment, plasma ZrN metallurgy and shot peening composite treatment improves the FW resistance and enhances the FF resistance of the Ti6Al4V alloy. This is attributed to the introduction of a compressive stress field. The combination of toughness, strength, FW resistance and fatigue resistance enhance the FF resistance for titanium alloy. PMID:28773345

Fractographic Analysis of HfB2-SiC and ZrB2-SiC Composites

NASA Technical Reports Server (NTRS)

Mecholsky, J.J., Jr.; Ellerby, D. T.; Johnson, S. M.; Stackpoole, M. M.; Loehman, R. E.; Arnold, Jim (Technical Monitor)

2001-01-01

Hafnium diboride-silicon carbide and zirconium diboride-silicon carbide composites are potential materials for high temperature leading edge applications on reusable launch vehicles. In order to establish material constants necessary for evaluation of in-situ fracture, bars fractured in four point flexure were examined using fractographic principles. The fracture toughness was determined from measurements of the critical crack sizes and the strength values, and the crack branching constants were established to use in forensic fractography of materials for future flight applications. The fracture toughnesses range from about 13 MPam (sup 1/2) at room temperature to about 6 MPam (sup 1/2) at 1400 C for ZrB2-SiC composites and from about 11 MPam (sup 1/2) at room temperature to about 4 MPam (sup 1/2) at 1400 C for HfB2-SiC composites.

Zr, Hf, Mo and W-containing oxide phases as pinning additives in Bi-2212 superconductor

NASA Astrophysics Data System (ADS)

Makarova, M. V.; Kazin, P. E.; Tretyakov, Yu. D.; Jansen, M.; Reissner, M.; Steiner, W.

2005-02-01

Phase formation was investigated in Bi-Sr-Ca-Cu-M-O (M = Mo, W) systems at 850-900 °C. It was found that Sr 2CaMO 6 phases were chemically compatible with Bi-2212. The composites Bi-2212-Sr 2CaMO 6 and Bi-2212-SrAO 3 (A = Zr, Hf) were obtained from a sol-gel precursor using crystallisation from the melt. The materials consisted of Bi-2212 matrix and submicron or micron grains of the corresponding dispersed phase. Tc was equal or exceeded that for undoped Bi-2212, reaching Tc = 97 K in the Mo-containing composite. The composites exhibited enhanced pinning in comparison with similar prepared pure Bi-2212, especially at T = 60 K. The best pinning parameters were observed for the Bi-2212-Sr 2CaWO 6 composite.

Synthesis and characterization of micro/nanoscopic Pb(Zr0.52Ti0.48)O3 fibers by electrospinning

NASA Astrophysics Data System (ADS)

Wang, Y.; Furlan, R.; Ramos, I.; Santiago-Aviles, J. J.

Micro/nanoscopic Pb(Zr0.52Ti0.48)O3 fibers were synthesized from commercially available zirconium n-pro-poxide, titanium isopropoxide, and lead 2-ethylhexanoate. Using xylene as a solvent, they were mixed to form a precursor solution with a suitable viscosity for electrospinning. The solution was analyzed using thermo-gravimetric and differential thermal methods. Ultra-fine fibers and mats were electrostatically drawn from the precursor solution. The as-deposited materials were sintered for 2 h at 400, 500, 600, 700 and 800 °C, respectively. Sintered mats or fibers were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Auger electron spectroscopy (AES), Raman micro-spectrometry and scanning-probe microscopy (SPM). The SEM results revealed that the fibers had diameters varying from hundreds of nanometers to 10 μm. Using AES, the elements Pb, Zr, Ti and O, as well as residual C, were detected on the surface of the fibers. Raman and XRD spectra indicated that the precursors began to transform into the intermediate pyrochlore phase at 400 °C, followed by the perovskite Pb(Zr0.52Ti0.48)O3 phase above 600 °C. Scanning-probe microscopy (SPM), operated in the piezo-response imaging mode, revealed spontaneous polarization domains in the fibers, with diameters ranging from 100 to 500 nm.

Effect of Mn and AlTiB Addition and Heattreatment on the Microstructures and Mechanical Properties of Al-Si-Fe-Cu-Zr Alloy.

PubMed

Yoo, Hyo-Sang; Kim, Yong-Ho; Lee, Seong-Hee; Son, Hyeon-Taek

2018-09-01

The microstructure and mechanical properties of as-extruded Al-0.1 wt%Si-0.2 wt%Fe- 0.4 wt%Cu-0.04 wt%Zr-xMn-xAlTiB (x = 1.0 wt%) alloys under various annealing processes were investigated and compared. After the as-cast billets were kept at 400 °C for 1 hr, hot extrusion was carried out with a reduction ratio of 38:1. In the case of the as-extruded Al-Si-Fe-Cu-Zr alloy at annealed at 620 °C, large equiaxed grain was observed. When the Mn content is 1.0 wt%, the phase exhibits a skeleton morphology, the phase formation in which Mn participated. Also, the volume fraction of the intermetallic compounds increased with Mn and AlTiB addition. For the Al-0.1Si-0.2Fe-0.4Cu-0.04Zr alloy with Mn and AlTiB addition from 1.0 wt%, the ultimate tensile strength increased from 100.47 to 119.41 to 110.49 MPa. The tensile strength of the as-extruded alloys improved with the addition of Mn and AlTiB due to the formation of Mn and AlTiB-containing intermetallic compounds.

Deposition And Characterization of (Ti,Zr)N Thin Films Grown Through PAPVD By The Pulsed Arc Technique

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

Marulanda, D. M.; Trujillo, O.; Devia, A.

The Plasma Assisted Physic Vapor Deposition (PAPVD) by the pulsed arc technique has been used for deposition of Titanium Zirconium Nitride (Ti,Zr)N coatings, using a segmented target of TiZr. The deposition was performed in a vacuum chamber with two faced electrodes (target and substrate) using nitrogen as working gas, and a power-controlled source used to produce the arc discharges. Films were deposited on stainless steel 304, and they were characterized using the X-Ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD), Energy Dispersion Spectroscopy (EDS) and Scanning Probe Microscopy (SPM) techniques. The XRD patterns show different planes in which the film grows.more » Through SPM, using Atomic Force Microscopy (AFM) and Lateral Force Microscopy (LFM) modes, a nanotribologic study of the thin film was made, determining hardness and friction coefficient.« less

Low-cost, high-strength Fe--Ni--Cr alloys for high temperature exhaust valve application

DOEpatents

Muralidharan, Govindarajan

2017-09-05

An Fe--Ni--Cr alloy is composed essentially of, in terms of wt. %: 2.4 to 3.7 Al, up to 1.05 Co, 14.8 to 15.9 Cr, 25 to 36 Fe, up to 1.2 Hf, up to 4 Mn, up to 0.6 Mo, up to 2.2 Nb, up to 1.05 Ta, 1.9 to 3.6 Ti, up to 0.08 W, up to 0.03 Zr, 0.18 to 0.27 C, up to 0.0015 N, balance Ni, wherein, in terms of atomic percent: 8.5.ltoreq.Al+Ti+Zr+Hf+Ta.ltoreq.11.5, 0.53.ltoreq.Al/(Al+Ti+Zr+Hf+Ta).ltoreq.0.65, and 0.16.ltoreq.Cr/(Fe+Ni+Cr+Mn).ltoreq.0.21, the alloy being essentially free of Cu, Si, and V.

A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

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

Powell, C.J.; Smekal, W.; Werner, W.S.M.

2005-09-09

We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. Wemore » report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.« less

A model for Nb-Zr-REE-Ga enrichment in Lopingian altered alkaline volcanic ashes: Key evidence of H-O isotopes

NASA Astrophysics Data System (ADS)

Dai, Shifeng; Nechaev, Victor P.; Chekryzhov, Igor Yu.; Zhao, Lixin; Vysotskiy, Sergei V.; Graham, Ian; Ward, Colin R.; Ignatiev, Alexander V.; Velivetskaya, Tatyana A.; Zhao, Lei; French, David; Hower, James C.

2018-03-01

Clay-altered volcanic ash with highly-elevated concentrations of Nb(Ta), Zr(Hf), rare earth elements (REE), and Ga, is a new type of critical metal deposit with high commercial prospects that has been discovered in Yunnan Province, southwest China. Previous studies showed that the volcanic ashes had been subjected to hydrothermal fluids, the nature of which, however, is not clear. Here we show that the volcanic ashes were originated from alkaline magmatism, followed by a continuous hydrothermal-weathering process. Heated meteoric waters, which were sourced from acidic rains and mixed with CO2 from degassing of the Emeishan plume, have caused partial, but widespread, acidic leaching of Nb, Ta, Zr, Hf, REE, and Ga into ground water and residual enrichment of these elements, along with Al and Ti, in the deeply altered rocks. Subsequent alteration occurring under cooler, neutral or alkaline conditions, caused by water-rock interaction, resulted in precipitation of the leached critical metals in the deposit. Polymetallic mineralization of similar origin may be found in other continental regions subjected to explosive alkaline volcanism associated with deep weathering in humid conditions.

Ferroelectric switching in epitaxial PbZr0.2Ti0.8O3/ZnO/GaN heterostructures

NASA Astrophysics Data System (ADS)

Wang, Juan; Salev, Pavel; Grigoriev, Alexei

As a wide-bandgap semiconductor, ZnO has gained substantial interest due to its favorable properties including high electron mobility, strong room-temperature luminescence, etc. The main obstacle of its application is the lack of reproducible and low-resistivity p-type ZnO. P-type doping of ZnO through the interface charge injection, which can be achieved by the polarization switching of ferroelectric films, is a tempting solution. We explored ferroelectric switching behavior of PbZr0.2Ti0.8O3/ZnO/GaN heterostructures epitaxially grown on Sapphire substrates by RF sputtering. The electrical measurements of Pt/PbZr0.2Ti0.8O3/ZnO/GaN ferroelectric-semiconductor capacitors revealed unusual behavior that is a combination of polarization switching and a diode I-V characteristics.

The effects of strain relaxation on the dielectric properties of epitaxial ferroelectric Pb(Zr0.2Ti0.8)TiO3 thin films

NASA Astrophysics Data System (ADS)

Khan, Asif Islam; Yu, Pu; Trassin, Morgan; Lee, Michelle J.; You, Long; Salahuddin, Sayeef

2014-07-01

We study the effects of strain relaxation on the dielectric properties of epitaxial 40 nm Pb(Zr0.2Ti0.8)TiO3 (PZT) films. A significant increase in the defect and dislocation density due to strain relaxation is observed in PZT films with tetragonality c/a < 1.07 grown on SrTiO3 (001) substrates, which results in significant frequency dispersion of the dielectric constant and strong Rayleigh type behavior in those samples. This combined structural-electrical study provides a framework for investigating strain relaxation in thin films and can provide useful insights into the mechanisms of fatigue in ferroelectric materials.

Effect of Surface Modifications of Ti40Zr10Cu38Pd12 Bulk Metallic Glass and Ti-6Al-4V Alloy on Human Osteoblasts In Vitro Biocompatibility

PubMed Central

Blanquer, Andreu; Hynowska, Anna; Nogués, Carme; Ibáñez, Elena; Sort, Jordi; Baró, Maria Dolors; Özkale, Berna; Pané, Salvador; Pellicer, Eva

2016-01-01

The use of biocompatible materials, including bulk metallic glasses (BMGs), for tissue regeneration and transplantation is increasing. The good mechanical and corrosion properties of Ti40Zr10Cu38Pd12 BMG and its previously described biocompatibility makes it a potential candidate for medical applications. However, it is known that surface properties like topography might play an important role in regulating cell adhesion, proliferation and differentiation. Thus, in the present study, Ti40Zr10Cu38Pd12 BMG and Ti6-Al-4V alloy were surface-modified electrochemically (nanomesh) or physically (microscratched) to investigate the effect of material topography on human osteoblasts cells (Saos-2) adhesion, proliferation and differentiation. For comparative purposes, the effect of mirror-like polished surfaces was also studied. Electrochemical treatments led to a highly interconnected hierarchical porous structure rich in oxides, which have been described to improve corrosion resistance, whereas microscratched surfaces showed a groove pattern with parallel trenches. Cell viability was higher than 96% for the three topographies tested and for both alloy compositions. In all cases, cells were able to adhere, proliferate and differentiate on the alloys, hence indicating that surface topography plays a minor role on these processes, although a clear cell orientation was observed on microscratched surfaces. Overall, our results provide further evidence that Ti40Zr10Cu38Pd12 BMG is an excellent candidate, in the present two topographies, for bone repair purposes. PMID:27243628

Effect of multinary substitution on electronic and transport properties of TiCoSb based half-Heusler alloys

NASA Astrophysics Data System (ADS)

Choudhary, Mukesh K.; Ravindran, P.

2018-05-01

The electronic structures of TixZrx/2CoPbxTex, TixZrx/2Hfx/2CoPbxTex (x = 0.5), and the parent compound TiCoSb were investigated using the full potential linearized augmented plane wave method. The thermoelectric transport properties of these alloys are calculated on the basis of semi-classical Boltzmann transport theory. From the band structure calculations we show that the substitution of Zr,Hf in the Ti site and Pb and Te in the Sb site lower the band gap value and also change the indirect band (IB) gap of TiCoSb to the direct band (DB) gap. The calculated band gap of TiCoSb, TixZrx/2CoPbxTex, and TixZrx/2Hfx/2CoPbxTex are 1.04 eV (IB), 0.92 eV (DB), and 0.93 eV (DB), respectively. All these alloys follow the empirical rule of 18 valence-electron content which is essential for bringing semiconductivity in half Heusler alloys. It is shown that the substitution of Hf at the Ti site improve the ZT value (˜1.05) at room temperature, whereas there is no significant difference in ZT is found at higher temperature. Based on the calculated thermoelectric transport properties, we conclude that the appropriate concentration of Hf substitution can further improve the thermoelectric performance of TixZrx/2Hfx/2CoPbxTex.

Thermal Conductivity and Water Vapor Stability of Ceramic HfO2-Based Coating Materials

NASA Technical Reports Server (NTRS)

Zhu, Dong-Ming; Fox, Dennis S.; Bansal, Narottam P.; Miller, Robert A.

2004-01-01

HfO2-Y2O3 and La2Zr2O7 are candidate thermal/environmental barrier coating materials for gas turbine ceramic matrix composite (CMC) combustor liner applications because of their relatively low thermal conductivity and high temperature capability. In this paper, thermal conductivity and high temperature phase stability of plasma-sprayed coatings and/or hot-pressed HfO2-5mol%Y2O3, HfO2-15mol%Y2O3 and La2Zr2O7 were evaluated at temperatures up to 1700 C using a steady-state laser heat-flux technique. Sintering behavior of the plasma-sprayed coatings was determined by monitoring the thermal conductivity increases during a 20-hour test period at various temperatures. Durability and failure mechanisms of the HfO2-Y2O3 and La2Zr2O7 coatings on mullite/SiC Hexoloy or CMC substrates were investigated at 1650 C under thermal gradient cyclic conditions. Coating design and testing issues for the 1650 C thermal/environmental barrier coating applications will also be discussed.

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

2017-01-24

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ~50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B = Ti and ~16 GPa B = Zr. But, the A-site cation affected the kinetics of the phase transformation,more » with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. Our results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

Spin texture induced by oxygen vacancies in strontium perovskite (001) surfaces: A theoretical comparison between SrTiO3 and SrHfO3

NASA Astrophysics Data System (ADS)

Garcia-Castro, A. C.; Vergniory, M. G.; Bousquet, E.; Romero, A. H.

2016-01-01

The electronic structure of SrTiO3 and SrHfO3 (001) surfaces with oxygen vacancies is studied by means of first-principles calculations. We reveal how oxygen vacancies within the first atomic layer of the SrTiO3 surface (i) induce a large antiferrodistortive motion of the oxygen octahedra at the surface, (ii) drive localized magnetic moments on the Ti 3 d orbitals close to the vacancies, and (iii) form a two-dimensional electron gas localized within the first layers. The analysis of the spin texture of this system exhibits a splitting of the energy bands according to the Zeeman interaction, lowering of the Ti 3 dx y level in comparison with dx z and dy z, and also an in-plane precession of the spins. No Rashba-like splitting for the ground state or for the ab initio molecular dynamics trajectory at 400 K is recognized as suggested recently by A. F. Santander-Syro et al. [Nat. Mater. 13, 1085 (2014), 10.1038/nmat4107]. Instead, a sizable Rashba-like splitting is observed when the Ti atom is replaced by a heavier Hf atom with a much larger spin-orbit interaction. However, we observe the disappearance of the magnetism and the surface two-dimensional electron gas when full structural optimization of the SrHfO3 surface is performed. Our results uncover the sensitive interplay of spin-orbit coupling, atomic relaxations, and magnetism when tuning these Sr-based perovskites.

Effect of two-stage sintering on dielectric properties of BaTi0.9Zr0.1O3 ceramics

NASA Astrophysics Data System (ADS)

Rani, Rekha; Rani, Renu; Kumar, Parveen; Juneja, J. K.; Raina, K. K.; Prakash, Chandra

2011-09-01

The effect of two-stage sintering on the dielectric properties of BaTi0.9Zr0.1O3 ceramics prepared by solid state route was investigated and is presented here. It has been found that under suitable two-stage sintering conditions, dense BaTi0.9Zr0.1O3 ceramics with improved electrical properties can be synthesized. The density was found to have a value of 5.49 g cc-1 for normally sintered samples, whereas in the case of the two-stage sintered sample it was 5.85 g cc-1. Dielectric measurements were done as a function of frequency and temperature. A small decrease in the Curie temperature was observed with modification in dielectric loss for two-stage sintered ceramic samples.

Mechanical properties of ZrB2- and HfB2-based ultra-high temperature ceramics fabricated by spark plasma sintering

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

Zapata-Solvas, E.; Jayaseelan, D.; Lin, Hua-Tay

2013-01-01

Flexural strengths at room temperature, at 1400 C in air and at room temperature after 1 h oxidation at 1400 C were determined for ZrB2- and HfB2-based ultra-high temperature ceramics (UHTCs). Defects caused by electrical discharge machining (EDM) lowered measured strengths significantly and were used to calculate fracture toughness via a fracture mechanics approach. ZrB2 with 20 vol.% SiC had room temperature strength of 700 90 MPa, fracture toughness of 6.4 0.6 MPa, Vickers hardness at 9.8 N load of 21.1 0.6 GPa, 1400 C strength of 400 30 MPa and room temperature strength after 1 h oxidation at 1400more » C of 678 15 MPa with an oxide layer thickness of 45 5 m. HfB2 with 20 vol.% SiC showed room temperature strength of 620 50 MPa, fracture toughness of 5.0 0.4 MPa, Vickers hardness at 9.8 N load of 27.0 0.6 GPa, 1400 C strength of 590 150 MPa and room temperature strength after 1 h oxidation at 1400 C of 660 25 MPa with an oxide layer thickness of 12 1 m. 2 wt.% La2O3 addition to UHTCs slightly reduced mechanical performance while increasing tolerance to property degradation after oxidation and effectively aided internal stress relaxation during spark plasma sintering (SPS) cooling, as quantified by X-ray diffraction (XRD). Slow crack growth was suggested as the failure mechanism at high temperatures as a consequence of sharp cracks formation during oxidation.« less

Influence of Carbon interstitials to Ti1-xMexN (Me = Zr, Al, Cr) coatings by pulsed laser ablation on wear resistance

NASA Astrophysics Data System (ADS)

Jeon, Seol; Hong, Eunpyo; Kwon, Se-Hun; Lee, Heesoo

2018-06-01

The wear resistance of Ti1-xMexN (Me = Zr, Al, Cr) coatings by the laser carburization process was investigated in terms of local atomic structural changes. The repeated pulsed laser ablation was performed to the Ti1-xMexN coating surfaces after Graphite paste was covered. The friction coefficients of the coating specimens were decreased from ∼0.7 to 0.2, and the formation of cracks and debris was suppressed by implementing the laser ablation process. ToF-SIMS depth profiles showed that the laser carburization helps Carbon penetrate into the coating layer as deep as ∼20 nm below its surface. XPS and XAFS analyses revealed that the improvement of the wear resistance of the coatings was achieved not by formation of TiC or ZrC lattices on the coatings surfaces but by Carbon interstitials to the Ti1-xMexN lattices.

Evidence for the antiferromagnetic ground state of Zr2TiAl: a first-principles study

NASA Astrophysics Data System (ADS)

Sreenivasa Reddy, P. V.; Kanchana, V.; Vaitheeswaran, G.; Ruban, Andrei V.; Christensen, N. E.

2017-07-01

A detailed study on the ternary Zr-based intermetallic compound Zr2TiAl has been carried out using first-principles electronic structure calculations. From the total energy calculations, we find an antiferromagnetic L11-like (AFM) phase with alternating (1 1 1) spin-up and spin-down layers to be a stable phase among some others with magnetic moment on Ti being 1.22 {μ\\text{B}} . The calculated magnetic exchange interaction parameters of the Heisenberg Hamiltonian and subsequent Heisenberg Monte Carlo simulations confirm that this phase is the magnetic ground structure with Néel temperature between 30 and 100 K. The phonon dispersion relations further confirm the stability of the magnetic phase while the non-magnetic phase is found to have imaginary phonon modes and the same is also found from the calculated elastic constants. The magnetic moment of Ti is found to decrease under pressure eventually driving the system to the non-magnetic phase at around 46 GPa, where the phonon modes are found to be positive indicating stability of the non-magnetic phase. A continuous change in the band structure under compression leads to the corresponding change of the Fermi surface topology and electronic topological transitions (ETT) in both majority and minority spin cases, which are also evident from the calculated elastic constants and density of state calculations for the material under compression.

Regulation of depletion layer width in Pb(Zr,Ti)O3/Nb:SrTiO3 heterostructures

NASA Astrophysics Data System (ADS)

Bai, Yu; Jie Wang, Zhan; Cui, Jian Zhong; Zhang, Zhi Dong

2018-05-01

Improving the tunability of depletion layer width (DLW) in ferroelectric/semiconductor heterostructures is important for the performance of some devices. In this work, 200-nm-thick Pb(Zr0.4Ti0.6)O3 (PZT) films were deposited on different Nb-doped SrTiO3 (NSTO) substrates, and the tunability of DLW at PZT/NSTO interfaces were studied. Our results showed that the maximum tunability of the DLW was achieved at the NSTO substrate with 0.5 wt% Nb. On the basis of the modified capacitance model and the ferroelectric semiconductor theory, we suggest that the tunability of the DLW in PZT/NSTO heterostructures can be attributed to a delicate balance of the depletion layer charge and the ferroelectric polarization charge. Therefore, the performance of some devices related to the tunability of DLW in ferroelectric/semiconductor heterostructures can be improved by modulating the doping concentration in semiconducting electrode materials.

The improvement of retention time of metal-ferroelectric (PbZr0.53Ti0.47O3)-insulator (ZrO2)-semiconductor transistors and capacitors by leakage current reduction using surface treatment

NASA Astrophysics Data System (ADS)

Shih, Wen-Chieh; Kang, Kun-Yung; Lee, Joseph Ya-Min

2007-11-01

Metal-ferroelectric-insulator-semiconductor transistors (MFISFETs) and capacitors with the structure of Al /Pb (Zr0.53,Ti0.47) O3/ZrO2/Si were fabricated. The wafers were pretreated with H2O2 before ZrO2 deposition and/or post-treated with HCl after ZrO2 deposition. The leakage current density at 5V is reduced from 10-1to5×10-6A /cm2. The subthreshold slope was improved to 91mV/decade. The MFISFETs maintain a threshold voltage window of about 1.1V after an elapsed time of 3000s. The mobility is 267cm2/Vs. The improvements are most likely due to the reduction of interfacial layer thickness and the interface states at the ZrO2/Si interface.

First-principles study of transition-metal nitrides as diffusion barriers against Al

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

Mei, Zhi-Gang; Yacout, Abdellatif M.; Kim, Yeon Soo

2016-04-01

Using density-functional theory based first-principles calculations we provided a comparative study of the diffusion barrier properties of TiN, ZrN, and HfN against Al for U-Mo dispersion fuel applications. We firstly examined the thermodynamic stability of these transition-metal nitrides with Al. The calculated heats of reaction show that both TiN and ZrN are thermodynamically unstable diffusion barrier materials, which might be decomposed by Al at relatively high temperatures. As a comparison, HfN is a stable diffusion barrier material for Al. To evaluate the kinetic stability of these nitride systems against Al diffusion, we investigated the diffusion mechanisms of Al in TiN,more » ZrN and HfN using atomic scale simulations. The effect of non-stoichiometry on the defect formation and Al migration was systematically studied. (C) 2015 ELSEVIER B.V. All rights reserved« less

Hf-Nd isotope decoupling in the oceanic lithosphere: constraints from spinel peridotites from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Sen, Gautam; Salters, Vincent J. M.

2004-01-01

We present a detailed geochemical investigation on the Hf, Nd and Sr isotope compositions and trace and major element contents of clinopyroxene mineral separates from spinel lherzolite xenoliths from the island of Oahu, Hawaii. These peridotites are believed to represent the depleted oceanic lithosphere beneath Oahu, which is a residue of a MORB-related melting event some 80-100 Ma ago at a mid-ocean ridge. Clinopyroxenes from peridotites from the Salt Lake Crater (SLC) show a large range of Hf isotopic compositions, from ɛHf=12.2 (similar to the Honolulu volcanics series) to extremely radiogenic, ɛHf=65, at nearly constant 143Nd/ 144Nd ratios ( ɛNd=7-8). None of these samples show any isotopic evidence for interaction with Koolau-type melts. A single xenolith from the Pali vent is the only sample with Hf and Nd isotopic compositions that falls within the MORB field. The Hf isotopes correlate positively with the degree of depletion in the clinopyroxene (e.g. increasing Mg#, Cr#, decreasing Ti and heavy REE contents), but also with increasing Zr and Hf depletions relative to the adjacent REE in a compatibility diagram. The Lu/Hf isotope systematics of the SLC clinopyroxenes define apparent ages of 500 Ma or older and these compositions cannot be explained by mixing between any type of Hawaiian melts and the depleted Pacific lithosphere. Metasomatism of an ancient (e.g. 1 Ga or older) depleted peridotite protolith can, in principle, explain these apparent ages and the Nd-Hf isotope decoupling, but requires that the most depleted samples were subject to the least amount of metasomatism. Alternatively, the combined isotope, trace and major element compositions of these clinopyroxenes are best described by metasomatism of the 80-100 Ma depleted oceanic lithosphere by melts products of extensive mantle-melt interaction between Honolulu Volcanics-type melts and the depleted lithosphere.